Note: Descriptions are shown in the official language in which they were submitted.
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MICROCAPSULE-CONTAINING DETERGENT OR CLEANING AGENT
FIELD OF INVENTION
The invention relates to microcapsules, methods of making and using same as
well as consumer
products comprising such microcapsules and methods of making and using same.
BACKGROUND OF THE INVENTION
Many consumer products, for example, cleaning and/or treatment composition
contain sensitive
ingredients. It is disadvantageous that such ingredients, which are used in
such agents,
frequently lose their activity, or at a minimum their activity is greatly
reduced, during storage
and/or before the desired date of application, for example by chemical
reactions resulting from
interaction with other components of the consumer product and/or through
physical influences.
For this reason, certain ingredients such as perfumes are encapsulated.
Microcapsules that are free or nearly free of formaldehyde free are desired
for use in consumer
products as the use of formaldehyde scavengers can be avoided or minimized.
Thus, the use of
microcapsules having a shell that comprises the reaction product of a material
that comprises
an aromatic alcohol moiety and a material that comprises an aldehyde moiety
for use in laundry
applications has been proposed. Unfortunately, such capsules can discolor a
consumer product,
fail to provide a benefit across all consumer touch points and may fail to
deliver a sufficient
amount of their core when subjected to external stimuli like temperature,
infrared radiation,
visible light, and/or ultraviolet radiation.
Surprisingly, it was found that the source of the discoloration was, in large
part, due to the
capsule's color intensity bleeding through the consumer product and the
diffusion of unreacted
capsule components into the formulation rather than simply the reaction of the
capsules with
other formulation ingredients and that combination of such microcapsules with
judiciously
selected materials solve such problem. In addition, Applicants recognized that
when the proper
di-aldehyde is employed, release that is triggered by electromagnetic
radiation can be obtained.
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SUMMARY OF THE INVENTION
The invention relates to microcapsules, methods of making and using same as
well as consumer
products comprising such microcapsules and methods of making and using same.
DETAILED DESCRIPTION OF THE INVENTION
Definitions
As used herein "consumer product" means baby care, beauty care, fabric & home
care,
family care, feminine care, health care, snack and/or beverage products or
devices generally
intended to be used or consumed in the form in which it is sold. Such products
include but are
not limited to diapers, bibs, wipes; products for and/or methods relating to
treating hair (human,
dog, and/or cat), including, bleaching, coloring, dyeing, conditioning,
shampooing, styling;
deodorants and antiperspirants; personal cleansing; cosmetics; skin care
including application of
creams, lotions, and other topically applied products for consumer use
including fine fragrances;
and shaving products, products for and/or methods relating to treating
fabrics, hard surfaces and
any other surfaces in the area of fabric and home care, including: air care
including air
fresheners and scent delivery systems, car care, dishwashing, fabric
conditioning (including
softening and/or freshing), laundry detergency, laundry and rinse additive
and/or care, hard
surface cleaning and/or treatment including floor and toilet bowl cleaners,
and other cleaning for
consumer or institutional use; products and/or methods relating to bath
tissue, facial tissue, paper
handkerchiefs, and/or paper towels; tampons, feminine napkins; products and/or
methods relating
to oral care including toothpastes, tooth gels, tooth rinses, denture
adhesives, tooth whitening;
over-the-counter health care including cough and cold remedies, pain
relievers, RX
pharmaceuticals, pet health and nutrition; processed food products intended
primarily for
consumption between customary meals or as a meal accompaniment (non-limiting
examples
include potato chips, tortilla chips, popcorn, pretzels, corn chips, cereal
bars, vegetable chips or
crisps, snack mixes, party mixes, multigrain chips, snack crackers, cheese
snacks, pork rinds,
corn snacks, pellet snacks, extruded snacks and bagel chips); and coffee.
As used herein, the term "cleaning and/or treatment composition" is a subset
of consumer
products that includes, unless otherwise indicated, beauty care, fabric & home
care products.
Such products include, but are not limited to, products for treating hair
(human, dog, and/or cat),
including, bleaching, coloring, dyeing, conditioning, shampooing, styling;
deodorants and
antiperspirants; personal cleansing; cosmetics; skin care including
application of creams, lotions,
and other topically applied products for consumer use including fine
fragrances; and shaving
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products, products for treating fabrics, hard surfaces and any other surfaces
in the area of fabric
and home care, including: air care including air fresheners and scent delivery
systems, car care,
dishwashing, fabric conditioning (including softening and/or freshing),
laundry detergency,
laundry and rinse additive and/or care, hard surface cleaning and/or treatment
including floor and
toilet bowl cleaners, granular or powder-form all-purpose or "heavy-duty"
washing agents,
especially cleaning detergents; liquid, gel or paste-form all-purpose washing
agents, especially
the so-called heavy-duty liquid types; liquid fine-fabric detergents; hand
dishwashing agents or
light duty dishwashing agents, especially those of the high-foaming type;
machine dishwashing
agents, including the various tablet, granular, liquid and rinse-aid types for
household and
institutional use; liquid cleaning and disinfecting agents, including
antibacterial hand-wash types,
cleaning bars, mouthwashes, denture cleaners, dentifrice, car or carpet
shampoos, bathroom
cleaners including toilet bowl cleaners; hair shampoos and hair-rinses; shower
gels , fine
fragrances and foam baths and metal cleaners; as well as cleaning auxiliaries
such as bleach
additives and "stain-stick" or pre-treat types, substrate-laden products such
as dryer added sheets,
dry and wetted wipes and pads, nonwoven substrates, and sponges; as well as
sprays and mists all
for consumer or/and institutional use; and/or methods relating to oral care
including toothpastes,
tooth gels, tooth rinses, denture adhesives, tooth whitening.
As used herein, the term "fabric and/or hard surface cleaning and/or treatment
composition" is a subset of cleaning and treatment compositions that includes,
unless otherwise
indicated, granular or powder-form all-purpose or "heavy-duty" washing agents,
especially
cleaning detergents; liquid, gel or paste-form all-purpose washing agents,
especially the so-called
heavy-duty liquid types; liquid fine-fabric detergents; hand dishwashing
agents or light duty
dishwashing agents, especially those of the high-foaming type; machine
dishwashing agents,
including the various tablet, granular, liquid and rinse-aid types for
household and institutional
use; liquid cleaning and disinfecting agents, including antibacterial hand-
wash types, cleaning
bars, car or carpet shampoos, bathroom cleaners including toilet bowl
cleaners; and metal
cleaners, fabric conditioning products including softening and/or freshing
that may be in liquid,
solid and/or dryer sheet form ; as well as cleaning auxiliaries such as bleach
additives and "stain-
stick" or pre-treat types, substrate-laden products such as dryer added
sheets, dry and wetted
wipes and pads, nonwoven substrates, and sponges; as well as sprays and mists.
All of such
products which are applicable may be in standard, concentrated or even highly
concentrated form
even to the extent that such products may in certain aspect be non-aqueous.
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As used herein, articles such as "a" and "an" when used in a claim, are
understood to
mean one or more of what is claimed or described.
As used herein, the terms "include", "includes" and "including" are meant to
be non-
limiting.
As used herein, the term "solid" includes granular, powder, bar and tablet
product forms.
As used herein, the term "fluid" includes liquid, gel, paste and gas product
forms.
As used herein, the term "situs" includes paper products, fabrics, garments,
hard surfaces,
hair and skin.
Unless otherwise noted, all component or composition levels are in reference
to the active
portion of that component or composition, and are exclusive of impurities, for
example, residual
solvents or by-products, which may be present in commercially available
sources of such
components or compositions.
All percentages and ratios are calculated by weight unless otherwise
indicated. All
percentages and ratios are calculated based on the total composition unless
otherwise indicated.
It should be understood that every maximum numerical limitation given
throughout this
specification includes every lower numerical limitation, as if such lower
numerical limitations
were expressly written herein. Every minimum numerical limitation given
throughout this
specification will include every higher numerical limitation, as if such
higher numerical
limitations were expressly written herein. Every numerical range given
throughout this
specification will include every narrower numerical range that falls within
such broader
numerical range, as if such narrower numerical ranges were all expressly
written herein.
Compositions
A composition comprising
i) surfactants and/or builders, as well as
ii) microcapsules comprising a wall having an exterior surface and a core,
said wall
encapsulating said core, said wall comprising a resin which can be obtained by
reacting
a) at least one aromatic alcohol or its ether or derivatives with
b) at least one aldehydic component which comprises at least two carbon atoms
per
molecule, and
c) optionally in the presence of at least one (meth)acrylate polymer
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iii) a material selected from the group consisting of a hueing dye, a
structurant, a density
balancing agent, a deposition aid, a perfume delivery system in addition to
said
microcapsules, a fabric softener and mixtures thereof
is disclosed.
5 In one aspect, said microcapsules comprise a deposition aid comprising a
material
selected from the group consisting of poly(meth)acrylate, poly(ethylene-maleic
anhydride),
polyamine, wax, polyvinylpyrrolidone, polyvinylpyrrolidone co-polymers,
polyvinylpyrrolidone-
ethyl acrylate, polyvinylpyrrolidone- vinyl acrylate, polyvinylpyrrolidone
methylacrylate,
polyvinylpyrrolidone/vinyl acetate, polyvinyl acetal, polyvinyl butyral,
polysiloxane,
poly(propylene maleic anhydride), maleic anhydride derivatives, co-polymers of
maleic
anhydride derivatives, polyvinyl alcohol, styrene-butadiene latex, gelatin,
gum Arabic,
carboxymethyl cellulose, carboxymethyl hydroxyethyl cellulose, hydroxyethyl
cellulose, other
modified celluloses, sodium alginate, chitosan, casein, pectin, modified
starch, polyvinyl acetal,
polyvinyl butyral, polyvinyl methyl ether/maleic anhydride, polyvinyl
pyrrolidone and its co
polymers, poly(vinyl pyrrolidone/methacrylamidopropyl trimethyl ammonium
chloride),
polyvinylpyrrolidone/vinyl acetate, polyvinyl pyrrolidone/dimethylaminoethyl
methacrylate,
polyvinyl amines, polyvinyl formamides, polyallyl amines and copolymers of
polyvinyl amines,
polyvinyl formamides, and polyallyl amines and mixtures thereof, said
deposition aid coating
the exterior of said microcapsules' wall.
In one aspect,
a) said structurant comprising a material selected from the group
consisting of
castor oil, hydrogenated castor oil, polysaccharides, modified celluloses,
modified
proteins, inorganic salts, quaternized polymeric materials, imidazoles;
nonionic
polymers having a pKa less than 6.0, polyurethanes, plant cellulose, bacterial
cellulose, coated bacterial cellulose, non-polymeric crystalline hydroxyl-
functional materials, polymeric structuring agents, di-amido gellants and
mixtures
thereof;
b) said hueing dye is selected from the group consisting of small molecule
dyes,
polymeric dyes, dye-clay conjugates, and organic and inorganic pigments, in
one
aspect, said hueing dye comprises a chromophore selected from one or more of
the following: acridine, anthraquinone, azine, azo, azulene, benzodifurane and
benzodifuranone, carotenoid, coumarin, cyanine, diazahemicyanine,
diphenylmethane, formazan, hemicyanine, indigoids, methane, naphthalimides,
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naphthoquinone, nitro and nitroso, oxazine, phthalocyanine, pyrazoles,
stilbene,
styryl, triarylmethane, triphenylmethane, xanthenes and mixtures thereof, in
one
aspect said fabric hueing agent may be selected from the fabric hueing agents
described in the section titled "Fabric Hueing Agents" which is found in the
Adjunct Materials section of this specification;
c) said additional perfume delivery comprises a material selected from the
group
consisting of a second microcapsule, a polymer assisted delivery system; a
molecule-assisted delivery system; a fiber-assisted delivery system; a
cyclodextrin
delivery system; a starch encapsulated accord; and/or an inorganic carrier
delivery
system; and
d) said fabric softener comprises from 1% to 49% by weight of the
composition of a
bis-(2-hydroxypropy1)-dimethylammonium methylsulphate fatty acid ester having
a molar ratio of fatty acid moieties to amine moieties of from 1.85 to 1.99,
an
average chain length of the fatty acid moieties of from 16 to 18 carbon atoms
and
an iodine value of the fatty acid moieties, calculated for the free fatty
acid, of
from 0.5 to 60.
Said second microcapsule, is of different type than said microcapsules
obtained by
reacting at least one aromatic alcohol or its ether or derivatives with at
least one aldehydic
component which comprises at least two carbon atoms per molecule, and
optionally in the
presence of at least one (meth)acrylate polymer. In one aspect, said second
microcapsule may be
a acrylate microcapsule and/or aminoplast microcapsule such as a melamine
formaldehyde
microcapsule.
In one aspect, the at least one aromatic alcohol (ii)(a) is chosen from
phenols, o-cresol, m-
cresol, p-cresol, a-naphthol, 13-naphthol, thymol, catechol, resorcin,
hydroquinone and 1,4-
naphthohydroquinone, phloroglucin, pyrogallol and hydroxy hydroquinone, and is
in particular
resorcinol and/or phloroglucin.
In one aspect, the aldehydic component (ii)(b) is chosen from azobenzene-4,4'-
dicarboxaldehyde, valeraldehyde, capronaldehyde, caprylaldehyde, decanal,
succindialdehyde,
cyclohexanecarbaldehyde, cyclopentanecarbaldehyde, 2-methyl-l-propanal, 2-
methylproprionaldehyde, acetaldehyde, acrolein, aldosterone, antimycin A, 8'-
apo-13-carotene-8'-al,
benzaldehyde, butanal, chloral, citral, citronellal, crotonaldehyde,
dimethylaminobenzaldehyde,
folinic acid, fosmidomycin, furfural, glutaraldehyde, glycerin aldehyde,
glycol aldehyde, glyoxal,
glyoxylic acid, heptanal, 2- hydroxybenzaldehyde, 3-hydroxy butanal, hydroxy
methyl furfural, 4-
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hydroxynonenal, isobutanal, isobutyraldehyde, methacrolein, 2-methylundecanal,
mucochloric acid,
N-methylformamide, 2-nitrobenzaldehyde, nonanal, octanal, oleocanthal,
orlistate, pentanal, phenyl
ethanal, phycocyanin, piperonal, propanal, propenal, protocatechualdehyde,
retinal, salicylaldehyde,
secologanin, streptomycin, strophanthidin, tylosin, vanillin, and cinnamic
aldehyde, but preferably
has at least two free aldehyde groups per molecule, in particular glutar-
and/or succindialdehyde.
In one aspect, the (meth)acrylate polymer is a homo- or copolymer of a polar
functionalized (meth)acrylate monomer, preferably one containing a sulfonic
acid group, wherein
the (meth)acrylate polymer is in particular a copolymer of 2-acrylamido-2-
methyl
propanesulfonic acid or its salts along with one or more other (meth)acrylate
monomers, chosen
from the group of (meth)acrylates, vinyl compounds, unsaturated di- or
polycarboxylic acids and
the salts of amyl compounds or allyl compounds.
In one aspect, said microcapsules are present in said composition in amounts
of 0.0001 to
50 wt %, 0.01 to 20 wt %, 0.05 to 5%, 0.1 to 5 wt %, or 0.1 to 2%, based on
the product as a
whole.
In one aspect, said composition contains, based on total composition weight,
0.05 wt %
to 50 wt %, advantageously 1 to 40 wt %, 3 to 30 wt % or 5 wt % to 20 wt %
surfactant
selected from the groups of anionic surfactants, nonionic surfactants,
cationic, zwitterionic
and/or amphoteric surfactants.
In one aspect, said composition contains, based on total composition weight, a
nonionic
surfactant, in one aspect, said composition contains, based on total
composition weight, from
0.01 to 25 wt %, from 1 to 20 wt %, or from 3 to 15 wt %, nonionic surfactant.
In one aspect, said composition contains, based on total composition weight,
from 0.1 to
80 wt %, 1 to 60 wt %, or 5 to 50 wt % builders.
In one aspect, said composition contains a soluble builder system, in one
aspect, said
soluble builder system comprises soda, silicate, citrate and/or
polycarboxylates.
In one aspect, said microcapsules contain aromatic substances.
In one aspect, said benefit agent delivery particles may have any combination
of the
aforementioned parameters as listed in the aforementioned aspects.
In one aspect, a method for manufacturing a liquid composition, comprising
stirring in a
microcapsule dispersion comprising microcapsules, the capsule walls of which
contain a resin,
which can be obtained by reacting
a) at least one aromatic alcohol or its ether or derivatives with
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b) at least one aldehydic component that has at least two carbon atoms per
molecule,
and
c) optionally in the presence of at least one (meth)acrylate polymer
in a liquid composition or by continuously adding said microcapsule dispersion
into a liquid
composition and mixing the ingredients by means of static mixing elements, in
one aspect, the
microcapsule dispersion is mixed with surfactant beforehand
is disclosed.
In one aspect, a method for manufacturing a solid composition, selected from
the group
consisting of (a) by mixing a microcapsule dispersion comprising
microcapsules, the capsule
walls of which contain a resin which can be obtained by reacting:
(i) at least one aromatic alcohol or its ether or derivatives with
(ii) at least one aldehydic component that has at least two C atoms per
molecule, and
(iii)optionally in the presence of at least one (meth)acrylate polymer
into a solid composition;
(b) by mixing said microcapsules in granulated or supported form into a solid
composition;
or
(c) by mixing said microcapsules in dried form into the solid composition
is disclosed.
In one aspect, the use of a composition described herein in a washing or
cleaning process
to deposit microcapsules on the treated object to enable the targeted release
of, in one aspect,
liquid active substances such as, in particular, aromatic substances, onto the
objects by
mechanical stimulus is disclosed.
In one aspect, the use of a composition described herein in a washing or
cleaning process
to deposit microcapsules on the treated object to enable the long-lasting
release of, in one aspect,
liquid active substances such as, in particular, aromatic substances, onto the
objects by diffusion
is disclosed.
In one aspect, compositions of the present invention, for example shampoos,
may include
the following components:
A. Detersive Surfactant
The composition of the present invention may include a detersive surfactant.
The
detersive surfactant component may comprise anionic detersive surfactant,
zwitterionic or
amphoteric detersive surfactant, or a combination thereof. The concentration
of the anionic
surfactant component in the composition should be sufficient to provide the
desired cleaning and
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lather performance, and generally range from about 5% to about 50%.
Anionic surfactants suitable for use in the compositions are the alkyl and
alkyl ether
sulfates. Other suitable anionic detersive surfactants are the water-soluble
salts of organic,
sulfuric acid reaction products conforming to the formula R1--S03-M where R1-
is a straight or
branched chain, saturated, aliphatic hydrocarbon radical having from about 8
to about 24, or
about 10 to about 18, carbon atoms; and M is a cation described hereinbefore.
Still other
suitable anionic detersive surfactants are the reaction products of fatty
acids esterified with
isethionic acid and neutralized with sodium hydroxide where, for example, the
fatty acids are
derived from coconut oil or palm kernel oil; sodium or potassium salts of
fatty acid amides of
methyl tauride in which the fatty acids, for example, are derived from coconut
oil or palm kernel
oil.
Other anionic detersive surfactants suitable for use in the compositions are
the
succinnates, examples of which include disodium N-octadecylsulfosuccinnate;
disodium lauryl
sulfosuccinate; diammonium lauryl sulfosuccinate; tetrasodium N-(1,2-
dicarboxyethyl)-N-
octadecylsulfosuccinnate; diamyl ester of sodium sulfosuccinic acid; dihexyl
ester of sodium
sulfosuccinic acid; and dioctyl esters of sodium sulfosuccinic acid.
Other suitable anionic detersive surfactants include olefin sulfonates having
about 10 to
about 24 carbon atoms. In addition to the true alkene sulfonates and a
proportion of
hydroxy-alkanesulfonates, the olefin sulfonates can contain minor amounts of
other materials,
such as alkene disulfonates depending upon the reaction conditions, proportion
of reactants, the
nature of the starting olefins and impurities in the olefin stock and side
reactions during the
sulfonation process.
Another class of anionic detersive surfactants suitable for use in the
compositions is the
beta-alkyloxy alkane sulfonates. These surfactants conform to the formula
oR2
R1 ___________________________________________ so3m
H
where R1- is a straight chain alkyl group having from about 6 to about 20
carbon atoms, R2 is a
lower alkyl group having from about 1 to about 3 carbon atoms, or even 1
carbon atom, and M is
a water-soluble cation.
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B. Cationic Surfactant System
The composition of the present invention may comprise a cationic surfactant
system. The
cationic surfactant system can be one cationic surfactant or a mixture of two
or more cationic
surfactants. If present, the cationic surfactant system is included in the
composition at a level by
5 weight of from about 0.1% to about 10%, from about 0.5% to about 8%, from
about 1% to about
5%, or even from about 1.4% to about 4%, in view of balance among ease-to-
rinse feel, rheology
and wet conditioning benefits.
A variety of cationic surfactants including mono- and di-alkyl chain cationic
surfactants
can be used in the compositions of the present invention. Examples of suitable
materials include
10 mono-alkyl chain cationic surfactants in view of the desired gel matrix
and wet conditioning
benefits. The mono-alkyl cationic surfactants are those having one long alkyl
chain which has
from 12 to 22 carbon atoms, from 16 to 22 carbon atoms, or a C18-C22 alkyl
group, in view of
providing balanced wet conditioning benefits. The remaining groups attached to
nitrogen are
independently selected from an alkyl group of from 1 to about 4 carbon atoms
or an alkoxy,
polyoxyalkylene, alkylamido, hydroxyalkyl, aryl or alkylaryl group having up
to about 4 carbon
atoms. Such mono-alkyl cationic surfactants include, for example, mono-alkyl
quaternary
ammonium salts and mono-alkyl amines. Mono-alkyl quaternary ammonium salts
include, for
example, those having a non-functionalized long alkyl chain. Mono-alkyl amines
include, for
example, mono-alkyl amidoamines and salts thereof.
Mono-long alkyl quaternized ammonium salts useful herein are those having the
formula
(II):
(II) R75
76 1 a 78
xe
R -N -R
1
R77
wherein one of R75, R76, R77 and R78 is selected from an alkyl group of from
12 to 30 carbon
atoms or an aromatic, alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, aryl
or alkylaryl
group having up to about 30 carbon atoms; the remainder of R75, R76, R77 and
R78 are
independently selected from an alkyl group of from 1 to about 4 carbon atoms
or an alkoxy,
polyoxyalkylene, alkylamido, hydroxyalkyl, aryl or alkylaryl group having up
to about 4 carbon
atoms; and X- is a salt-forming anion such as those selected from halogen,
(e.g. chloride,
bromide), acetate, citrate, lactate, glycolate, phosphate, nitrate, sulfonate,
sulfate, alkylsulfate,
and alkyl sulfonate radicals. The alkyl groups can contain, in addition to
carbon and hydrogen
atoms, ether and/or ester linkages, and other groups such as amino groups. The
longer chain
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alkyl groups, e.g., those of about 12 carbons, or higher, can be saturated or
unsaturated. In one
aspectõ one of R75, R76, R77 and R78 is selected from an alkyl group of from
12 to 30 carbon
atoms, in another aspect, from 16 to 22 carbon atoms, in another aspect, from
18 to 22 carbon
atoms, or even 22 carbon atoms; the remainder of R75, R76, R77 and R78 are
independently
selected from CH3, C2H5, C2H4OH, and mixtures thereof; and X is selected from
the group
consisting of Cl, Br, CH30S03, C2H50S03, and mixtures thereof.
Examples of suitable mono-long alkyl quaternized ammonium salt cationic
surfactants
include: behenyl trimethyl ammonium salt; stearyl trimethyl ammonium salt;
cetyl trimethyl
ammonium salt; and hydrogenated tallow alkyl trimethyl ammonium salt. Among
them, highly
useful materials are behenyl trimethyl ammonium salt and stearyl trimethyl
ammonium salt.
Mono-alkyl amines are also suitable as cationic surfactants. Primary,
secondary, and
tertiary fatty amines are useful. Particularly useful are tertiary amido
amines having an alkyl
group of from about 12 to about 22 carbons. Exemplary tertiary amido amines
include:
stearamidopropyldimethylamine, stearamidopropyldiethylamine,
stearamidoethyldiethylamine,
s tearamidoethyldimethyl amine, palmitamidopropyldimethylamine,
palmitamidopropyldiethylamine,
palmitamidoethyldiethylamine,
palmitamidoethyldimethyl amine,
behenamidopropyldimethylamine,
behenamidopropyldiethylamine, behenamidoethyldiethylamine,
behenamidoethyldimethylamine,
arachidamidopropyldimethylamine,
arachidamidoprop yldiethyl amine,
arachidamidoethyldiethylamine, arachidamidoethyldimethylamine,
diethylaminoethylstearamide.
These amines can also be used in combination with acids such as t-glutamic
acid, lactic acid,
hydrochloric acid, malic acid, succinic acid, acetic acid, fumaric acid,
tartaric acid, citric acid, t-
glutamic hydrochloride, maleic acid, and mixtures thereof; in one aspect, t-
glutamic acid, lactic
acid, citric acid are highly useful. In one aspect, amines herein are
partially neutralized with any
of the acids at a molar ratio of the amine to the acid of from about 1 : 0.3
to about 1 : 2, or even
from about 1: 0.4 to about 1: 1.
Although the mono-alkyl chain cationic surfactants are useful, other cationic
surfactants
such as di-alkyl chain cationic surfactants may also be used alone, or in
combination with the
mono-alkyl chain cationic surfactants. Such di-alkyl chain cationic
surfactants include, for
example, dialkyl (14-18) dimethyl ammonium chloride, ditallow alkyl dimethyl
ammonium
chloride, dihydrogenated tallow alkyl dimethyl ammonium chloride, distearyl
dimethyl
ammonium chloride, and dicetyl dimethyl ammonium chloride.
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C. High Melting Point Fatty Compound
The composition of the present invention may include a high melting point
fatty
compound. The high melting point fatty compound useful herein has a melting
point of 25 C or
higher, and is selected from the group consisting of fatty alcohols, fatty
acids, fatty alcohol
derivatives, fatty acid derivatives, and mixtures thereof. It is understood by
the artisan that the
compounds disclosed in this section of the specification can in some instances
fall into more than
one classification, e.g., some fatty alcohol derivatives can also be
classified as fatty acid
derivatives. However, a given classification is not intended to be a
limitation on that particular
compound, but is done so for convenience of classification and nomenclature.
Further, it is
understood by the artisan that, depending on the number and position of double
bonds, and length
and position of the branches, certain compounds having certain required carbon
atoms may have
a melting point of less than 25 C. Such compounds of low melting point are not
intended to be
included in this section.
Among a variety of high melting point fatty compounds, fatty alcohols are used
in one
aspect the present invention. The fatty alcohols useful herein are those
having from about 14 to
about 30 carbon atoms, or even from about 16 to about 22 carbon atoms. These
fatty alcohols are
saturated and can be straight or branched chain alcohols. In one aspect, fatty
alcohols include,
for example, cetyl alcohol, stearyl alcohol, behenyl alcohol, and mixtures
thereof.
High melting point fatty compounds of a single compound of high purity are
typically
used. In one aspect, single compounds of pure fatty alcohols selected from the
group of pure
cetyl alcohol, stearyl alcohol, and behenyl alcohol are employed. By "pure"
herein, what is
meant is that the compound has a purity of at least about 90%, or even at
least about 95%. These
single compounds of high purity provide good rinsability from the hair when
the consumer rinses
off the composition.
The high melting point fatty compound is included in the composition at a
level of from
about 0.1% to about 40%, from about 1% to about 30%, from about 1.5% to about
16% by
weight of the composition, or even from about 1.5% to about 8% in view of
providing improved
conditioning benefits such as slippery feel during the application to wet
hair, softness and
moisturized feel on dry hair.
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13
D. Cationic Polymers
The compositions of the present invention may contain a cationic polymer.
Concentrations of the cationic polymer in the composition typically range from
about 0.05% to
about 3%, in another embodiment from about 0.075% to about 2.0%, and in yet
another
embodiment from about 0.1% to about 1.0%. Suitable cationic polymers will have
cationic
charge densities of at least about 0.5 meq/gm, in another embodiment at least
about 0.9 meq/gm,
in another embodiment at least about 1.2 meq/gm, in yet another embodiment at
least about 1.5
meq/gm, but in one embodiment also less than about 7 meq/gm, and in another
embodiment less
than about 5 meq/gm, at the pH of intended use of the composition, which pH
will generally
range from about pH 3 to about pH 9, in one embodiment between about pH 4 and
about pH 8.
Herein, "cationic charge density" of a polymer refers to the ratio of the
number of positive
charges on the polymer to the molecular weight of the polymer. The average
molecular weight
of such suitable cationic polymers will generally be between about 10,000 and
10 million, in one
embodiment between about 50,000 and about 5 million, and in another embodiment
between
about 100,000 and about 3 million.
Suitable cationic polymers for use in the compositions of the present
invention contain
cationic nitrogen-containing moieties such as quaternary ammonium or cationic
protonated
amino moieties. The cationic protonated amines can be primary, secondary, or
tertiary amines (in
one aspect, secondary or tertiary), depending upon the particular species and
the selected pH of
the composition. Any anionic counterion can be used in association with the
cationic polymers
so long as the polymers remain soluble in water, in the composition, or in a
coacervate phase of
the composition, and so long as the counterions are physically and chemically
compatible with
the essential components of the composition or do not otherwise unduly impair
product
performance, stability or aesthetics. Non limiting examples of such
counterions include halides
(e.g., chloride, fluoride, bromide, iodide), sulfate and methyl sulfate.
Non limiting examples of suitable cationic polymers include copolymers of
vinyl
monomers having cationic protonated amine or quaternary ammonium
functionalities with water
soluble spacer monomers such as acrylamide, methacrylamide, alkyl and dialkyl
acrylamides,
alkyl and dialkyl methacrylamides, alkyl acrylate, alkyl methacrylate, vinyl
caprolactone or vinyl
pyrrolidone.
Suitable cationic protonated amino and quaternary ammonium monomers, for
inclusion in
the cationic polymers of the composition herein, include vinyl compounds
substituted with
dialkylaminoalkyl acrylate, dialkylaminoalkyl methacrylate,
monoalkylaminoalkyl acrylate,
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monoalkylaminoalkyl methacrylate, trialkyl methacryloxyalkyl ammonium salt,
trialkyl
acryloxyalkyl ammonium salt, diallyl quaternary ammonium salts, and vinyl
quaternary
ammonium monomers having cyclic cationic nitrogen-containing rings such as
pyridinium,
imidazolium, and quaternized pyrrolidone, e.g., alkyl vinyl imidazolium, alkyl
vinyl pyridinium,
alkyl vinyl pyrrolidone salts.
Other suitable cationic polymers for use in the compositions include
copolymers of 1-
vinyl-2-pyrrolidone and 1-vinyl-3-methylimidazolium salt (e.g., chloride salt)
(referred to in the
industry by the Cosmetic, Toiletry, and Fragrance Association, "CTFA", as
Polyquaternium-16);
copolymers of 1-viny1-2-pyrrolidone and dimethylaminoethyl methacrylate
(referred to in the
industry by CTFA as Polyquaternium-11); cationic diallyl quaternary ammonium-
containing
polymers, including, for example, dimethyldiallylammonium chloride
homopolymer, copolymers
of acrylamide and dimethyldiallylammonium chloride (referred to in the
industry by CTFA as
Polyquaternium 6 and Polyquaternium 7, respectively); amphoteric copolymers of
acrylic acid
including copolymers of acrylic acid and dimethyldiallylammonium chloride
(referred to in the
industry by CTFA as Polyquaternium 22), terpolymers of acrylic acid with
dimethyldiallylammonium chloride and acrylamide (referred to in the industry
by CTFA as
Polyquaternium 39), and terpolymers of acrylic acid with methacrylamidopropyl
trimethylammonium chloride and methyl acrylate (referred to in the industry by
CTFA as
Polyquaternium 47). In one aspect, cationic substituted monomers may be the
cationic
substituted dialkylaminoalkyl acrylamides, dialkylaminoalkyl methacrylamides,
and
combinations thereof. Such monomers conform the to the formula
R3
X
R2- N+ - R4
(CH2)n
NH
C=0
-[-CH2 C
R1
wherein R1 is hydrogen, methyl or ethyl; each of R2, R3 and R4 are
independently hydrogen or a
short chain alkyl having from about 1 to about 8 carbon atoms, from about 1 to
about 5 carbon
atoms, or even from about 1 to about 2 carbon atoms; n is an integer having a
value of from
about 1 to about 8, or even from about 1 to about 4; and X is a counterion.
The nitrogen attached
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to R2, R3 and R4 may be a protonated amine (primary, secondary or tertiary),
but is in one aspect,
a quaternary ammonium wherein each of R2, R3 and R4 are alkyl groups a non
limiting example
of which is polymethacrylamidopropyl trimonium chloride, available under the
trade name
Polycare 133, from Rhone-Poulenc, Cranberry, N.J., U.S .A.
5
Other suitable cationic polymers for use in the composition include
polysaccharide
polymers, such as cationic cellulose derivatives and cationic starch
derivatives. Suitable cationic
polysaccharide polymers include those which conform to the formula
R1
1
A-0-(R-N+-R'õ
X)
I
R2
wherein A is an anhydroglucose residual group, such as a starch or cellulose
anhydroglucose
10
residual; R is an alkylene oxyalkylene, polyoxyalkylene, or hydroxyalkylene
group, or
combination thereof; R1, R2, and R3 independently are alkyl, aryl, alkylaryl,
arylalkyl,
alkoxyalkyl, or alkoxyaryl groups, each group containing up to about 18 carbon
atoms, and the
total number of carbon atoms for each cationic moiety (i.e., the sum of carbon
atoms in R1, R2
and R3) is typically about 20 or less; and X is an anionic counterion as
described in hereinbefore.
15
Useful cationic cellulose polymers include salts of hydroxyethyl cellulose
reacted with
trimethyl ammonium substituted epoxide, referred to in the industry (CTFA) as
Polyquaternium
10 and available from Amerchol Corp. (Edison, N.J., USA) in their UcareTm
Polymer LR,
UcareTm Polymer JR, and UcareTm Polymer KG series of polymers. Other suitable
types of
cationic cellulose include the polymeric quaternary ammonium salts of
hydroxyethyl cellulose
reacted with lauryl dimethyl ammonium-substituted epoxide referred to in the
industry (CTFA)
as Polyquaternium 24. These materials are available from Amerchol Corp. under
the trade name
UcareTm Polymer LM-200.
Other suitable cationic polymers include cationic guar gum derivatives, such
as guar
hydroxypropyltrimonium chloride, specific examples of which include the Jaguar
series
commercially available from Rhone-Poulenc Incorporated and the NHance series
commercially available from Aqualon Division of Hercules, Inc. Other suitable
cationic
polymers include quaternary nitrogen-containing cellulose ethers. Other
suitable polymers
include synthetic polymers. Other suitable cationic polymers include
copolymers of etherified
cellulose, guar and starch. When used, the cationic polymers herein are either
soluble in the
composition or are soluble in a complex coacervate phase in the composition
formed by the
cationic polymer and the anionic, amphoteric and/or zwitterionic detersive
surfactant component
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described hereinbefore. Complex coacervates of the cationic polymer can also
be formed with
other charged materials in the composition.
E. Nonionic polymers
The composition of the present invention may include a nonionic polymer.
Polyalkylene glycols
having a molecular weight of more than about 1000 are useful herein. Useful
are those having
the following general formula:
H(OCH2CH)OH
1x
R"
wherein R95 is selected from the group consisting of H, methyl, and mixtures
thereof.
Polyethylene glycol polymers useful herein are PEG-2M (also known as Polyox
WSR N-10,
which is available from Union Carbide and as PEG-2,000); PEG-5M (also known as
Polyox
WSR N-35 and Polyox WSR N-80, available from Union Carbide and as PEG-5,000
and
Polyethylene Glycol 300,000); PEG-7M (also known as Polyox WSR N-750
available from
Union Carbide); PEG-9M (also known as Polyox WSR N-3333 available from Union
Carbide);
and PEG-14 M (also known as Polyox WSR N-3000 available from Union Carbide).
F. Conditioning agents
Conditioning agents, and in particular silicones, may be included in the
composition.
Conditioning agents include any material which is used to give a particular
conditioning benefit
to hair and/or skin. In hair treatment compositions, suitable conditioning
agents are those which
deliver one or more benefits relating to shine, softness, compatibility,
antistatic properties, wet-
handling, damage, manageability, body, and greasiness. The conditioning agents
useful in the
compositions of the present invention typically comprise a water insoluble,
water dispersible,
non-volatile, liquid that forms emulsified, liquid particles. Suitable
conditioning agents for use in
the composition are those conditioning agents characterized generally as
silicones (e.g., silicone
oils, cationic silicones, silicone gums, high refractive silicones, and
silicone resins), organic
conditioning oils (e.g., hydrocarbon oils, polyolefins, and fatty esters) or
combinations thereof,
or those conditioning agents which otherwise form liquid, dispersed particles
in the aqueous
surfactant matrix herein. Such conditioning agents should be physically and
chemically
compatible with the essential components of the composition, and should not
otherwise unduly
impair product stability, aesthetics or performance.
The concentration of the conditioning agent in the composition should be
sufficient to
provide the desired conditioning benefits, and as will be apparent to one of
ordinary skill in the
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17
art. Such concentration can vary with the conditioning agent, the conditioning
performance
desired, the average size of the conditioning agent particles, the type and
concentration of other
components, and other like factors.
1. Silicones
The conditioning agent of the compositions of the present invention can be an
insoluble
silicone conditioning agent. The silicone conditioning agent particles may
comprise volatile
silicone, non-volatile silicones, or combinations thereof. In one aspect, non-
volatile silicones
conditioning agents are employed. If volatile silicones are present, it will
typically be incidental
to their use as a solvent or carrier for commercially available forms of non-
volatile silicone
materials ingredients, such as silicone gums and resins. The silicone
conditioning agent particles
may comprise a silicone fluid conditioning agent and may also comprise other
ingredients, such
as a silicone resin to improve silicone fluid deposition efficiency or enhance
glossiness of the
hair.
The concentration of the silicone conditioning agent typically ranges from
about 0.01%
to about 10%, from about 0.1% to about 8%, from about 0.1% to about 5%, or
even from about
0.2% to about 3%. The silicone conditioning agents for use in the compositions
of the present
invention typically have a viscosity, as measured at 25 C, from about 20
centistokes to about
2,000,000 centistokes ("cst"), from about 1,000 cst to about 1,800,000 cst,
from about 50,000cst
to about 1,500,000 cst, or even from about 100,000 cst to about 1,500,000 csk.
The dispersed silicone conditioning agent particles typically have a number
average
particle diameter ranging from about 0.011.tm to about 50 m. For small
particle application to
hair, the number average particle diameters typically range from about 0.01 m
to about 4i.tm,
from about 0.01 m to about 2i.tm, or even from about 0.01 m to about 0.5 m.
For larger
particle application to hair, the number average particle diameters typically
range from about
4jim to about 50 ,m, from about 6i.tm to about 30 ,m, from about 9i.tm to
about 20 ,m, or even
from about 121.tm to about 18 m.
a. Silicone oils
Silicone fluids may include silicone oils, which are flowable silicone
materials having a
viscosity, as measured at 25 C, less than 1,000,000 cst, from about 5 cst to
about 1,000,000 cst,
or even from about 100 cst to about 600,000 cst. Suitable silicone oils for
use in the
compositions of the present invention include polyalkyl siloxanes, polyaryl
siloxanes,
polyalkylaryl siloxanes, polyether siloxane copolymers, and mixtures thereof.
Other insoluble,
non-volatile silicone fluids having hair conditioning properties may also be
used.
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b. Amino and Cationic silicones
Compositions of the present invention may include an aminosilicone.
Aminosilicones, as
provided herein, are silicones containing at least one primary amine,
secondary amine, tertiary
amine, or a quaternary ammonium group. Useful aminosilicones may have less
than about 0.5%
nitrogen by weight of the aminosilicone, less than about 0.2%, or even less
than about 0.1%.
Higher levels of nitrogen (amine functional groups) in the amino silicone tend
to result in less
friction reduction, and consequently less conditioning benefit from the
aminosilicone. It should
be understood that in some product forms, higher levels of nitrogen are
acceptable in accordance
with the present invention.
In one aspect, the aminosilicones used in the present invention have a
particle size of less
than about 5011 once incorporated into the final composition. The particle
size measurement is
taken from dispersed droplets in the final composition. Particle size may be
measured by means
of a laser light scattering technique, using a Horiba model LA-930 Laser
Scattering Particle Size
Distribution Analyzer (Horiba Instruments, Inc.).
In one embodiment, the aminosilicone typically has a viscosity of from about
1,000 cst
(centistokes) to about 1,000,000 cst, from about 10,000 to about 700,000 cst,
from about 50,000
cst to about 500,000 cst, or even from about 100,000 cst to about 400,000 cst.
This embodiment
may also comprise a low viscosity fluid, such as, for example, those materials
described below in
Section F.(1). The viscosity of aminosilicones discussed herein is measured at
25 C.
In another embodiment, the aminosilicone typically has a viscosity of from
about 1,000
cst to about 100,000 cst, from about 2,000 cst to about 50,000 cst, from about
4,000 cst to about
40,000 cst, or even from about 6,000 cst to about 30,000 cs.
The aminosilicone typically is contained in the composition of the present
invention at a
level by weight of from about 0.05% to about 20%, from about 0.1% to about
10%, and or even
from about 0.3% to about 5%.
c. Silicone gums
Other silicone fluids suitable for use in the compositions of the present
invention are the
insoluble silicone gums. These gums are polyorganosiloxane materials having a
viscosity, as
measured at 25 C, of greater than or equal to 1,000,000 csk. Specific non-
limiting examples of
silicone gums for use in the compositions of the present invention include
polydimethylsiloxane,
(polydimethylsiloxane) (methylvinylsiloxane) copolymer, poly(dimethylsiloxane)
(diphenyl
siloxane)(methylvinylsiloxane) copolymer and mixtures thereof.
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d. High refractive index silicones
Other non-volatile, insoluble silicone fluid conditioning agents that are
suitable for use in
the compositions of the present invention are those known as "high refractive
index silicones,"
having a refractive index of at least about 1.46, at least about 1.48, m at
least about 1.52, or even
at least about 1.55. The refractive index of the polysiloxane fluid will
generally be less than
about 1.70, typically less than about 1.60. In this context, polysiloxane
"fluid" includes oils as
well as gums.
The high refractive index polysiloxane fluid includes those represented by
general
Formula (III) above, as well as cyclic polysiloxanes such as those represented
by Formula (VIII)
below:
wherein R is as defined above, and n is a number from about 3 to about 7, or
even from about 3
to about 5.
e. Silicone resins
Silicone resins may be included in the conditioning agent of the compositions
of the
present invention. These resins are highly cross-linked polymeric siloxane
systems. The cross-
linking is introduced through the incorporation of trifunctional and
tetrafunctional silanes with
monofunctional or difunctional, or both, silanes during manufacture of the
silicone resin.
Silicone materials and silicone resins in particular, can conveniently be
identified
according to a shorthand nomenclature system known to those of ordinary skill
in the art as
"MDTQ" nomenclature. Under this system, the silicone is described according to
presence of
various siloxane monomer units which make up the silicone. Briefly, the symbol
M denotes the
monofunctional unit (CH3)35i00 5; D denotes the difunctional unit (CH3)25i0; T
denotes the
trifunctional unit (CH3)SiOi 5; and Q denotes the quadra- or tetra-functional
unit 5i02. Primes
of the unit symbols (e.g. M', D', T', and Q') denote substituents other than
methyl, and must be
specifically defined for each occurrence.
In one aspect, silicone resins for use in the compositions of the present
invention include,
but are not limited to MQ, MT, MTQ, MDT and MDTQ resins. In one aspect, Methyl
is a highly
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suitable silicone substituent. In another aspect, silicone resins are
typically MQ resins, wherein
the M:Q ratio is typically from about 0.5:1.0 to about 1.5:1.0 and the average
molecular weight
of the silicone resin is typically from about 1000 to about 10,000.
f. Modified silicones or silicone copolymers
5 Other modified silicones or silicone copolymers are also useful herein.
Examples include
silicone-based quaternary ammonium compounds (Kennan quats), end-terminal
quaternary
siloxanes; silicone aminopolyalkyleneoxide block copolymers; hydrophilic
silicone emulsions;
and polymers made up of one or more crosslinked rake or comb silicone
copolymer segments.
In alternative embodiments of the present invention, the above-noted silicone-
based
10 quaternary ammonium compounds may be combined with the silicone
polymers.
2. Organic conditioning oils
The compositions of the present invention may also comprise from about 0.05%
to about
3%, from about 0.08% to about 1.5%, or even from about 0.1% to about 1%, of at
least one
organic conditioning oil as the conditioning agent, either alone or in
combination with other
15 conditioning agents, such as the silicones (described herein). Suitable
conditioning oils include
hydrocarbon oils, polyolefins, and fatty esters. Suitable hydrocarbon oils
include, but are not
limited to, hydrocarbon oils having at least about 10 carbon atoms, such as
cyclic hydrocarbons,
straight chain aliphatic hydrocarbons (saturated or unsaturated), and branched
chain aliphatic
hydrocarbons (saturated or unsaturated), including polymers and mixtures
thereof. Straight chain
20 hydrocarbon oils are typically from about C12 to about C19. Branched
chain hydrocarbon oils,
including hydrocarbon polymers, typically will contain more than 19 carbon
atoms. Suitable
polyolefins include liquid polyolefins, liquid poly-cc-olefins, or even
hydrogenated liquid poly-cc-
olefins. Polyolefins for use herein may be prepared by polymerization of C4 to
about C14 or
even C6 to about C12. Suitable fatty esters include, but are not limited to,
fatty esters having at
least 10 carbon atoms. These fatty esters include esters with hydrocarbyl
chains derived from
fatty acids or alcohols (e.g. mono-esters, polyhydric alcohol esters, and di-
and tri-carboxylic
acid esters). The hydrocarbyl radicals of the fatty esters hereof may include
or have covalently
bonded thereto other compatible functionalities, such as amides and alkoxy
moieties (e.g., ethoxy
or ether linkages, etc.).
3. Other conditioning agents
Also suitable for use in the compositions herein are the conditioning agents.
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G. Anti-dandruff Actives
The compositions of the present invention may also contain an anti-dandruff
agent.
Suitable, non-limiting examples of anti-dandruff actives include:
antimicrobial actives,
pyridinethione salts, azoles, selenium sulfide, particulate sulfur,
keratolytic acid, salicylic acid,
octopirox (piroctone olamine), coal tar, and combinations thereof. In one
aspect, the anti-
dandruff actives typically are pyridinethione salts. Such anti-dandruff
particulate should be
physically and chemically compatible with the essential components of the
composition, and
should not otherwise unduly impair product stability, aesthetics or
performance.
It is contemplated that when ZPT is used as the anti-dandruff particulate in
the
compositions herein, that the growth or re-growth of hair may be stimulated or
regulated, or
both, or that hair loss may be reduced or inhibited, or that hair may appear
thicker or fuller.
H. Humectant
The compositions of the present invention may contain a humectant. The
humectants
herein are selected from the group consisting of polyhydric alcohols, water
soluble alkoxylated
nonionic polymers, and mixtures thereof. The humectants, when used herein, are
typically used
at levels of from about 0.1% to about 20%, or even from about 0.5% to about
5%.
I. Suspending Agent
The compositions of the present invention may further comprise a suspending
agent at
concentrations effective for suspending water-insoluble material in dispersed
form in the
compositions or for modifying the viscosity of the composition. Such
concentrations range from
about 0.1% to about 10%, or even from about 0.3% to about 5.0%.
Suspending agents useful herein include anionic polymers and nonionic
polymers. Useful
herein are vinyl polymers such as cross linked acrylic acid polymers with the
CTFA name
Carbomer, cellulose derivatives and modified cellulose polymers such as methyl
cellulose, ethyl
cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, nitro
cellulose, sodium
cellulose sulfate, sodium carboxymethyl cellulose, crystalline cellulose,
cellulose powder,
polyvinylpyrrolidone, polyvinyl alcohol, guar gum, hydroxypropyl guar gum,
xanthan gum,
arabia gum, tragacanth, galactan, carob gum, guar gum, karaya gum,
carrageenan, pectin, agar,
quince seed (Cydonia oblonga Mill), starch (rice, corn, potato, wheat), algae
colloids (algae
extract), microbiological polymers such as dextran, succinoglucan, pulleran,
starch-based
polymers such as carboxymethyl starch, methylhydroxypropyl starch, alginic
acid-based
polymers such as sodium alginate, alginic acid propylene glycol esters,
acrylate polymers such as
sodium polyacrylate, polyethylacrylate, polyacrylamide, polyethyleneimine, and
inorganic water
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soluble material such as bentonite, aluminum magnesium silicate, laponite,
hectonite, and
anhydrous silicic acid.
Commercially available viscosity modifiers highly useful herein include
Carbomers with
trade names Carbopol 934, Carbopol 940, Carbopol 950, Carbopol 980, and
Carbopol 981,
all available from B. F. Goodrich Company, acrylates/steareth-20 methacrylate
copolymer with
trade name ACRYSOLTm 22 available from Rohm and Hass, nonoxynyl
hydroxyethylcellulose
with trade name AmercellTm POLYMER HM-1500 available from Amerchol,
methylcellulose
with trade name BENECEL , hydroxyethyl cellulose with trade name NATROSOL ,
hydroxypropyl cellulose with trade name KLUCEL , cetyl hydroxyethyl cellulose
with trade
name POLYSURF 67, all supplied by Hercules, ethylene oxide and/or propylene
oxide based
polymers with trade names CARBOWAX PEGs, POLYOX WASRs, and UCON FLUIDS, all
supplied by Amerchol. Other optional suspending agents include crystalline
suspending agents
which can be categorized as acyl derivatives, long chain amine oxides, and
mixtures thereof.
These suspending agents include ethylene glycol esters of fatty acids in one
aspect having
from about 16 to about 22 carbon atoms. In one aspect, useful suspending
agents include
ethylene glycol stearates, both mono and distearate, but in one aspect, the
distearate containing
less than about 7% of the mono stearate. Other suitable suspending agents
include alkanol
amides of fatty acids, having from about 16 to about 22 carbon atoms, or even
about 16 to 18
carbon atoms, examples of which include stearic monoethanolamide, stearic
diethanolamide,
stearic monoisopropanolamide and stearic monoethanolamide stearate. Other long
chain acyl
derivatives include long chain esters of long chain fatty acids (e.g., stearyl
stearate, cetyl
palmitate, etc.); long chain esters of long chain alkanol amides (e.g.,
stearamide diethanolamide
distearate, stearamide monoethanolamide stearate); and glyceryl esters (e.g.,
glyceryl distearate,
trihydroxystearin,
..................................................... a commercial example of
which is Thixin R available from
Rheox, Inc. Long chain acyl derivatives, ethylene glycol esters of long chain
carboxylic acids,
long chain amine oxides, and alkanol amides of long chain carboxylic acids in
addition to the
materials listed above may be used as suspending agents.
Other long chain acyl derivatives suitable for use as suspending agents
include N,N-
dihydrocarbyl amido benzoic acid and soluble salts thereof (e.g., Na, K),
particularly N,N-
di(hydrogenated) C16, C18 and tallow amido benzoic acid species of this
family, which are
commercially available from Stepan Company (Northfield, Ill., USA).
Examples of suitable long chain amine oxides for use as suspending agents
include alkyl
dimethyl amine oxides, e.g., stearyl dimethyl amine oxide.
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Other suitable suspending agents include primary amines having a fatty alkyl
moiety
having at least about 16 carbon atoms, examples of which include palmitamine
or stearamine,
and secondary amines having two fatty alkyl moieties each having at least
about 12 carbon
atoms, examples of which include dipalmitoylamine or di(hydrogenated
tallow)amine. Still
other suitable suspending agents include di(hydrogenated tallow)phthalic acid
amide, and
crosslinked maleic anhydride-methyl vinyl ether copolymer.
J. Aqueous Carrier
The formulations of the present invention can be in the form of pourable
liquids (under
ambient conditions). Such compositions will therefore typically comprise an
aqueous carrier,
which is present at a level of from about 20% to about 95%, or even from about
60% to about
85%. The aqueous carrier may comprise water, or a miscible mixture of water
and organic
solvent, and in one aspect may comprise water with minimal or no significant
concentrations of
organic solvent, except as otherwise incidentally incorporated into the
composition as minor
ingredients of other essential or optional components.
The carrier useful in the present invention includes water and water solutions
of lower
alkyl alcohols and polyhydric alcohols. The lower alkyl alcohols useful herein
are monohydric
alcohols having 1 to 6 carbons, in one aspect, ethanol and isopropanol. The
polyhydric alcohols
useful herein include propylene glycol, hexylene glycol, glycerin, and propane
diol.
K. Dispersed Particles
The compositions may optionally comprise particles. The particles may be
dispersed
water-insoluble particles. The particles may be inorganic, synthetic, or semi-
synthetic. In one
embodiment, the particles have an average mean particle size of less than
about 300 m.
L. Gel Matrix
The above cationic surfactants, together with high melting point fatty
compounds and an
aqueous carrier, may form a gel matrix in the composition of the present
invention.
The gel matrix is suitable for providing various conditioning benefits such as
slippery feel
during the application to wet hair and softness and moisturized feel on dry
hair. In view of
providing the above gel matrix, the cationic surfactant and the high melting
point fatty compound
are contained at a level such that the weight ratio of the cationic surfactant
to the high melting
point fatty compound is in the range of, from about 1:1 to about 1:10, or even
from about 1:1 to
about 1:6.
The detergents or cleaning agents according to the invention have the
advantage that they have, at
most, a very low formaldehyde content, because they are manufactured, at most,
with very little
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formaldehyde introduced or, in particular, with no formaldehyde introduced at
all. The detergents
or cleaning agents according to the invention enable the targeted release of
active substances, in
particular aromatic substances that are stored in the capsules. The capsules
are stable within the
detergent or cleaning agent matrix and can be opened by targeted stimulation,
in particular
mechanical force. During use of the detergent or cleaning agent, for example
when washing
laundry, the microcapsules are deposited on the item to be cleaned, and after
the item is dried, they
can be easily opened, for example through friction. In this manner a targeted
release of active
substance is achieved, increasing the performance profile of the product as a
whole. In so doing, the
fragrance effect acquires a particular importance, because in many cases the
consumer judges
product performance in proportion to the pleasant scent. However, the release
of the active
substances, in particular fragrances, can be accomplished in a diffuse manner,
in which the active
substances, in particular fragrances, migrate through the polymer shell
material and then are slowly
released. The present detergent or cleaning agent enables in particular a long-
lasting release of
active substance, in particular a durable scenting of the items to be cleaned,
as well as a targeted
release of active substance, in particular release of scent, even after long
periods of time, through
the use of microencapsulated active substances, in particular fragrances.
The microcapsules that can be used according to the invention are contained in
the detergent or
cleaning agent in amounts of preferably 0.0001 to 50 wt%, advantageously 0.001
to 40 wt%,
more advantageously 0.005 to 30 wt%, even more advantageously 0.01 to 20 wt%,
in a further
advantageous manner 0.05 to 10 wt%, and in particular 0.1 to 5 wt%, based on
the product as a
whole.
The microcapsules contain, in particular, liquids, preferably comprising
i. aromatic substances (perfume oils)
ii. liquid detergent and cleaning agent ingredients, such as, preferably,
surfactants, in
particular nonionic surfactants, silicone oils, paraffins
iii liquid non-pharmaceutical additives or active substances, for
example oils such as, for
example, almond oil or cooling substances, and
mixtures of the above.
However, it is most preferable if aromatic substances (perfume oils) are
contained in the
microcapsules. In the context of this invention, the terms "aromatic
substances" and "fragrances"
are used synonymously.
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In the following, first the microcapsules that can be used are described in
detail.
In the context of the present invention, aryl oxy alkanols, aryl alkanols and
oligoalkanol aryl ethers
5 are preferred as aromatic alcohols (ii)(a). Also preferred are aromatic
compounds in which at least
one free hydroxy group; particularly preferred at least two free hydroxy
groups are directly
aromatically bound; it is particularly preferred if at least two free hydroxy
groups are directly
bound to an aromatic ring, and most particularly preferred are arranged in
meta position to one
another. It is preferred that the aromatic alcohols are chosen from phenols,
cresols, (o-, m- and p-
10 cresol), naphthols (a- and 13-naphthol) and thymol, as well as from
ethyl phenols, propyl phenols,
fluorophenols and methoxyphenols.
Aromatic alcohols preferred according to the invention are also those that are
used to
manufacture polycarbonate plastics (e.g. for compact discs, plastic bowls,
baby bottles) and
15 epoxy resin finishes (e.g. for coatings of cans and foil packages), in
particular 2,2-bis-(4-
hydroxyphenyl) propane (Bisphenol A).
It is particularly preferred if the aromatic alcohol is chosen from phenols
with two or more
hydroxy groups, preferably from catechol, resorcin, hydroquinone, and 1,4-
20 naphthohydroquinone, phloroglucin, pyrogallol, or hydroxy-hydroquinone;
resorcin and/or
phloroglucin being particularly preferred as aromatic alcohols.
In summary, compositions according to the invention are preferred in which the
at least one
aromatic alcohol (ii)(a) is chosen from phenols, cresols (o-, m- and p-
cresol), naphthols (a- and
25 13-naphthol), thymol, catechol, resorcin, hydroquinone and 1,4-
naphthohydroquinone,
phloroglucin, pyrogallol and hydroxy-hydroquinone.
In another embodiment of the present invention, the detergents or cleaning
agents contain
microcapsules, in the manufacture of which aromatic alcohol is used in the
form of ether, the
ether being a derivative of each free form of the aromatic alcohol to be
converted according to
the invention. The free alcohol can also be present at the same time; there is
then, accordingly, a
mixture. For this case, the molar ratio between the free form of the aromatic
alcohol to be
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converted according to the invention and the named additional components
(ether form of an
aromatic alcohol) can be between 0:100, preferably 1: 1 or 1:2 or 1:4.
The advantage of the mixture of aromatic alcohol with an ether form is that it
can be used to
influence the reactivity of the system. In particular, with a suitable choice
of the ratio, a system
can be created, the reactivity of which stands in a balanced ratio to the
storage stability of the
system. Esters are preferred as derivatives of the aromatic alcohols.
According to the present invention, preferred as aldehydes (ii)(b) with at
least two C atoms are both
aliphatic and aromatic aldehydes. Particularly preferred aldehydes are one or
more aldehydeschosen
from the following group: azobenzene-4,4'-dicarboxaldehyde, valeraldehyde,
capronaldehyde,
caprylaldehyde, decanal, succindialdehyde, cyclohexanecarbaldehyde,
cyclopentanecarbaldehyde, 2-
methyl- 1-propanal, 2-methyl-propionaldehyde, acetaldehyde, acrolein,
aldosterone, antimycin A, 8'-
apo-13-carotene-8'-al, benzaldehyde, butanal, chloral, citral, citronellal,
crotonaldehyde,
dimethylaminobenzaldehyde, folinic acid, fosmidomycin, furfural,
glutaraldehyde, glycerin aldehyde,
glycol aldehyde, glyoxal, glyoxylic acid, heptanal, 2-hydroxy-benzaldehyde, 3-
hydroxy-butanal,
hydroxy-methyl-furfural, 4-hydroxy-nonenal, isobutanal, isobutyraldehyde,
methacrolein, 2-methyl-
undecanal, mucochloric acid, N-methyl formamide, 2-nitrobenzaldehyde, nonanal,
octanal,
oleocanthal, orlistate, pentanal, phenyl ethanol, phycocyanine, piperonal,
propanal, propenal,
protcatechualdehyde, retinal, salicylic aldehyde, secologanin, streptomycin,
strophanthidin, tylosin,
vanillin, and cinnamic aldehyde.
For the purposes of the present invention, the aldehydic components can have
one or two, particularly
preferably two, three or four, in particular two free aldehyde groups per
molecule, preference being
given to at least glyoxal, glutardialdehyde and/or succindialdehyde being
present as the aldehydic
component; particular preference being given to glutardialdehyde.
In the microcapsules that can be used according to the invention, the molar
ratio of (a) the at least
one aromatic alcohol (or ether or derivative thereof) to (b) the at least one
aldehydic component
is generally between 1: 1 and 1: 5, particularly preferably between 1 to 2 and
1 to 3 and most
particularly preferably for resorcin at approximately 1 to 2.6. The weight
ratio of components (a)
+ (b) to (c), i.e. the ratio of the sum weight of (a) + (b) to the weight of
component (c) is
generally between 1: 1 and 1: 0.01, particularly preferably between 1: 0.2 and
1: 0.05.
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In summary, preferred compositions according to the invention are those in
which the aldehydic
component (ii)(b) is chosen from valeraldehyde, capronaldehyde,
caprylaldehyde, decanal,
succindialdehyde, cyclohexanecarbaldehyde, cyclopentanecarbaldehyde, 2-methyl-
l-propanal, 2-
methylproprionaldehyde, acetaldehyde, acrolein, aldosterone, antimycin A, 8'-
apo-13-carotene-8'-al,
benzaldehyde, butanal, chloral, citral, citronellal, crotonaldehyde,
dimethylaminobenzaldehyde,
folinic acid, fosmidomycin, furfural, glutaraldehyde, glycerinaldehyde, glycol
aldehyde, glyoxal,
glyoxylic acid, heptanal, 2- hydroxybenzaldehyde, 3-hydroxybutanal,
hydroxymethylfurfural, 4-
hydroxynonenal, isobutanal, isobutyraldehyde, methacrolein, 2-methylundecanal,
mucochloric
acid, N-methylformamide, 2-nitrobenzaldehyde, nonanal, octanal, oleocanthal,
orlistate,
pentanal, phenylethanal, phycocyanin, piperonal, propanal, propenal,
protocatechualdehyde,
retinal, salicylaldehyde, secologanin, streptomycin, strophanthidin, tylosin,
vanillin, and
cinnamic aldehyde.
The optionally used (meth)acrylate polymers can be homo- or copolymers of
methacrylate
monomers and/or acrylate monomers. In this invention, the term
"(meth)acrylate" refers to both
methacrylates and acrylates. (Meth)acrylate polymers are, for example, homo-
or copolymers,
preferably copolymers, of one or more polar functionalized (meth)acrylate
monomers, such as
(meth)acrylate monomers containing sulfonic acid groups, carboxylic acid
groups, phosphoric
acid groups, nitrile groups, phosphonic acid groups, ammonium groups, amine
groups or nitrate
groups. The polar groups can also be present in salt form. (Meth)acrylate
polymers are suitable as
protective colloids and can be used advantageously in the manufacture of
microcapsules.
(Meth)acrylate copolymers can consist, for example, of two or more
(meth)acrylate monomers
(e.g. acrylate + 2-acrylamido-2-methyl propanesulfonic acid) or of one or more
(meth)acrylate
monomers and one or more monomers that are different from meth(acrylate)
monomers (e.g.
methacrylate + styrene).
Examples of (meth)acrylate polymers include homopolymers of (meth)acrylates
containing
sulfonic acid groups (e.g. 2-acrylamido-2-methyl propanesulfonic acid or its
salts (AMPS),
which is commercially available as Lupasol PA 140, BASF) or their copolymers,
copolymers of
acrylamide and (meth)acrylic acid, copolymers of alkyl (meth)acrylates and N-
vinylpyrrolidone
(commercially available as Luviskol K15, K30 or K90, BASF), copolymers of
(meth)acrylates
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with polycarboxylates or polystyrene sulfonates, copolymers of (meth)acrylates
with vinyl ethers
and/or maleic acid anhydride, copolymers of (meth)acrylates with ethylene
and/or maleic acid
anhydride, copolymers of (meth)acrylates with isobutylene and/or maleic acid
anhydride, or
copolymers of (meth)acrylates with styrene maleic acid anhydride.
Preferred (meth)acrylate polymers are homo- or copolymers, preferably
copolymers, of 2-
acrylamido-2-methyl propanesulfonic acid or its salts (AMPS). Preferred are
copolymers of 2-
acrylamido-2-methyl propanesulfonic acid or its salts, for example copolymers
with one or more
comonomers from the group of the (meth)acrylates; vinyl compounds, such as
vinyl esters or
styrenes; unsaturated di- or polycarboxylic acids, such as maleic acid ester;
or the salts of amyl
compounds or allyl compounds. Listed below are preferred comonomers for AMPS;
however,
these comonomers can also be copolymerized with other polar functionalized
(meth)acrylate
monomers:
(1) Vinyl compounds, for example vinyl esters such as vinyl acetate, vinyl
laurate, vinyl
propionate or vinyl esters of neononanoic acid, or aromatic vinyl compounds
such as styrene
comonomers, for example styrene, alpha-methyl styrene or polar functionalized
styrenes such as
styrenes containing hydroxy groups, amino, nitrile or carboxylic acid groups,
phosphonic acid or
phosphoric acid groups, nitro or sulfonic acid groups and their salts; the
styrenes preferably being
polar functionalized in para position.
(2) Unsaturated di- or polycarboxylic acids, for example maleic acid esters
such as dibutyl
maleinate or diocytyl maleinate, as salts of allyl compounds, for example
sodium allyl sulfonate,
and as salts of amyl derivatives, for example sodium amyl sulfonate.
(3) (Meth)acrylate comonomers; these are esters of acrylic acid and
methacrylic acid, wherein the
ester groups are, for example, saturated or unsaturated, straight-chained,
branched or cyclic
hydrocarbon groups which can contain one or more heteroatoms such as N, 0, S,
P, F, Cl, Br, or I.
Examples of such hydrocarbon groups are straight-chained, branched or cyclic
alkyl; straight-
chained, branched or cyclic alkenyl; aryls such as phenyl; or heterocylyls
such as tetrahydrofurfuryl.
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Possible (meth)acrylate comonomers, preferably for AMPS, include:
(a) acrylic acid, CrCn-alkyl acrylic acid, such as methacrylic acid;
(b) (meth)acrylamides such as acrylamide, methacrylamide, diacetone
acrylamide, diacetone
methacrylamide, N-butoxymethyl acrylamide, N-iso-butoxymethyl acrylamide, N-
butoxymethyl
methacrylamide, N-iso-butoxymethyl methacrylamide, N-methylol acrylamide and N-
methylol
methacrylamide;
(c) heterocyclyl (meth)acrylates such as tetrahydrofurfuryl acrylate and
tetrahydrofurfuryl
methacrylate or carbocyclic (meth)acrylates such as isobornyl acrylate and
isobornyl
methacrylate.
(d) urethane (meth)acrylates such as diurethane diacrylate and diurathane
methacrylate (CAS:
72869-86-4);
(e) CrCn-alkyl acrylates such as methyl, ethyl, n-propyl, isopropyl, n-butyl,
sec-butyl, isobutyl,
tert-butyl, n-pentyl, isopentyl, hexyl (e.g. n-hexyl, isohexyl or cyclohexyl),
heptyl, octyl (e.g. 2-
ethyl hexyl), nonyl, decyl (e.g. 2-propylheptyl or isodecyl), undecyl,
dodecyl, tridecyl (e.g.
isotridecyl) and tetradecyl acrylate; the alkyl groups can optionally be
substituted with one or
more halogen atoms (e.g. fluorine, chlorine, bromine or iodine), for example
trifluoroethyl
acrylate, or with one or more amino groups, for example diethylaminoethyl
acrylate, or with one
or more alkoxy groups such as methoxy propyl acrylate, or with one or more
aryloxy groups such
as phenoxy ethyl acrylate.
(0 C2-C14 alkenyl acrylates such as ethenyl, n-propenyl, isopropenyl, n-
butenyl, sec-butenyl,
isobutenyl, tert-butenyl, n-pentenyl, isopentenyl, hexenyl (e.g. n-hexenyl,
isohexenyl or
cyclohexenyl), heptenyl, octenyl (e.g. 2-ethyl hexenyl), nonenyl, decenyl
(e.g. 2-propenyl heptyl
or isodecenyl), undecenyl, dodecenyl, tridecenyl (e.g. isotridecenyl) and
tetradecenyl acrylate,
and their epoxides such as glycidyl acrylate, or aziridines such as aziridine
acrylate.
(g) Ci-C14hydroxyalkyl acrylates such as hydroxymethyl, hydroxyethyl, hydroxy-
n-propyl, hydroxy
isopropyl, hydroxy-n-butyl, hydroxy-sec-butyl, hydroxy isobutyl, hydroxy-tert-
butyl, hydroxy-n-
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pentyl, hydroxy isopentyl, hydroxy hexyl (e.g. hydroxy-n-hexyl, hydroxy
isohexyl or hydroxy
cyclohexyl), hydroxy heptyl, hydroxy octyl (e.g. 2-ethyl hexyl), hydroxy
nonyl, hydroxy decyl (e.g.
hydroxy-2-propyl heptyl or hydroxy isodecyl), hydroxy undecyl, hydroxy
dodecyl, hydroxy tridecyl
(e.g. hydroxy isotridecyl) and hydroxy tetradecyl acrylate; the hydroxy groups
preferably being
5 located in the terminal position (w-position) (e.g. 4-hydroxy-n-butyl
acrylate) or in the (03-1) position
(e.g. 2-hydroxy-n-propylacrylate) of the alkyl group;
(h) alkylene glycol acrylates containing one or more alkylene glycol units.
Examples include (i)
monoalkylene glycol acrylates, such as acrylates of ethylene glycol, propylene
glycol (e.g. 1,2- or
10 1,3-propanediol), butylene glycol (e.g. 1,2- or 1,3- or 1,4-butanediol),
pentylene glycol (e.g. 1,5-
pentanediol) or hexylene glycol (e.g. 1,6-hexanediol), in which the second
hydroxy group is
etherified or esterified, for example by sulfuric acid, phosphoric acid,
acrylic acid or methacrylic
acid; or (ii) polyalkylene glycol acrylates such as polyethylene glycol
acrylates, polypropylene glycol
acrylates, polybutylene glycol acrylates, polypentylene glycol acrylates or
polyhexylene glycol
15 acrylates, the second hydroxy group of which can optionally be
etherified or esterified, for example
by sulfuric acid, phosphoric acid, acrylic acid or methacrylic acid;
Examples of (poly)alkylene glycol units containing etherified hydroxy groups
are CrCn-alkyloxy
(poly)alkylene glycols (e.g. CrCn-alkyloxy polyalkylene glycol acrylates);
examples of
20 (poly)alkylene glycol units containing esterified hydroxy groups are
sulfonium (poly)alkylene
glycols (e.g. sulfonium (poly)alkylene glycol acrylates) and their salts,
(poly)alkylene glycol
diacrylates such as 1,4-butanediol diacrylate or 1,6-hexanediol diacrylate or
(poly)alkylene
glycol methacrylate acrylates such as 1,4-butanediol methacrylate acrylate or
1,6-hexanediol
methacrylate acrylate;
Polyalkylene glycol acrylates can carry an acrylate group (e.g. polyethylene
glycol monoacrylate,
polypropylene glycol monoacrylate, polybutylene glycol monoacrylate,
polypentylene glycol
monoacrylate or polyhexylene glycol monoacrylate) or they can carry two or
more, preferably two,
acrylate groups such as polyethylene glycol diacrylate, polypropylene glycol
diacrylate, polybutylene
glycol diacrylate, polypentylene glycol diacrylate or polyhexylene glycol
diacrylate;
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Polyalkylene glycol acrylates can also contain two or more different
polyalkylene glycol blocks,
for example blocks of polymethylene glycol and polyethylene glycol or blocks
of polyethylene
glycol and polypropylene glycol.
The degree of polymerization of the polyalkylene glycol units or polyalkylene
glycol blocks
generally ranges from 1 to 20, preferably from 3 to 10, and particularly
preferably from 3 to 6.
(i) Ci-C14-alkyl methacrylates such as methyl, ethyl, n-propyl, isopropyl, n-
butyl, sec-butyl,
isobutyl, tert-butyl, n-pentyl, isopentyl, hexyl (e.g. n-hexyl, isohexyl or
cyclohexyl), heptyl, octyl
(e.g. 2-ethyl hexyl), nonyl, decyl (e.g. 2-propylheptyl or isodecyl), undecyl,
dodecyl, tridecyl
(e.g. isotridecyl) and tetradecyl methacrylate; the alkyl groups can
optionally be substituted with
one or more halogen atoms (e.g. fluorine, chlorine, bromine or iodine), for
example trifluoroethyl
methacrylate, or with one or more amino groups, for example diethylaminoethyl
methacrylate, or
with one or more alkoxy groups such as methoxy propyl methacrylate, or with
one or more
aryloxy groups such as phenoxyethyl methacrylate.
(j) C2-C14 alkenyl methacrylates such as ethenyl, n-propenyl, isopropenyl, n-
butenyl, sec-butenyl,
isobutenyl, tert-butenyl, n-pentenyl, isopentenyl, hexenyl (e.g. n-hexenyl,
isohexenyl or
cyclohexenyl), heptenyl, octenyl (e.g. 2-ethyl hexenyl), nonenyl, decenyl
(e.g. 2-propenyl heptyl
or isodecenyl), undecenyl, dodecenyl, tridecenyl (e.g. isotridecenyl) and
tetradecenyl
methacrylate, and their epoxides such as glycidyl methacrylate, or aziridines
such as aziridine
methacrylate.
(k) Ci-C14 hydroxyalkyl methacrylates such as hydroxymethyl, hydroxyethyl,
hydroxy-n-
propyl, hydroxy isopropyl, hydroxy-n-butyl, hydroxy sec-butyl, hydroxy
isobutyl, hydroxy tert-
butyl, hydroxy-n-pentyl, hydroxy isopentyl, hydroxy hexyl (e.g. hydroxy-n-
hexyl, hydroxy
isohexyl or hydroxy cyclohexyl), hydroxy heptyl, hydroxy octyl (e.g. 2-ethyl
hexyl), hydroxy
nonyl, hydroxy decyl (e.g. hydroxy-2-propyl heptyl or hydroxy isodecyl),
hydroxy undecyl,
hydroxy dodecyl, hydroxy tridecyl (e.g. hydroxy isotridecyl) and
hydroxytetradecyl
methacrylate; the hydroxy groups preferably being located in the terminal
position (w-position)
(e.g. 4-hydroxy-n-butyl methacrylate) or in the (03-1) position (e.g. 2-
hydroxy-n-propyl
methacrylate) of the alkyl group;
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(1) alkylene glycol methacrylates containing one or more alkylene glycol
units. Examples include
(i) monoalkylene glycol methacrylates, such as methacrylates of ethylene
glycol, propylene
glycol (e.g. 1,2- or 1,3-propanediol), butylene glycol (e.g. 1,2- or 1,3- or
1,4-butanediol),
pentylene glycol (e.g. 1,5-pentanediol) or hexylene glycol (e.g. 1,6-
hexanediol), in which the
second hydroxy group is etherified or esterified, for example by sulfuric
acid, phosphoric acid,
acrylic acid or methacrylic acid; or (ii) polyalkylene glycol methacrylates
such as polyethylene
glycol methacrylates, polypropylene glycol methacrylates, polybutylene glycol
methacrylates,
polypentylene glycol methacrylates or polyhexylene glycol methacrylates, the
second hydroxy
group of which can optionally be etherified or esterified, for example by
sulfuric acid, phosphoric
acid, acrylic acid or methacrylic acid;
Examples of (poly)alkylene glycol units containing etherified hydroxy groups
are Ci-C14-
alkyloxy (poly)alkylene glycols (e.g. Ci-C14-alkyloxy polyalkylene glycol
methacrylates).
Examples of (poly)alkylene glycol units containing esterified hydroxy groups
are sulfonium
(poly)alkylene glycols (e.g. sulfonium (poly)alkylene glycol methacrylates)
and their salts, or
(poly)alkylene glycol dimethacrylates such as 1,4-butanediol dimethacrylate;
The polyalkylene glycol methacrylates can carry a methacrylate group (e.g.
polyethylene glycol
monomethacrylate, polypropylene glycol monomethacrylate, polybutylene glycol
monomethacrylate, polypentylene glycol monomethacrylate or polyhexylene glycol
monomethacrylate) or they can carry two or more, preferably two, methacrylate
groups, such as
polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate,
polybutylene glycol
dimethacrylate, polypentalene glycol dimethacrylate or polyhexylene glycol
dimethacrylate;
The polyalkylene glycol methacrylates can also contain two or more different
polyalkylene
glycol blocks, for example blocks of polymethylene glycol and polyethylene
glycol or blocks of
polyethylene glycol and polypropylene glycol (e.g. Bisomer PEM63PHD (Cognis)
CAS 5891 6-
75-9);
The degree of polymerization of the polyalkylene glycol units or polyalkylene
glycol blocks
generally ranges from 1 to 20, preferably from 3 to 10, and particularly
preferably from 3 to 6.
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Examples of preferred (meth)acrylate comonomers include 4-hydroxy butyl
acrylate, 2-hydroxy
propyl methacrylate, ammonium sulfatoethyl methacrylate, pentapropylene glycol
methacrylate,
acrylic acid, hexaethylene glycol methacrylate, hexapropylene glycol acrylate,
hexaethylene
glycol acrylate, hydroxy ethyl methacrylate, polyalkylene glycol methacrylate
(CAS No. 589-75-
9), Bisomer PEM63PHD, methoxy polyethylene glycol methacrylate, 2-propylheptyl
acrylate (2-
PHA), 1,3-butanediol dimethacrylate (BDDMA), triethylene glycol dimethacrylate
(TEGDMA),
hydroxy ethyl acrylate (HEA), 2-hydroxy propyl acrylate (HPA), ethylene glycol
dimethacrylate
(EGDMA), glycidyl methacrylate (GMA) and/or allyl methacrylate (ALMA).
The AMPS copolymers generally have a proportion of AMPS units greater than 50
mol%,
preferably in the range of 60 to 95 mol%, particularly preferably 80 to 90
mol%; the proportion
of comonomers is generally less than 50 mol%, preferably in the range of 5 to
40 mol%, and
particularly preferably from 1 to 20 mol%.
The copolymers can be obtained by methods known per se, for example in a batch
or semi-batch
method. For example, first, the appropriate amounts of water and monomers are
fed into a
temperature-controllable reactor and placed in an inert gas atmosphere. The
contents are then
stirred, brought to reaction temperature (preferably ranging from
approximately 70 to 80 C) and
initiator is added, preferably in the form of an aqueous solution. Suitable
initiators are known
initiators for radical polymerization, for example sodium, potassium or
ammonium peroxodisulfate,
or H202 based mixtures, for example mixtures of H202 and citric acid. The heat
is allowed to build
up until it reaches the maximum temperature, and as soon as the temperature in
the reactor drops,
either (a) the remaining monomers are added and then a post-reaction takes
place (semi-batch
method), or (b) the post-reaction takes place immediately (batch method). The
obtained reaction
mixture is then cooled to room temperature and the copolymer is isolated from
the aqueous
solution, for example by extraction with organic solvents such as hexane or
methylene chloride and
then the solvent is distilled off. The copolymer can then be washed with
organic solvent and dried.
The obtained reaction mixture can also be processed further directly; in this
case it is advantageous
to add a preservative to the aqueous copolymer solution.
The AMPS copolymers are suitable as protective colloids in the manufacture of
the
microcapsules that can be used according to the present invention.
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In summary, preference is given to compositions according to the invention in
which the
(meth)acrylate polymer is a copolymer of 2-acrylamido-2-methyl propanesulfonic
acid or its
salts, with one or more additional (meth)acrylate monomers chosen from the
group consisting
of (meth)acrylates, vinyl compounds, unsaturated di- or polycarboxylic acids
and the salts of
amyl compounds or allyl compounds.
In compositions particularly preferred according to the invention, the molar
ratio of the at least
one aromatic alcohol (ii)(a) to the at least one aldehydic component (ii)(b),
which has at least two
C atoms per molecule, is between 1 to 2 and 1 to 3.5, preferably between 1 to
2.4 and 1 to 2.8,
and particularly preferably 1 to 2.6.
Preferred detergents or cleaning agents according to the invention contain
microcapsules having
the following components (ii)(a), (ii)(b) and (ii)(c):
Phloroglucin, glutardialdehyde, AMPS/hydroxyethyl methacrylate copolymer;
Phloroglucin, succindialdehyde, AMPS/hydroxyethyl methacrylate copolymer;
Phloroglucin, glyoxal, AMPS/hydroxyethyl methacrylate copolymer;
Phloroglucin, glutardialdehyde, AMPS/hydroxyethyl acrylate copolymer;
Phloroglucin, succindialdehyde, AMPS/hydroxyethyl acrylate copolymer;
Phloroglucin, glyoxal, AMPS/hydroxy ethylacrylate copolymer;
Phloroglucin, glutardialdehyde, AMPS/hydroxypropyl methacrylate copolymer;
Phloroglucin, succindialdehyde, AMPS/hydroxypropyl methacrylate copolymer;
Phloroglucin, glyoxal, AMPS/hydroxypropyl methacrylate copolymer;
Phloroglucin, glutardialdehyde, AMPS/hydroxypropyl acrylate copolymer;
Phloroglucin, succindialdehyde, AMPS/hydroxypropyl acrylate copolymer;
Phloroglucin, glyoxal, AMPS/hydroxypropyl acrylate copolymer;
Phloroglucin, glutardialdehyde, AMPS/hydroxybutyl methacrylate copolymer;
Phloroglucin, succindialdehyde, AMPS/hydroxybutyl methacrylate copolymer;
Phloroglucin, glyoxal, AMPS/hydroxybutyl methacrylate copolymer;
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Phloroglucin, glutardialdehyde, AMPS/hydroxybutyl acrylate copolymer;
Phloroglucin, succindialdehyde, AMPS/hydroxybutyl acrylate copolymer;
Phloroglucin, glyoxal, AMPS/hydroxybutyl acrylate copolymer;
5 Phloroglucin, glutardialdehyde, AMPS/polyethylene glycol monomethacrylate
copolymer;
Phloroglucin, succindialdehyde, AMPS/polyethylene glycol monomethacrylate
copolymer;
Phloroglucin, glyoxal, AMPS/polyethylene glycol monomethacrylate copolymer;
Phloroglucin, glutardialdehyde, AMPS/polyethylene glycol monoacrylate
copolymer;
10 Phloroglucin, succindialdehyde, AMPS/polyethylene glycol monoacrylate
copolymer;
Phloroglucin, glyoxal, AMPS/polyethylene glycol monoacrylate copolymer;
Phloroglucin, glutardialdehyde, AMPS/polypropylene glycol monomethacrylate
copolymer;
Phloroglucin, succindialdehyde, AMPS/polypropylene glycol monomethacrylate
copolymer;
15 Phloroglucin, glyoxal, AMPS/polypropylene glycol monomethacrylate
copolymer;
Phloroglucin, glutardialdehyde, AMPS/polypropylene glycol monoacrylate
copolymer;
Phloroglucin, succindialdehyde, AMPS/polypropylene glycol monoacrylate
copolymer;
Phloroglucin, glyoxal, AMPS/polypropylene glycol monoacrylate copolymer;
Phloroglucin, glutardialdehyde, AMPS/methoxy polyethylene glycol
monomethacrylate
copolymer;
Phloroglucin, succindialdehyde, AMPS/methoxy polyethylene glycol
monomethacrylate
copolymer;
Phloroglucin, glyoxal, AMPS/methoxy polyethylene glycol monomethacrylate
copolymer;
Phloroglucin, glutardialdehyde, AMPS/methoxy polyethylene glycol monoacrylate
copolymer;
Phloroglucin, succindialdehyde, AMPS/methoxy polyethylene glycol monoacrylate
copolymer;
Phloroglucin, glyoxal, AMPS/methoxy polyethylene glycol monoacrylate
copolymer;
Resorcin, glutardialdehyde, AMPS/hydroxyethyl methacrylate copolymer;
Resorcin, succindialdehyde, AMPS/hydroxyethyl methacrylate copolymer;
Resorcin, glyoxal, AMPS/hydroxyethyl methacrylate copolymer;
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Resorcin, glutardialdehyde, AMPS/hydroxyethyl acrylate copolymer;
Resorcin, succindialdehyde, AMPS/hydroxyethyl acrylate copolymer;
Resorcin, glyoxal, AMPS/hydroxyethyl acrylate copolymer;
Resorcin, glutardialdehyde, AMPS/hydroxypropyl methacrylate copolymer;
Resorcin, succindialdehyde, AMPS/hydroxypropyl methacrylate copolymer;
Resorcin, glyoxal, AMPS/hydroxypropyl methacrylate copolymer;
Resorcin, glutardialdehyde, AMPS/hydroxypropyl acrylate copolymer;
Resorcin, succindialdehyde, AMPS/hydroxypropyl acrylate copolymer;
Resorcin, glyoxal, AMPS/hydroxypropyl acrylate copolymer;
Resorcin, glutardialdehyde, AMPS/hydroxybutyl methacrylate copolymer;
Resorcin, succindialdehyde, AMPS/hydroxybutyl methacrylate copolymer;
Resorcin, glyoxal, AMPS/hydroxybutyl methacrylate copolymer;
Resorcin, glutardialdehyde, AMPS/hydroxybutyl acrylate copolymer;
Resorcin, succindialdehyde, AMPS/hydroxybutyl acrylate copolymer;
Resorcin, glyoxal, AMPS/hydroxybutyl acrylate copolymer;
Resorcin, glutardialdehyde, AMPS/polyethylene glycol monomethacrylate
copolymer;
Resorcin, succindialdehyde, AMPS/polyethylene glycol monomethacrylate
copolymer;
Resorcin, glyoxal, AMPS/polyethylene glycol monomethacrylate copolymer;
Resorcin, glutardialdehyde, AMPS/polyethylene glycol monoacrylate copolymer;
Resorcin, succindialdehyde, AMPS/polyethylene glycol monoacrylate copolymer;
Resorcin, glyoxal, AMPS/polyethylene glycol monoacrylate copolymer;
Resorcin, glutardialdehyde, AMPS/polypropylene glycol monomethacrylate
copolymer;
Resorcin, succindialdehyde, AMPS/polypropylene glycol monomethacrylate
copolymer;
Resorcin, glyoxal, AMPS/polypropylene glycol monomethacrylate copolymer;
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Resorcin, glutardialdehyde, AMPS/polypropylene glycol monoacrylate copolymer;
Resorcin, succindialdehyde, AMPS/polypropylene glycol monoacrylate copolymer;
Resorcin, glyoxal, AMPS/polypropylene glycol monoacrylate copolymer;
Resorcin, glutardialdehyde, AMPS/methoxy polyethylene glycol monomethacrylate
copolymer;
Resorcin, succindialdehyde, AMPS/methoxy polyethylene glycol monomethacrylate
copolymer;
Resorcin, glyoxal, AMPS/methoxy polyethylene glycol monomethacrylate
copolymer;
Resorcin, glutardialdehyde, AMPS/methoxy polyethylene glycol monoacrylate
copolymer;
Resorcin, succindialdehyde, AMPS/methoxy polyethylene glycol monoacrylate
copolymer;
Resorcin, glyoxal, AMPS/methoxy polyethylene glycol monoacrylate copolymer;
In another embodiment of the invention, one or more nitrogen-containing or
silica-containing
agents can be used in addition to manufacture the microcapsules that can be
used according to the
invention. The nitrogen-containing agents can be polymerized into the resin
(e.g. in order to round
off the property profile of the resin) or for after-treatment.
For this purpose, preference is given to the use of heterocyclic compounds
having at least one
nitrogen atom as the heteroatom, which is adjacent either to an amino-
substituted carbon atom or to
a carbonyl group like, for example, pyridazine, pyrimidine, pyrazine,
pyrrolidone, aminopyridine,
and compounds derived therefrom. Advantageous compounds of this type are
aminopyridine and
compounds derived therefrom. Suitable in principle are all aminopyridines, for
example melamine,
2,6-diaminopyridine, substituted and dimeric aminopyridines and mixtures made
from these
compounds. Also advantageous are polyamides and dicyandiamide, urea and its
derivatives, as well
as pyrrolidone and compounds derived therefrom, for example hydantoin, the
derivatives of which
are particularly advantageous. Particularly advantageous of these compounds
are allantoin and its
derivatives. Also particularly advantageous are triamino-1,3,5-triazine
(melamine) and its
derivatives.
It should be emphasized in particular that the after-treatment is "purely" an
after-treatment of the
surface undertaken to arrive at this preferred embodiment of the microcapsules
that can be used
according to the invention. In other words: in this preferred embodiment, the
stated nitrogen-
containing agent is not uniformly involved in the composition of the entire
capsule wall, but instead is
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concentrated primarily on the outside surface of the capsule walls. The after-
treatment can also be
effected with silica gel (in particular amorphous hydrophobic silica gel) or
aromatic alcohols (a),
which are preferably used in the form of slurries.
The microcapsules that can be used according to the invention are introduced
into the detergent
or cleaning agent according to the invention in particular in the form of
microcapsule dispersions
that contain one or more of the microcapsules that can be used according to
the invention.
The microcapsules contained in the detergents or cleaning agents according to
the invention are
preferably manufactured by combining and reacting together, optionally in the
presence of at least
one (meth)acrylate polymer and if necessary in the presence of at least one
substance to be
encapsulated (the core material), the at least one aromatic alcohol to be
reacted according to the
invention and the at least one aldehydic component having at least two C atoms
per molecule to be
reacted according to the invention, and by subsequently hardening the capsules
by increasing the
temperature. In so doing, it is particularly preferred that the pH is
increased over the course of the
process.
During such a process, preferably first
(a) the at least one aromatic alcohol and/or its derivative or ether and
the at least one
aldehydic component and, optionally, at least one (meth)acrylate polymer and
at least
one substance to be encapsulated are combined at a temperature of 40 to 65 C
and a
pH between 6 and 9, preferably 7 and 8.5, and
(b) in a later method step the pH is raised at a temperature of 40 to 65 C
to more than 9,
preferably between 9.5 and 11,
(c) the capsules later being hardened by increasing the temperature to 60
C up to 110 C,
preferably 70 C up to 90 C, in particular 80 C.
However, if phloroglucin is used as the alcohol component, it is more
advantageous to harden the
capsules in the acidic range; preferably the pH is then no higher than 4,
particularly preferably
between 3 and 4, for example between 3.2 and 3.5.
The yield and quality of the microcapsules or microcapsule dispersions that
can be used according to
the invention are influenced by the chosen parameters of temperature, pH
and/or stirring speed. In
particular, a too-low temperature can lead to a less-thick capsule wall. This
is apparent to the person
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skilled in the art in a reduced yield as well as precipitation of core
material as condensate in the filter
of the dryer. On the other hand, it should be made sure that the reaction
speed is not too high, because
otherwise there will be only a little wall material around the capsules or
there will be too much free
wall material outside the capsules. This free wall material may then be
present in particles that are
larger than the capsules.
Alkalinity can also be important for the quality of the microcapsules that can
be used according
to the invention. In addition, within the scope of process control, the pH
influences the
tendency of the preparation to gel. If particles are formed (step (b), above)
at a pH of 9 or
lower, the preparation could gel. In one embodiment of the described method,
an alkali salt,
preferably alkali carbonate, in particular sodium carbonate, is used to adjust
the alkalinity.
Sodium carbonate is preferred because it reduces the risk of gelling.
In terms of the method presented here, at the beginning of the reaction
(method step (a)) of the
aromatic alcohol with the aldehydic component stirring can take place; the
stirring speed can be from
500 to 2,500 rpm, in particular from 1,000 to 2,000 rpm. With regard to the
pre-condensate obtained,
optionally the (meth)acrylate polymer and the substance to be encapsulated can
then be added.
Preferably, later and immediately before or during the raising of the
alkalinity (method step (b)), the
stirring speed is increased; it can then be from 3,000 to 5,000 rpm, in
particular from 3,500 to 4,500
rpm, and particularly 4,000 rpm. Preferably, the stirring speed increased in
this manner is maintained
until the viscosity values of the mixture drop, and when the reduction in
viscosity starts, the stirring
speed is lowered preferably to 500 to 2,500 rpm, particularly preferably to
1,000 to 2,000 rpm.
Reducing the stirring speed earlier can likewise lead to unwanted gelling of
the preparation.
Preferably, at least 20 minutes after the start of the described reduction in
viscosity, particularly
preferably between 30 and 180 minutes, the mixture is stirred again at a
stirring speed from 1,000 to
2,000 rpm and at a temperature from 40 to 65 C before the hardening of the
capsules is effected in
method step (c) by increasing the temperature. In the present invention, this
phase after the start of the
described reduction in viscosity and before the capsules are hardened is also
called the "dwell phase."
The dwell phase can preferably serve to achieve the pre-formation of
sufficiently stable capsule walls
or, in other words, render the capsule walls sufficiently stable that core
material can no longer escape.
It is also possible to manufacture solid spheres, i.e. capsules that do not
surround any core
material. These solid spheres can even have a diameter of less than 500 nm
(preferably between
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300 and 400 nm). These can preferably be monodisperse solid spheres. In one
embodiment,
phloroglucin can be used to manufacture these solid spheres.
The microcapsules generally have diameters ranging from 1 to 1,000 lam. For
the purposes of the
5 present invention, the term "microcapsule" also comprises nanocapsules,
i.e. capsules with a
diameter < 1 lam. However, the capsules preferably have diameters ranging from
1 to 100 lam,
preferably from 2 to 50 lam. The wall thickness can be, for example, 0.05 to
10 lam.
The choice of protective colloids, as well as bases and acids, for successful
encapsulation covers a
10 large range; in the case of the bases, preference is given to those that
generate catalytic effects
during the reaction of the aromatic alcohols with the aldehydes. This enables
both the formation of
resoles and the formation of novolak-analogous capsule walls.
The capsules can generally be loaded with gaseous, liquid and solid
substances. Preference is
15 given to the use of hydrophobic materials. Particularly preferred,
however, are liquid
substances, in particular aromatic substances, liquid detergent and cleaning
agent ingredients,
such as preferably surfactants, in particular nonionic surfactants, silicone
oils, paraffins, liquid
non-pharmaceutical additives or active substances, for example oils such as,
for example,
almond oil, and mixtures of the above. However, it is most preferred that
aromatic substances
20 (perfume oils) are contained in the microcapsules.
All substances and mixtures known for that purpose can be used as fragrances
or aromatic
substances or perfume oils. For the purposes of this invention, the terms
"aromatic substance(s),"
"fragrances" and "perfume oil(s)" are used synonymously. This means in
particular all substances
25 or mixtures thereof that humans and animals perceive as smells, in
particular those that humans
perceive as pleasant smells. The fragrance components used can be perfumes,
perfume oils or
perfume oil components. According to the invention, perfume oils and
fragrances can be individual
aromatic substance compounds, for example the synthetic products of the ester
type, ethers,
aldehydes, ketones, alcohols and hydrocarbons. Aromatic substance compounds of
the ester type
30 include benzyl acetate, phenoxy ethyl isobutyrate, p-tert.-butyl
cyclohexyl acetate, linalyl acetate,
dimethyl benzyl carbinyl acetate (DMBCA), phenyl ethyl acetate, benzyl
acetate, ethyl methyl
phenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate, benzyl
salicylate, cyclohexyl
salicylate, floramate, melusate and jasmecyclate. The ethers include, for
example, benzyl ethyl
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ether and ambroxan; the aldehydes include, for example, linear alkanals
containing 8 to 18 C
atoms, citral, citronellal, citronellyloxy acetaldehyde, cyclamen aldehyde,
lilial and bourgeonal.
The ketones include, for example, the jonones, alpha-isomethyl ionone and
methyl cedryl ketone;
the alcohols include anethol, citronellol, eugenol, geraniol, linalool, phenyl
ethyl alcohol and
terpineol; the hydrocarbons include mainly terpenes such as pinene. However,
preference is given
to the use of mixtures of various aromatic substances that together produce a
pleasing fragrance.
Such perfume oils can also contain mixtures of natural aromatic substances,
like those accessible
from plant-based sources, for example pine, citrus, jasmine, patchouli, rose
or ylang-ylang oil. Also
suitable are muscatel sage oil, chamomile oil, clove oil, melissa oil, mint
oil, cinnamon leaf oil,
linden-blossom oil, juniper-berry oil, vetiver oil, olibanum oil, galbanum oil
and labdanum oil, as
well as orange blossom oil, neroli oil, orange peel oil and sandalwood oil.
Aromatic substances that can be used according to the invention include
essential oils such as
angelica root oil, anise oil, arnica blossom oil, basil oil, bay oil, bergamot
oil, champaca blossom
oil, silver fir oil, silver fir cone oil, elemi oil, eucalyptus oil, fennel
oil, pine needle oil, galbanum
oil, geranium oil, ginger grass oil, guaiac wood oil, gurjun balm oil,
helichrysum oil, ho oil, ginger
oil, iris oil, cajeput oil, calamus oil, chamomile oil, camphor oil, canago
oil, cardamom oil, cassia
oil, pine needle oil, copaiba balsam oil, coriander oil, spearmint oil,
caraway oil, cumin oil,
lavender oil, lemongrass oil, lime oil, mandarin orange oil, melissa oil, musk
grain oil, myrrh oil,
clove oil, neroli oil, naiouli oil, olibanum oil, orange oil, origanum oil,
palmarosa oil, patchouli oil,
peru balsam, petitgrain oil, pepper oil, peppermint oil, allspice oil, pine
oil, rose oil, rosemary oil,
sandalwood oil, celery oil, lavender spike oil, star anise oil, turpentine
oil, thuja oil, thyme oil,
verbena oil, vetiver oil, juniper berry oil, wormwood oil, wintergreen oil,
ylang-ylang oil, hyssop
oil, cinnamon oil, cinnamon leaf oil, citronella oil and cypress oil. However,
higher boiling or solid
aromatic substances of natural or synthetic origin can also be used for the
purposes of the present
invention as adhesive aromatic substances or mixtures of aromatic substances,
i.e. fragrances.
These compounds include the following compounds or mixtures thereof:
ambrettolide, a-amyl
cinnamic aldehyde, anethole, anise aldehyde, anise alcohol, anisole,
anthranilic acid methyl ester,
acetophenone, benzyl acetone, benzaldehyde, benzoic acid ethyl ester,
benzophenone, benzyl
alcohol, benzyl acetate, benzyl benzoate, benzyl formate, benzyl valerianate,
borneol, bornyl
acetate, a-bromostyrene, n-decyl aldehyde, n-dodecyl aldehyde, eugenol,
eugenol methyl ether,
eucalyptol, farnesol, fenchone, fenchyl acetate, geranyl acetate, geranyl
formate, heliotropin, heptin
carboxylic acid methyl ester, heptaldehyde, hydroquinone dimethyl ether,
hydroxy cinnamic
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aldehyde, hydroxy cinnamic alcohol, indole, iran, isoeugenol, isoeugenol
methyl ether, isosafrol,
jasmone, camphor, carvacrol, carvone, p-cresol methyl ether, coumarin, p-
methoxy acetophenone,
methyl-n-amyl ketone, methyl anthranilic acid methyl ester, p-methyl
acetophenone, methyl
chavicol, p-methyl quinoline, methyl-13-naphthyl ketone, methyl-n-nonyl
acetaldehyde, methyl-n-
nonyl ketone, muscone, 13-naphthol ethyl ether, 13-naphthol methyl ether,
neroli, nitrobenzene, n-
nonyl aldehyde, nonyl alcohol, n-octyl aldehyde, p-oxy acetophenone,
pentadecanolide, 13-phenyl
ethyl alcohol, phenyl acetaldehyde dimethyl acetal, phenyl acetic acid,
pulegone, safrole, salicylic
acid isoamyl ester, salicylic acid methyl ester, salicylic acid hexyl ester,
salicylic acid cyclohexyl
ester, santalol, scatole, terpineol, thyme, thymol, y-undecalactone, vanillin,
veratrum aldehyde,
cinnamic aldehyde, cinnamic alcohol, cinnamic acid, cinnamic acid ethyl ester,
and cinnamic acid
benzyl ester.
Highly volatile aromatic substances include in particular lower boiling
aromatic substances of
natural or synthetic origin that can be used alone or in mixtures. Examples of
highly volatile
aromatic substances include alkyl isothiocyanates (alkyl mustard oils),
butanedione, limonene,
linalool, linalyl acetate and linalyl propionate, menthol, menthone, methyl-n-
heptenone,
phellandrene, phenyl acetaldehyde, terpinyl acetate, citral, and citronellal.
Aromatic substance
compounds that can be preferably used (in particular aromatic substances to be
encapsulated) of the
aldehyde type include hydroxy citronellal (CAS 107-75-05), helional (CAS 1205-
17-0), citral
(5392-40-5), bourgeonal (18127-01-0), triplal (CAS 27939-60-2), ligustral (CAS
68039-48-5),
vertocitral (CAS 68039-49-6), florhydral (CAS 125109-85-5), citronellal (CAS
106-23-0),
citronellyl oxyacetaldehyde (CAS 7492-67-3).
It is also preferred that the perfume to be encapsulated does not contain any
2-methyl-undecanal,
decanal, benzene acetaldehyde or 3-phenylprop-2-enal.
The microcapsules can also preferably contain one or more (preferably liquid)
skin-care and/or
skin-protecting active ingredients. Skin-care active ingredients are all
active ingredients that
provide the skin a sensory and/or cosmetic benefit. Skin-care active
ingredients are preferably
chosen from the following substances:
a) waxes such as, for example, carnauba, spermaceti, beeswax, lanolin and/or
derivatives of the
same and others;
b) hydrophobic plant extracts;
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c) hydrocarbons such as, for example, squalene and/or squalane;
d) higher fatty acids, preferably those containing at least 12 carbon atoms,
for example lauric
acid, stearic acid, behenic acid, myristic acid, palmitic acid, oleic acid,
linoleic acid, linolenic
acid, isostearic acid and/or polyunsaturated fatty acids and others;
e) higher fatty alcohols, preferably those containing at least 12 carbon
atoms, for example lauryl
alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, behenyl alcohol,
cholesterol and/or 2-
hexadecanaol and others;
f) esters, preferably those such as cetyl octanoate, lauryl lactate,
myristyl lactate, cetyl lactate,
isopropyl myristate, myristyl myristate, isopropyl palmitate, isopropyl
adipate, butyl stearate,
decyl oleate, cholesterol isostearate, glycerol monostearate, glycerol
distearate, glycerol
tristearate, alkyl lactate, alkyl citrate and/or alkyl tartrate and others;
g) lipids such as, for example, cholesterol, ceramides and/or sucrose esters
and others;
h) vitamins such as, for example, vitamins A, C and E, vitamin alkyl esters,
including vitamin C
alkyl ester and others;
i) sunscreens;
j) phospholipids;
k) derivatives of alpha hydroxy acids;
1) germicides for cosmetic use, both synthetic such as, for example,
salicylic acid and/or others,
as well as natural such as, for example, neem oil and/or others;
m) silicones;
n) natural oils, for example almond oil;
as well as mixtures of any of the above components.
The detergent or cleaning agent according to the invention contains, in
addition to the described
microcapsules, other ingredients, namely, at a minimum, surfactants and/or
builders.
Described in greater detail below are other possible ingredients of the
detergents or cleaning agents.
However, it should first be made clear that for the purposes of this
invention, the term "detergent"
comprises in particular detergents or cleaning agents as well as after-
treatment agents (such as,
preferably, fabric softeners, fragrant rinses, conditioning sheets for use in
clothes dryers, hygiene
rinses, etc.). Fabric detergent is the term for the formulations needed for
washing fabrics, for example
present in the form of powders, granules, pearls, tablets, pastes, gels,
sheets, portions or liquids,
which are preferably used in aqueous solutions, in particular in washing
machines. Fabric softeners
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are fabric after-treatment agents for the treatment of fabrics and preferably
contain active substances
that make the treated fabric feel softer, in particular cationic active
substances (preferably cationic
surfactants, for example quaternary ammonium compounds), fatty acid
derivatives and/or silicone
oils. Fragrant rinses are fabric after-treatment agents containing perfume to
treat fabrics; they give the
fabrics a particularly appealing fragrance. Conditioning sheets for use in
clothes dryers are
nonwovens or sheets containing active substances (in particular fabric
softeners). Hygiene rinses are
fabric after-treatment agents for treating fabrics that contain at least one
antimicrobial active
substance, for example quaternary ammonium compounds such as, for example,
benzalkonium
chloride, and help reduce the laundry's bacterial load. The term "cleaning
agent" comprises all
clean(s)ers for hard or soft surfaces, but preferably hard surfaces, in
particular dishwashing detergents
(including dishwashing liquids and machine dishwashing detergents), all-
purpose cleaners, toilet-
bowl cleaners, bathroom cleaners and glass cleaners. All detergents or
cleaning agents can be, for
example, in the form of powders, granules, pearls, tablets, pastes, gels,
sheets, portions or liquids.
They can be single-phase or multi-phase. They can also be present in single-
serve packages, so-called
"pouches," wherein in one variant, the microcapsules are embedded in the film
materials used for the
pouch, for example PVA.
The detergents or cleaning agents according to the invention contain, in
addition to
microcapsules, surfactants and/or builders as necessary components.
Possible surfactants include, in particular, anionic surfactants, nonionic
surfactants, cationic
surfactants, zwitterionic surfactants and/or amphoteric surfactants, However,
it is particularly
preferred if the detergent or cleaning agent according to the invention
contains anionic, nonionic
and/or cationic surfactants. Particularly advantageous is the use of a mixture
of anionic and
nonionic surfactants. The detergent or cleaning agent according to the
invention preferably contains
0.05 wt% to 50 wt%, advantageously 1 to 40 wt%, more advantageously 3 to 30
wt%, and in
particular 5 wt% to 20 wt% surfactant(s), in particular from the groups of
anionic surfactants,
nonionic surfactants, cationic, zwitterionic and/or amphoteric surfactants.
This corresponds to a
preferred embodiment of the invention and enables optimum cleaning
performance.
It is particularly preferred if the detergent or cleaning agent according to
the invention contains
anionic surfactant, advantageously in amounts from 0.1 to 25 wt%, more
advantageously 1 to 20
wt%, and in particular in amounts of 3 to 15 wt%, based on the product as a
whole. This
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corresponds to a preferred embodiment of the invention and enables
particularly advantageous
cleaning performance. One particularly suitable anionic surfactant is alkyl
benzene sulfonate,
preferably linear alkyl benzene sulfonate (LAS). If the detergent or cleaning
agent according to the
invention contains alkyl benzene sulfonate, advantageously in amounts of 0.1
to 25 wt%, more
5 advantageously 1 to 20 wt%, and in particular in amounts of 3 to 15 wt%,
based on the product as a
whole, this constitutes a preferred embodiment of the invention.
Other particularly suitable anionic surfactants are alkyl sulfates, in
particular fatty alcohol sulfates
(FAS) such as, for example, C12-C18 fatty alcohol sulfate. C8-C18 alkyl
sulfates can preferably be
10 used; particularly preferred are C13 alkyl sulfate and C13-C15 alkyl
sulfate and C13-C17 alkyl sulfate,
advantageously branched, in particular alkyl-branched C13-C17 alkyl sulfate.
Particularly suitable fatty
alcohol sulfates can be derived from lauryl and myristyl alcohol; i.e. fatty
alcohol sulfates containing
12 or 14 carbon atoms. Long-chained FAS types (C16 to C18) are very suitable
for washing laundry at
higher temperatures. Other preferred anionic surfactants that can be used
include alkane sulfonates
15 (e.g. secondary C13-C18 alkane sulfonate), methyl ester sulfonates (e.g.
C12-C18 methyl ester sulfonate)
and a-olefin sulfonates (e.g. C14-C18 olefin sulfonate) and alkyl ether
sulfates (e.g. C12-C14 fatty
alcohol-2E0 ether sulfate) and/or soaps. Other suitable anionic surfactants
will be described further
below. However, particularly suitable are FAS and/or LAS.
20 The anionic surfactants, including the soaps, can be in the form of
their sodium, potassium or
ammonium salts, as well as soluble salts of organic bases such as mono-, di-
or triethanolamine.
Preferably, the anionic surfactants are present in the form of their sodium or
potassium salts, in
particular in the form of sodium salts.
It is particularly preferred if the detergent or cleaning agent according to
the invention contains
25 nonionic surfactants, advantageously in amounts of 3 to 15 wt %, more
advantageously 1 to 20 wt
%, and in particular in amounts of 3 to 15 wt %, based on the product as a
whole. This corresponds
to one preferred embodiment of the invention. Particularly preferred is the
use of alkyl polyglycol
ethers, in particular in combination with anionic surfactant, such as,
preferably, LAS. Other
suitable nonionic surfactants are alkyl phenol polyglycol ether (APEO),
(ethoxylated) sorbitan fatty
30 acid ester (sorbitans), alkyl polyglucosides (APG), fatty acid
glucamides, fatty acid ethoxylates,
amine oxides, ethylene oxide propylene oxide block polymers, polyglycerol
fatty acid ester, and/or
fatty acid alkanol amides. Other suitable nonionic surfactants will be
described further below.
Sugar-based nonionic surfactants, such as, in particular, APG, are
particularly preferred.
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For the purposes of the invention, builders include in particular zeolites,
polycarboxylates,
citrates (such as, for example, sodium citrate, soda, sodium hydrogen
carbonate, phosphates,
sodium silicates (soluble glass), phosphonates, alkaline amorphous
disilicates, and crystalline
layered silicates. Builders are contained in the detergent or cleaning agent
according to the
invention preferably in amounts of 0.1 to 80 wt %, advantageously 1 to 60 wt
%, and more
advantageously 5 to 50 wt %. In addition, it is most particularly preferred
that the detergent or
cleaning agent according to the invention contain a builder system (i.e. at
least two substances
having a builder effect), preferably a builder system containing zeolite,
preferably comprising
zeolite in amounts > 1 wt %, advantageously > 5 wt %, more advantageously > 10
wt %, in
particular? 15 wt %, wt % based on the product as a whole. A useful maximum
amount can be
40 wt %, 30 wt % or 20 wt %, based on the product as a whole. This corresponds
to a preferred
embodiment of the invention. A combination of zeolite and soda is preferred.
It is also particularly preferred if the detergent or cleaning agent according
to the invention contains
a soluble builder system, preferably comprising soda, silicate, citrate and/or
polycarboxylates,
advantageously in amounts of 0.1 to 50 wt %, based on the product as a whole.
This corresponds to
a preferred embodiment of the invention. If such a soluble builder system is
contained in the
product, it is most preferable if the product contains only minor amounts of
insoluble builders, such
as, in particular, zeolite, for example < 5 wt % to 0.1 wt %, and in
particular, if the product in such
cases contains no insoluble builder at all.
It is also possible for the detergent or cleaning agent according to the
invention to contain
phosphates. Phosphate is preferably contained in amounts of 1 to 40 wt %, in
particular 5 to 30 wt
%, based on the product as a whole. However, according to another preferred
embodiment, the
detergent or cleaning agent according to the invention is free of phosphates.
The detergents or cleaning agents according to the invention, which, for
example, can be present
as, in particular, solids in powder form, in passivated particle form, as
homogenous solutions or
suspensions, can also in principle contain all known ingredients that are
customary in such
products. The products according to the invention can, as was already shown,
contain in
particular builder substances, surfactants, also bleaching agents, bleach
activators, water-miscible
organic solvents, enzymes, sequestering agents, electrolytes, pH regulators,
and other additives
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such as optical brighteners, fluorescing agents, anti-redeposition agents,
shrinkage blockers, anti-
creasing agents, color-transfer inhibitors, antimicrobial active substances,
germicides, fungicides,
antioxidants, preservatives, corrosion inhibitors, glass corrosion inhibitors,
disintegrating agents,
static inhibitors, bitters, ironing aids, water-repellent and impregnating
agents, swelling and anti-
slip agents, neutral filling salts, as well as UV absorbers, foam regulators,
as well as colorants
and aromatic substances.
The detergents and cleaning agents according to the invention can additionally
also contain so-
called "free," non-microencapsulated perfume oils (aromatic substances). This
corresponds to a
particularly preferred embodiment of the invention. The composition of these
perfume oils can be
the same as or different from the perfume oils to be encapsulated. Based on
the detergent or
cleaning agent as a whole, preferably 0.0001 to 15 wt %, advantageously 0.001
to 10 wt %, and
in particular 0.01 to 5 wt % aromatic substances can be contained therein.
Another subject matter of the invention is a method for manufacturing a solid
detergent or
cleaning agent, characterized
(a) by mixing a microcapsule dispersion comprising microcapsules, the capsule
walls of which
include a resin which can be obtained by reacting
a) at least one aromatic alcohol or its ether or derivatives with
b) at least one aldehydic component that has at least two C atoms per
molecule, and
c) optionally in the presence of at least one (meth)acrylate polymer
into the remaining detergent or cleaning agent matrix,
or (b) by mixing the above microcapsules in granulated or supported form into
the remaining
detergent or cleaning agent matrix,
or (c) by mixing the above microcapsules in dried form into the remaining
detergent or cleaning
agent matrix.
To manufacture products according to the invention with increased bulk weight,
in particular
ranging from 650 g/L to 950 g/L, a method having an extrusion step and
granulation are
preferred.
To manufacture products according to the invention in tablet form, which can
be single-phase or
multiphase, monochromatic or polychromatic, and which can in particular
consist of one layer or of
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several (in particular two) layers, preferably one starts by mixing all the
components ¨ if necessary
one layer at a time ¨ together in a mixer and pressing the mixture by means of
conventional tablet
presses, for example eccentric presses or rotary presses. In particular in the
case of multi-layered
tablets, it can be advantageous if at least one layer is pressed beforehand.
In this way, unbreakable
tablets are obtained without difficulty, which nevertheless dissolve
sufficiently rapidly during use.
The tablets can be of any shape, round, oval or square; intermediate forms are
also possible. It is
advantageous to round off corners and edges.
Liquid or pasty products according to the invention in the form of solutions
containing typical
solvents are generally manufactured by mixing ingredients that can be placed
as a substance or
solution in an automatic mixer. The microcapsules according to the invention
can then be
suspended, for example afterwards, in the otherwise "finished" composition.
Another subject matter of the invention is a method for manufacturing a liquid
detergent or cleaning
agent, characterized by stirring a microcapsule dispersion comprising
microcapsules, the capsule
walls of which contain a resin which can be obtained by reacting
a) at least one aromatic alcohol or its ether or derivatives with
b) at least one aldehydic component that has at least two C atoms per
molecule, and
c) optionally in the presence of at least one (meth)acrylate polymer
in the liquid detergent or cleaning agent matrix or by continuously adding the
microcapsule
dispersion into a liquid detergent or cleaning agent matrix and mixing the
ingredients by means
of static mixing elements; the microcapsule dispersion preferably having been
mixed with
surfactant beforehand.
When manufacturing the detergents or cleaning agents according to the
invention, whether
solid or liquid, it is generally advantageous to introduce the microcapsules
to be introduced in
the form of a microcapsule slurry (aqueous dispersion of microcapsules). For
that purpose, it
has proved very advantageous to mix the microcapsule slurry with surfactant to
stabilize it; the
surfactant used being cationic, anionic and/or nonionic surfactant, preferably
nonionic
surfactant; ethoxylated oxo alcohol being particularly suitable. Such
stabilized microcapsule
slurries are easier to work with. Otherwise, the workability of the
microcapsule slurry may be
complicated by a reversible flocculation.
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Anionic surfactants are advantageously used in the method in amounts of 1 to
40 wt %, for
example 2 to 30 wt % and in particular 3 to 20 wt %, to stabilize the
dispersions (wt % based on the
dispersion as a whole). Cationic surfactants can be advantageously used in
amounts of 0.001 to 4
wt %, for example 0.01 to 3 wt % and in particular 0.1 to 2 wt %, to stabilize
the dispersions (wt %
based on the dispersion as a whole). Nonionic surfactants can be
advantageously used in amounts
of 0.01 to 20 wt %, for example 0.1 to 15 wt % and in particular 1 to 10 wt %,
to stabilize the
dispersions (wt % based on the dispersion as a whole). Suitable anionic
surfactants include alkyl
benzene sulfonates, preferably secondary Cio-C13-n-alkyl benzene sulfonate,
alkane sulfonates,
methyl ester sulfonates, a-olefin sulfonates, alkyl sulfates, preferably fatty
alcohol sulfate, alkyl
ether sulfates, preferably fatty alcohol ether sulfate and sulfosuccinates.
Suitable cationic
surfactants include quaternary ammonium compounds, in particular quaternary
ammonium
compounds with one or two hydrophobic alkyl groups, quaternary phosphonium
salts or tertiary
sulfonium salts. Particularly preferred are so-called "esterquats." Esterquat
is the collective name
for cationic surface-active compounds containing, preferably, two hydrophobic
groups that are
linked by ester bonds having a quaternized di(tri)ethanol amine or an
analogous bond.
The use of nonionic surfactants to stabilize aqueous microcapsule dispersions
has proved to be
particularly advantageous. Advantageously usable compounds include in
particular fatty alcohol
ethoxylates, oxo alcohol ethoxylates, alkyl phenol polyglycol ethers, fatty
acid ethoxylates, fatty
amine ethoxylates, ethoxylated triacylglycerols and mixed ethers (polyethylene
glycol ethers
alkylated on both sides) as well as alkyl polyglucosides, sucrose esters,
sorbitan esters, fatty acid
glucamides and amine oxides.
However, the use of oxo alcohol ethoxylates is particularly advantageous in
terms of the desired
stabilization of the aqueous microcapsule dispersions. They enable the best
results for the
purposes of the invention. Preferred oxo alcohol ethoxylates are derived from
oxo alcohols
containing 9 to 15 carbon atoms, to which preferably 3 to 15 mol ethylene
oxide are attached.
One particularly preferred oxo alcohol ethoxylate for the purposes of the
invention is C13-C15 oxo
alcohol, to which 7 mol ethylene oxide are attached. A suitable commercial
product is, for
example, Lutensol AO 7 from BASF. The use of oxo alcohol ethoxylates can
completely
repress the reversible flocculation.
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The above-described stabilized microcapsule dispersions are particularly
advantageous for the
manufacture of liquid detergents or cleaning agents. A method according to the
invention, in
which a liquid detergent or cleaning agent is mixed with a microcapsule
dispersion, as described
above, preferably by stirring the microcapsule dispersion into the detergent
or cleaning agent
5 matrix or by continuously adding it into a liquid detergent or cleaning
agent and mixing the
ingredients by means of static mixing elements, therefore is a preferred
embodiment of the
invention.
Stabilized microcapsule dispersions are just as advantageous for the
manufacture of solid
10 detergents or cleaning agents. A method according to the invention, in
which a solid detergent or
cleaning agent is mixed with a microcapsule dispersion, as described above,
for example by
spraying the microcapsule dispersion onto the solid detergent or cleaning
agent matrix or onto
detergent or cleaning agent granules, therefore is a preferred embodiment of
the invention.
15 Also particularly advantageous is a method for manufacturing a solid
detergent or cleaning agent
in which the microcapsule dispersion is granulated before it is mixed with a
detergent or cleaning
agent.
Another subject matter of the invention is a method for washing fabrics that
uses a detergent or
20 cleaning agent according to the invention (as described above),
preferably in an automatic
washing machine, wherein the washing temperature is < 60 C, preferably < 40 C.
Fabric after-treatment agents are preferred detergents or cleaning agents
according to the invention.
These fabric after-treatment agents, as well, contain the microcapsules used
according to the
25 invention, as well as surfactants and/or builders. They are preferably
fabric softeners, i.e. fabric
after-treatment agents, containing a cationic surfactant. Preferred contained
cationic surfactants are
esterquats. Esterquats are quaternary ammonium compounds containing,
preferably, two
hydrophobic groups, each of which contains an ester group as a so-called
"predetermined breaking
point" for easier biodegradability. The amount of cationic surfactant is
preferably 2 to 80 wt %,
30 advantageously 4 to 40 wt %, further preferred 6 to 20 wt % and in
particular 8 to 15 wt % in each
instance based on the product as a whole. Polyquaternized polymers (e.g.
Luviquat Care from
BASF) and cationic chitin-based biopolymers and their derivatives, for example
the polymer sold
under the trade name Chitosan (manufacturer: Cognis) can also be used as
cationic surfactants.
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Another subject matter of the invention is a fabric conditioning method that
uses a fabric after-
treatment agent according to the invention (as described above) in the rinse
cycle of an automatic
washing machine.
Another subject matter of the invention is a fabric drying method that uses a
detergent or
cleaning agent according to the invention in an automatic clothes dryer.
Another subject matter of the invention is a fabric conditioning method that
uses a fabric after-
treatment agent according to the invention in the form of a conditioning
substrate in an automatic
clothes dryer.
Another subject matter of the invention is the use of a fabric after-treatment
agent according to the
invention to condition fabrics.
For the purposes of the invention, preferred products are also cleaning
agents, in particular
cleansers for hard surfaces. These, as well, contain the microcapsules used
according to the
invention as well as surfactants and/or builders. Also included as cleaning
additives in connection
with automatic dishwasher detergents are, for the purposes of the invention,
fragrance delivery
systems that comprise a container and particles for the deodorizing and
scenting of automatic
dishwashers; said particles comprising microcapsules that contain aromatic
substances.
If the cleaning agent according to the invention is chosen from the group
consisting of
dishwashing liquids, machine dishwashing detergents, toilet-bowl cleaners and
bathroom
cleaners, pipe cleaners and drain cleaners, universal or all-purpose cleaners,
sanitary cleaners,
oven cleaners and grill cleaners, metal cleaning agents, glass cleaners and
window cleaners,
cleaning aids, floor cleaners and special cleaning agents, this constitutes a
preferred
embodiment of the invention.
Also in connection with cleaning agents, an advantage of the invention lies in
that it enables a
retarded and/or targeted release of liquids, for example fragrances, from the
microcapsules
containing them. This makes possible an often strived-for slow-release effect
or long-lasting effect
and/or a carefully targeted release of active substance. The cleaned surface,
for example a floor, is
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uniformly scented over a long period of time or fragrances are released when
the deposited
microcapsules are broken up by mechanical stress. Other incorporated liquids,
for example liquids
containing antimicrobial agents, germicides, fungicides or other active
substances, can also be
released in a retarded and/or targeted manner, for example by the action of
mechanical force.
Another subject matter of the present invention is a particulate detergent or
cleaning agent additive
comprising the previously described microcapsules that can be used according
to the invention, as
well as surfactants and/or builders.
It has now been found that through the use of these particles according to the
invention, as described
above, if they contain aromatic substance, a particularly advantageous
olfactory impression
(increased appeal / higher intensity / better longevity) can be obtained
during washing or cleaning of
surfaces, in particular of fabrics. Retarded and/or targeted release of
fragrance is made possible.
Another subject matter of the invention is the use of a detergent or cleaning
agent according to the
invention in a washing or cleaning process to deposit microcapsules on the
treated objects (surfaces)
in order to enable the targeted release of, preferably, liquid active
substances such as, in particular,
aromatic substances, on the objects by mechanical stimulus.
Another subject matter of the invention is the use of a detergent or cleaning
agent according to the
invention in a washing or cleaning process to deposit microcapsules on the
treated objects (surfaces)
in order to enable the long-lasting release of, preferably, liquid active
substances such as, in
particular, aromatic substances, on the objects by diffusion.
Adjunct Materials
The disclosed compositions may include additional adjunct ingredients that
include:
fabric hueing agents, bleach activators, surfactants, builders, chelating
agents, dye transfer
inhibiting agents, dispersants, enzymes, and enzyme stabilizers, catalytic
metal complexes,
polymeric dispersing agents, clay and soil removal/anti-redeposition agents,
brighteners, suds
suppressors, dyes, additional perfumes and perfume delivery systems, structure
elasticizing
agents, fabric softeners, carriers, hydrotropes, processing aids and/or
pigments. Other
embodiments of Applicants' compositions do not contain one or more of the
following adjuncts
materials: fabric hueing agents, bleach activators, surfactants, builders,
chelating agents, dye
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transfer inhibiting agents, dispersants, enzymes, and enzyme stabilizers,
catalytic metal
complexes, polymeric dispersing agents, clay and soil removal/anti-
redeposition agents,
brighteners, suds suppressors, dyes, additional perfumes and perfume delivery
systems, structure
elasticizing agents, fabric softeners, carriers, hydrotropes, processing aids
and/or pigments. The
precise nature of these additional components, and levels of incorporation
thereof, will depend on
the physical form of the composition and the nature of the operation for which
it is to be used.
However, when one or more adjuncts are present, such one or more adjuncts may
be present as
detailed below. The following is a non-limiting list of suitable additional
adjuncts.
Fabric Hueing Agents - The composition may comprise a fabric hueing agent
(sometimes
referred to as shading, bluing or whitening agents). Typically the hueing
agent provides a blue or
violet shade to fabric. Hueing agents can be used either alone or in
combination to create a
specific shade of hueing and/or to shade different fabric types. This may be
provided for
example by mixing a red and green-blue dye to yield a blue or violet shade.
Hueing agents may
be selected from any known chemical class of dye, including but not limited to
acridine,
anthraquinone (including polycyclic quinones), azine, azo (e.g., monoazo,
disazo, trisazo,
tetrakisazo, polyazo), including premetallized azo, benzodifurane and
benzodifuranone,
carotenoid, coumarin, cyanine, diazahemicyanine, diphenylmethane, formazan,
hemicyanine,
indigoids, methane, naphthalimides, naphthoquinone, nitro and nitroso,
oxazine, phthalocyanine,
pyrazoles, stilbene, styryl, triarylmethane, triphenylmethane, xanthenes and
mixtures thereof.
Suitable fabric hueing agents include dyes, dye-clay conjugates, and organic
and inorganic
pigments. Suitable dyes include small molecule dyes and polymeric dyes.
Suitable small
molecule dyes include small molecule dyes selected from the group consisting
of dyes falling
into the Colour Index (C.I.) classifications of Acid, Direct, Basic, Reactive
or hydrolysed
Reactive, Solvent or Disperse dyes for example that are classified as Blue,
Violet, Red, Green or
Black, and provide the desired shade either alone or in combination. In
another aspect, suitable
small molecule dyes include small molecule dyes selected from the group
consisting of Colour
Index (Society of Dyers and Colourists, Bradford, UK) numbers Direct Violet
dyes such as 9, 35,
48, 51, 66, and 99, Direct Blue dyes such as 1, 71, 80 and 279, Acid Red dyes
such as 17, 73, 52,
88 and 150, Acid Violet dyes such as 15, 17, 24, 43, 49 and 50, Acid Blue dyes
such as 15, 17,
25, 29, 40, 45, 75, 80, 83, 90 and 113, Acid Black dyes such as 1, Basic
Violet dyes such as 1, 3,
4, 10 and 35, Basic Blue dyes such as 3, 16, 22, 47, 66, 75 and 159, Disperse
or Solvent dyes US
8,268,016 B2, or dyes as disclosed in US 7,208,459 B2, and mixtures thereof.
In another aspect,
suitable small molecule dyes include small molecule dyes selected from the
group consisting of
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C. I. numbers Acid Violet 17, Acid Blue 80, Acid Violet 50, Direct Blue 71,
Direct Violet 51,
Direct Blue 1, Acid Red 88, Acid Red 150, Acid Blue 29, Acid Blue 113 or
mixtures thereof.
Suitable polymeric dyes include polymeric dyes selected from the group
consisting of
polymers containing covalently bound (sometimes referred to as conjugated)
chromogens, (dye-
polymer conjugates), for example polymers with chromogens co-polymerized into
the backbone
of the polymer and mixtures thereof. Polymeric dyes include those described in
US 7,686,892
B2.
In another aspect, suitable polymeric dyes include polymeric dyes selected
from the
group consisting of fabric-substantive colorants sold under the name of
Liquitint (Milliken,
Spartanburg, South Carolina, USA), dye-polymer conjugates formed from at least
one reactive
dye and a polymer selected from the group consisting of polymers comprising a
moiety selected
from the group consisting of a hydroxyl moiety, a primary amine moiety, a
secondary amine
moiety, a thiol moiety and mixtures thereof. In still another aspect, suitable
polymeric dyes
include polymeric dyes selected from the group consisting of Liquitint Violet
CT,
carboxymethyl cellulose (CMC) covalently bound to a reactive blue, reactive
violet or reactive
red dye such as CMC conjugated with C.I. Reactive Blue 19, sold by Megazyme,
Wicklow,
Ireland under the product name AZO-CM-CELLULOSE, product code S-ACMC,
alkoxylated
triphenyl-methane polymeric colourants, alkoxylated thiophene polymeric
colourants, and
mixtures thereof.
Suitable dye clay conjugates include dye clay conjugates selected from the
group
comprising at least one cationic/basic dye and a smectite clay, and mixtures
thereof. In another
aspect, suitable dye clay conjugates include dye clay conjugates selected from
the group
consisting of one cationic/basic dye selected from the group consisting of
C.I. Basic Yellow 1
through 108, C.I. Basic Orange 1 through 69, C.I. Basic Red 1 through 118,
C.I. Basic Violet 1
through 51, C.I. Basic Blue 1 through 164, C.I. Basic Green 1 through 14, C.I.
Basic Brown 1
through 23, CI Basic Black 1 through 11, and a clay selected from the group
consisting of
Montmorillonite clay, Hectorite clay, Saponite clay and mixtures thereof. In
still another aspect,
suitable dye clay conjugates include dye clay conjugates selected from the
group consisting of:
Montmorillonite Basic Blue B7 C.I. 42595 conjugate, Montmorillonite Basic Blue
B9 C.I. 52015
conjugate, Montmorillonite Basic Violet V3 C.I. 42555 conjugate,
Montmorillonite Basic Green
G1 C.I. 42040 conjugate, Montmorillonite Basic Red R1 C.I. 45160 conjugate,
Montmorillonite
C.I. Basic Black 2 conjugate, Hectorite Basic Blue B7 C.I. 42595 conjugate,
Hectorite Basic
Blue B9 C.I. 52015 conjugate, Hectorite Basic Violet V3 C.I. 42555 conjugate,
Hectorite Basic
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Green G1 C.I. 42040 conjugate, Hectorite Basic Red R1 C.I. 45160 conjugate,
Hectorite C.I.
Basic Black 2 conjugate, Saponite Basic Blue B7 C.I. 42595 conjugate, Saponite
Basic Blue B9
C.I. 52015 conjugate, Saponite Basic Violet V3 C.I. 42555 conjugate, Saponite
Basic Green G1
C.I. 42040 conjugate, Saponite Basic Red R1 C.I. 45160 conjugate, Saponite
C.I. Basic Black 2
5 conjugate and mixtures thereof.
The hueing agent may be incorporated into the detergent composition as part of
a reaction
mixture which is the result of the organic synthesis for a dye molecule, with
optional purification
step(s). Such reaction mixtures generally comprise the dye molecule itself and
in addition may
comprise un-reacted starting materials and/or by-products of the organic
synthesis route.
10
Suitable polymeric hueing agents may be alkoxylated. As with all such
alkoxylated
compounds, the organic synthesis may produce a mixture of molecules having
different degrees
of alkoxylation. Such mixtures may be used directly to provide the hueing
agent, or may
undergo a purification step to increase the proportion of the target
molecule.Suitable pigments
include pigments selected from the group consisting of flavanthrone,
indanthrone, chlorinated
15 indanthrone containing from 1 to 4 chlorine atoms, pyranthrone,
dichloropyranthrone,
monobromodichloropyranthrone, dibromodichloropyranthrone,
tetrabromopyranthrone, perylene-
3,4,9,10-tetracarboxylic acid diimide, wherein the imide groups may be
unsubstituted or
substituted by Cl-C3 -alkyl or a phenyl or heterocyclic radical, and wherein
the phenyl and
heterocyclic radicals may additionally carry substituents which do not confer
solubility in water,
20 anthrapyrimidinecarboxylic acid amides, violanthrone, isoviolanthrone,
dioxazine pigments,
copper phthalocyanine which may contain up to 2 chlorine atoms per molecule,
polychloro-
copper phthalocyanine or polybromochloro-copper phthalocyanine containing up
to 14 bromine
atoms per molecule and mixtures thereof. In another aspect, suitable pigments
include pigments
selected from the group consisting of Ultramarine Blue (C.I. Pigment Blue 29),
Ultramarine
25 Violet (C.I. Pigment Violet 15), Monastral Blue and mixtures thereof.
The aforementioned fabric hueing agents can be used in combination (any
mixture of
fabric hueing agents can be used).
Deposition Aid - In one aspect, the fabric treatment composition may comprise
from
about 0.01% to about 10%, from about 0.05 to about 5%, or from about 0.15 to
about 3% of a
30 deposition aid. In one aspect, the deposition aid may be a cationic or
amphoteric polymer. In
another aspect, the deposition aid may be a cationic polymer. Cationic
polymers in general and
their method of manufacture are known in the literature. In one aspect, the
cationic polymer may
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have a cationic charge density of from about 0.005 to about 23 meq/g, from
about 0.01 to about
12 meq/g, or from about 0.1 to about 7 meq/g, at the pH of the composition.
For amine-
containing polymers, wherein the charge density depends on the pH of the
composition, charge
density is measured at the intended use pH of the product. Such pH will
generally range from
about 2 to about 11, more generally from about 2.5 to about 9.5. Charge
density is calculated by
dividing the number of net charges per repeating unit by the molecular weight
of the repeating
unit. The positive charges may be located on the backbone of the polymers
and/or the side
chains of polymers.
In another aspect, the deposition aid may comprise a cationic acrylic based
polymer. In a
further aspect, the deposition aid may comprise a cationic polyacrylamide. In
another aspect, the
deposition aid may comprise a polymer comprising polyacrylamide and
polymethacrylamidopropyl trimethylammonium cation. In another aspect, the
deposition aid
may comprise poly(acrylamide- N-dimethyl aminoethyl acrylate) and its
quaternized derivatives.
In another aspect, the deposition aid may be selected from the group
consisting of
cationic or amphoteric polysaccharides. In one aspect, the deposition aid may
be selected from
the group consisting of cationic and amphoteric cellulose ethers, cationic or
amphoteric
galactomannan, cationic guar gum, cationic or amphoteric starch, and
combinations thereof
Another group of suitable cationic polymers may include alkylamine-
epichlorohydrin
polymers which are reaction products of amines and oligoamines with
epichlorohydrin. Another
group of suitable synthetic cationic polymers may include polyamidoamine-
epichlorohydrin
(PAE) resins of polyalkylenepolyamine with polycarboxylic acid. The most
common PAE resins
are the condensation products of diethylenetriamine with adipic acid followed
by a subsequent
reaction with epichlorohydrin.
The weight-average molecular weight of the polymer may be from about 500
Daltons to about 5,000,000 Daltons, or from about 1,000 Daltons to about
2,000,000 Daltons, or
from about 2,500 Daltons to about 1,500,000 Daltons, as determined by size
exclusion
chromatography relative to polyethylene oxide standards with RI detection. In
one aspect, the
MW of the cationic polymer may be from about 500 Daltons to about 37,500
Daltons.
Surfactants: Surfactants utilized can be of the anionic, nonionic,
zwitterionic, ampholytic
or cationic type or can comprise compatible mixtures of these types.
Anionic and nonionic
surfactants are typically employed if the fabric care product is a laundry
detergent. On the other
hand, cationic surfactants are typically employed if the fabric care product
is a fabric softener.
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In addition to the anionic surfactant, the fabric care compositions of the
present
invention may further contain a nonionic surfactant. The compositions of the
present invention
can contain up to about 30%, alternatively from about 0.01% to about 20%, more
alternatively
from about 0.1% to about 10%, by weight of the composition, of a nonionic
surfactant. In one
embodiment, the nonionic surfactant may comprise an ethoxylated nonionic
surfactant. Suitable
for use herein are the ethoxylated alcohols and ethoxylated alkyl phenols of
the formula
R(0C2H4)n OH, wherein R is selected from the group consisting of aliphatic
hydrocarbon
radicals containing from about 8 to about 20 carbon atoms and alkyl phenyl
radicals in which the
alkyl groups contain from about 8 to about 12 carbon atoms, and the average
value of n is from
about 5 to about 15.
Suitable nonionic surfactants are those of the formula R1(0C2H4)n0H, wherein
R1 is a
Cio -C16 alkyl group or a C8 -C12 alkyl phenyl group, and n is from 3 to about
80. In one aspect,
particularly useful materials are condensation products of C9-C15 alcohols
with from about 5 to
about 20 moles of ethylene oxide per mole of alcohol.
The fabric care compositions of the present invention may contain up to about
30%, alternatively from about 0.01% to about 20%, more alternatively from
about 0.1% to about
20%, by weight of the composition, of a cationic surfactant. For the purposes
of the present
invention, cationic surfactants include those which can deliver fabric care
benefits. Non-limiting
examples of useful cationic surfactants include: fatty amines; quaternary
ammonium surfactants;
and imidazoline quat materials.
Non-limiting examples of fabric softening actives are N, N-bis(stearoyl-oxy-
ethyl) N,N-
dimethyl ammonium chloride, N,N-bis(tallowoyl-oxy-ethyl) N,N-dimethyl ammonium
chloride,
N,N-bis(stearoyl-oxy-ethyl) N-(2 hydroxyethyl) N-methyl ammonium
methylsulfate; 1, 2 di
(stearoyl-oxy) 3 trimethyl ammoniumpropane chloride;
dialkylenedimethylammonium salts such
as dicanoladimethylammonium chloride, di(hard)tallowdimethylammonium chloride
dicanoladimethylammonium methylsulfate;
1-methyl-1- stearoylamidoethy1-2-
stearoylimidazolinium methylsulfate; 1-tallowylamidoethy1-2-
tallowylimidazoline; N,N" -
dialkyldiethylenetriamine ;the reaction product of N-(2-hydroxyethyl)-1,2-
ethylenediamine or N-
(2-hydroxyisopropy1)-1,2-ethylenediamine with glycolic acid, esterified with
fatty acid, where
the fatty acid is (hydrogenated) tallow fatty acid, palm fatty acid,
hydrogenated palm fatty acid,
oleic acid, rapeseed fatty acid, hydrogenated rapeseed fatty acid;
polyglycerol esters (PGEs), oily
sugar derivatives, and wax emulsions and a mixture of the above.
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It will be understood that combinations of softener actives disclosed above
are suitable
for use herein.
Builders - The compositions may also contain from about 0.1% to 80% by weight
of a
builder. Compositions in liquid form generally contain from about 1% to 10% by
weight of the
builder component. Compositions in granular form generally contain from about
1% to 50% by
weight of the builder component. Detergent builders are well known in the art
and can contain,
for example, phosphate salts as well as various organic and inorganic
nonphosphorus builders.
Water-soluble, nonphosphorus organic builders useful herein include the
various alkali metal,
ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates
and
polyhydroxy sulfonates. Examples of polyacetate and polycarboxylate builders
are the sodium,
potassium, lithium, ammonium and substituted ammonium salts of ethylene
diamine tetraacetic
acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzene
polycarboxylic acids, and
citric acid. Other polycarboxylate builders are the oxydisuccinates and the
ether carboxylate
builder compositions comprising a combination of tartrate monosuccinate and
tartrate
disuccinate. Builders for use in liquid detergents include citric acid.
Suitable nonphosphorus,
inorganic builders include the silicates, aluminosilicates, borates and
carbonates, such as sodium
and potassium carbonate, bicarbonate, sesquicarbonate, tetraborate
decahydrate, and silicates
having a weight ratio of 5i02 to alkali metal oxide of from about 0.5 to about
4.0, or from about
1.0 to about 2.4. Also useful are aluminosilicates including zeolites.
Dispersants ¨ The compositions may contain from about 0.1%, to about 10%, by
weight
of dispersants Suitable water-soluble organic materials are the homo- or co-
polymeric acids or
their salts, in which the polycarboxylic acid may contain at least two
carboxyl radicals separated
from each other by not more than two carbon atoms. The dispersants may also be
alkoxylated
derivatives of polyamines, and/or quaternized derivatives.
Enzymes ¨ The compositions may contain one or more detergent enzymes which
provide
cleaning performance and/or fabric care benefits. Examples of suitable enzymes
include
hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases,
phospholipases, esterases,
cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases,
lipoxygenases,
ligninases, pullulanases, tannases, pentosanases, malanases, B-glucanases,
arabinosidases,
hyaluronidase, chondroitinase, laccase, and amylases, or mixtures thereof. A
typical combination
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may be a cocktail of conventional applicable enzymes like protease, lipase,
cutinase and/or
cellulase in conjunction with amylase. Enzymes can be used at their art-taught
levels, for
example at levels recommended by suppliers such as Novozymes and Genencor.
Typical levels
in the compositions are from about 0.0001% to about 5%. When enzymes are
present, they can
be used at very low levels, e.g., from about 0.001% or lower; or they can be
used in heavier-duty
laundry detergent formulations at higher levels, e.g., about 0.1% and higher.
In accordance with
a preference of some consumers for "non-biological" detergents, the
compositions may be either
or both enzyme-containing and enzyme-free.
Dye Transfer Inhibiting Agents - The compositions may also include from about
0.0001%, from about 0.01%, from about 0.05% by weight of the compositions to
about 10%,
about 2%, or even about 1% by weight of the compositions of one or more dye
transfer inhibiting
agents such as polyvinylpyrrolidone polymers, polyamine N-oxide polymers,
copolymers of N-
vinylpyrrolidone and N-vinylimidazole, polyvinyloxazolidones and
polyvinylimidazoles or
mixtures thereof.
Chelant ¨ The compositions may contain less than about 5%, or from about 0.01%
to
about 3% of a chelant such as citrates; nitrogen-containing, P-free
aminocarboxylates such as
EDDS, EDTA and DTPA; aminophosphonates such as diethylenetriamine
pentamethylenephosphonic acid and, ethylenediamine tetramethylenephosphonic
acid; nitrogen-
free phosphonates e.g., HEDP; and nitrogen or oxygen containing, P-free
carboxylate-free
chelants such as compounds of the general class of certain macrocyclic N-
ligands such as those
known for use in bleach catalyst systems.
Brighteners ¨ The compositions may also comprise a brightener (also referred
to as
"optical brightener") and may include any compound that exhibits fluorescence,
including
compounds that absorb UV light and reemit as "blue" visible light. Non-
limiting examples of
useful brighteners include: derivatives of stilbene or 4,4' -diaminostilbene,
biphenyl, five-
membered heterocycles such as triazoles, pyrazolines, oxazoles, imidiazoles,
etc., or six-
membered heterocycles (coumarins, naphthalamide, s-triazine, etc.). Cationic,
anionic, nonionic,
amphoteric and zwitterionic brighteners can be used. Suitable brighteners
include those
commercially marketed under the trade name Tinopal-UNPA-GX by Ciba Specialty
Chemicals
Corporation (High Point, NC).
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Bleach system ¨ Bleach systems suitable for use herein contain one or more
bleaching
agents. Non-limiting examples of suitable bleaching agents include catalytic
metal complexes;
activated peroxygen sources; bleach activators; bleach boosters;
photobleaches; bleaching
5 enzymes; free radical initiators; H202; hypohalite bleaches; peroxygen
sources, including
perborate and/or percarbonate and combinations thereof. Suitable bleach
activators include
perhydrolyzable esters and perhydrolyzable imides such as, tetraacetyl
ethylene diamine,
octanoylcaprolactam, benzoyloxybenzenesulphonate,
nonanoyloxybenzene¨isulphonate,
benzoylvalerolactam, dodecanoyloxybenzenesulphonate. Other bleaching agents
include metal
10 complexes of transitional metals with ligands of defined stability
constants.
Stabilizer - The compositions may contain one or more stabilizers and
thickeners. Any
suitable level of stabilizer may be of use; exemplary levels include from
about 0.01% to about
20%, from about 0.1% to about 10%, or from about 0.1% to about 3% by weight of
the
15 composition. Non-limiting examples of stabilizers suitable for use
herein include crystalline,
hydroxyl-containing stabilizing agents, trihydroxystearin, hydrogenated oil,
or a variation
thereof, and combinations thereof. In some aspects, the crystalline, hydroxyl-
containing
stabilizing agents may be water-insoluble wax-like substances, including fatty
acid, fatty ester or
fatty soap. In other aspects, the crystalline, hydroxyl-containing stabilizing
agents may be
20 derivatives of castor oil, such as hydrogenated castor oil derivatives,
for example, castor wax.
The hydroxyl containing stabilizers are disclosed in US Patents 6,855,680 and
7,294,611. Other
stabilizers include thickening stabilizers such as gums and other similar
polysaccharides, for
example gellan gum, carrageenan gum, and other known types of thickeners and
rheological
additives. Exemplary stabilizers in this class include gum-type polymers (e.g.
xanthan gum),
25 polyvinyl alcohol and derivatives thereof, cellulose and derivatives
thereof including cellulose
ethers and cellulose esters and tamarind gum (for example, comprising
xyloglucan polymers),
guar gum, locust bean gum (in some aspects comprising galactomannan polymers),
and other
industrial gums and polymers.
30
Silicones - Suitable silicones comprise Si-0 moieties and may be selected from
(a) non-
functionalized siloxane polymers, (b) functionalized siloxane polymers, and
combinations
thereof. The molecular weight of the organosilicone is usually indicated by
the reference to the
viscosity of the material. In one aspect, the organosilicones may comprise a
viscosity of from
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about 10 to about 2,000,000 centistokes at 25 C. In another aspect, suitable
organosilicones may
have a viscosity of from about 10 to about 800,000 centistokes at 25 C.
Suitable organosilicones may be linear, branched or cross-linked.
In one aspect, the organosilicone may comprise a cyclic silicone. The cyclic
silicone may
comprise a cyclomethicone of the formula RCH3)25i0l11 where n is an integer
that may range
from about 3 to about 7, or from about 5 to about 6.
In one aspect, the organosilicone may comprise a functionalized siloxane
polymer.
Functionalized siloxane polymers may comprise one or more functional moieties
selected from
the group consisting of amino, amido, alkoxy, hydroxy, polyether, carboxy,
hydride, mercapto,
sulfate phosphate, and/or quaternary ammonium moieties. These moieties may be
attached
directly to the siloxane backbone through a bivalent alkylene radical, (i.e.,
"pendant") or may be
part of the backbone. Suitable functionalized siloxane polymers include
materials selected from
the group consisting of aminosilicones, amidosilicones, silicone polyethers,
silicone-urethane
polymers, quaternary ABn silicones, amino ABn silicones, and combinations
thereof.
In one aspect, the functionalized siloxane polymer may comprise a silicone
polyether,
also referred to as "dimethicone copolyol." In general, silicone polyethers
comprise a
polydimethylsiloxane backbone with one or more polyoxyalkylene chains. The
polyoxyalkylene
moieties may be incorporated in the polymer as pendent chains or as terminal
blocks. In another
aspect, the functionalized siloxane polymer may comprise an aminosilicone.
In one aspect, the organosilicone may comprise amine ABn silicones and quat
ABn
silicones. Such organosilicones are generally produced by reacting a diamine
with an epoxide.
In another aspect, the functionalized siloxane polymer may comprise silicone-
urethanes.
These are commercially available from Wacker Silicones under the trade name
SLM-21200 .
Perfume: The optional perfume component may comprise a component selected from
the
group consisting of
(1) a perfume microcapsule, or a moisture-activated perfume microcapsule,
comprising a
perfume carrier and an encapsulated perfume composition, wherein said perfume
carrier may be selected from the group consisting of cyclodextrins, starch
microcapsules, porous carrier microcapsules, and mixtures thereof; and wherein
said
encapsulated perfume composition may comprise low volatile perfume
ingredients,
high volatile perfume ingredients, and mixtures thereof;
(2) a pro-perfume;
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(3) a low odor detection threshold perfume ingredients, wherein said low odor
detection
threshold perfume ingredients may comprise less than about 25%, by weight of
the
total neat perfume composition; and
(4) mixtures thereof; and
Porous Carrier Microcapsule - A portion of the perfume composition can also be
absorbed onto and/or into a porous carrier, such as zeolites or clays, to form
perfume porous
carrier microcapsules in order to reduce the amount of free perfume in the
multiple use fabric
conditioning composition.
Pro-perfume - The perfume composition may additionally include a pro-perfume.
Pro-
perfumes may comprise nonvolatile materials that release or convert to a
perfume material as a
result of, e.g., simple hydrolysis, or may be pH-change-triggered pro-perfumes
(e.g. triggered by
a pH drop) or may be enzymatically releasable pro-perfumes, or light-triggered
pro-perfumes.
The pro-perfumes may exhibit varying release rates depending upon the pro-
perfume chosen.
Examples
I. Synthesis examples:
Example 1.1: Manufacture of copolymers
a) AMPS hydroxybutyl acrylate
For 1,500 g preparation, 891 g demineralized water together with 585 g AMPS
(50% aqueous
solution) and 7.5 g 4-hydroxy butyl acrylate (HBA) are filled into the reactor
and placed in an
inert gas atmosphere. The reaction mixture is heated to 75 C while stirring
(400 rpm). 0.03 g of
the water-soluble initiator sodium peroxodisulfate are dissolved in 15 g water
and injected by
means of a syringe into the reactor when the reaction temperature is reached.
An hour of post-reaction starts after the maximum temperature is reached. The
preparation is
then cooled to room temperature and mixed with 1.5 g preservative.
The aqueous solution is characterized in terms of its viscosity, solids
content and pH. The
viscosity is 540 mPas (measured at 20 rpm Brookfield), the solids content is
21% and the pH is
3.3. 3 g copolymers are placed on a petri dish and dried for 24 hours at 160 C
in a drying cabinet.
The end weight is 0.69 g, which equals a yield of 21.6%.
b) AMPS polyalkylene glycol monomethacrylate
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The ingredients provided consist of 912 g of demineralized water, 240 g AMPS
and 7.5 g
poly(ethylene or propylene)glycol monomethacrylate (Bisomer PEM 63P HD from
Cognis, CAS
No. 589-75-9).
The mixture is placed in an inert gas atmosphere. The reaction mixture is
heated to 75 C while
stirring (400 rpm). 1.5 g sodium peroxodisulfate are dissolved in 15 g water
and transferred by
means of a syringe into the reactor. After the temperature has reached a
maximum in the reactor
and starts to drop, 240 g AMPS is dispensed by means of a peristaltic pump
along with 83 g PEM
63P over a period of one hour. A half-hour post-reaction then takes place. The
preparation is then
cooled to room temperature and mixed with 1.5 g preservative.
The aqueous solution is characterized in terms of its viscosity, solids
content and pH. The
viscosity is 110 mPas (measured at 20 rpm Brookfield), the solids content is
23% and the pH is
3.1. 3 g copolymers are placed on a petri dish and dried for 24 hours at 160 C
in a drying cabinet.
The end weight is 0.68 g, which equals a yield of 21.6%.
Example 1.2: Resorcin capsule
In a 400 mL beaker, 5.5 g resorcin are dissolved in water while stirring
(stirring speed:
approximately 1,500 rpm) and then mixed with 2.0 g sodium carbonate solution
(20 wt %), upon
which the pH is 7.9. The solution is heated to a temperature of approximately
52 C. 25.5 g
glutardialdehyde are then added.
The mixture is stirred for approximately an additional 10 minutes at a
stirring speed of
approximately 1,500 rpm and a temperature of approximately 52 C (pre-
condensation time).
Afterward, approximately 20 g water are added and approximately 2 minutes
later, 1 g of one of
the protective colloids (a) copolymer 1.1a, (b) copolymer 1.1b and (c) poly-
AMPS (AMPS
homopolymer) is added and approximately another 2 minutes later 55 g butyl
phenylacetate
(CAS No. 122-43-0; aromatic substance with a honey-like aroma) are added.
Immediately
afterward, the stirring speed is increased to approximately 4,000 rpm and at
approximately the
same time, 20.0 g sodium carbonate solution (20 wt %) are added. Afterward the
pH of the
mixture is approximately 9.7. Subsequently, the viscosity and the volume of
the mixture increase.
Stirring is continued at a stirring speed of approximately 4,000 rpm until the
viscosity drops
again. Only then is the stirring speed reduced to approximately 1,500 rpm. The
preparation is
stirred for an additional approximately 60 minutes at a temperature of
approximately 52 C and at
a roughly constant stirring speed. This phase is also called the dwell phase.
The mixture is then
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heated to approximately 80 C and the capsules are hardened at this temperature
for a period of 3
hours.
Capsule size distribution ¨ D (90) 5 to 10 pm; encapsulation efficiency
approx. 90%;
Drying yield > 90%; solids of the slurry approximately 40 wt %.
The capsules produced are formaldehyde-free and can be processed without any
problems from
the aqueous slurry into a dry, free-flowing powder as stable core/shell
microcapsules.
The capsules can also be loaded with other gaseous, liquid or solid
hydrophobic materials and
substance classes instead of with butyl phenyl acetate, in particular with
aromatic substances
and/or perfume oils.
In addition to the butyl-phenyl-acetate-containing resorcin microcapsules of
Example 1,
additional microcapsules were produced according to analogous methods:
- Example 1.3: hydroxycitronellal-containing resorcin microcapsules;
- Example 1.4: helional-containing resorcin microcapsules;
- Example 1.5: citral-containing resorcin microcapsules;
- Example 1.6: bourgeonal-containing resorcin microcapsules;
- Example 1.7: triplal-containing resorcin microcapsules;
- Example 1.8: ligustral-containing resorcin microcapsules;
- Example 1.9: vertocitral-containing resorcin microcapsules;
- Example 1.10: florhydral-containing resorcin microcapsules;
- Example 1.11: citronellal-containing resorcin microcapsules;
- Example 1.12: citronellyl-oxyacetaldehyde-containing resorcin
microcapsules.
In another series of examples, phloroglucin microcapsules were produced.
Analogously to the
method according to Example 1.2, the 5.5 g resorcin that were used there were
completely
replaced by 6.3 g phloroglucin, in this manner obtaining:
- Example 1.13: butyl-phenyl-acetate-containing phloroglucin microcapsules;
- Example 1.14: citronellal-containing phloroglucin microcapsules;
- Example 1.15: helional-containing phloroglucin microcapsules;
- Example 1.16: citral-containing phloroglucin microcapsules;
- Example 1.17: bourgeonal-containing phloroglucin microcapsules;
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- Example 1.18: triplal-containing phloroglucin microcapsules;
- Example 1.19: ligustral-containing phloroglucin microcapsules;
- Example 1.20: vertocitral-containing phloroglucin microcapsules;
- Example 1.21: florhydral-containing phloroglucin microcapsules;
5 - Example 1.22: citronellal-containing phloroglucin microcapsules;
- Example 1.23: citronellyl-oxyacetaldehyde-containing phloroglucin
microcapsules.
In the two series of examples, 1.3 through 1.12 (resorcin) and 1.13 through
1.23 (phloroglucin),
25.5 g glutardialdehyde can be replaced by 21.9 g succindialdehyde during the
synthesis of the
10 microcapsules. Such resorcin and phloroglucin microcapsules based on
succinaldehyde were
produced in example series 1.24 through 1.34 (resorcin and glutardialdehyde)
and 1.35 through
1.45 (phloroglucin and glutardialdehyde).
II. Examples of use
11.1
Granular laundry detergent compositions for hand washing or washing machines,
typically top-
loading washing machines.
A B C D E F
(wt %) (wt %) (wt %) (wt %) (wt %) (wt %)
Linear alkylbenzenesulfonate 20 22 20 15 19.5 20
C12-14 Dimethylhydroxyethyl
ammonium chloride 0.7 0.2 1 0.6 0.0 0
AE3S 0.9 1 0.9 0.0 0.4 0.9
AE7 0.0 0.0 0.0 1 0.1 3
Sodium tripolyphosphate 5 0.0 4 9 2 0.0
Zeolite A 0.0 1 0.0 1 4 1
1.6R Silicate (5i02:Na20 at
ratio 1.6:1) 7 5 2 3 3 5
Sodium carbonate 25 20 25 17 18 19
Polyacrylate MW 4500 1 0.6 1 1 1.5 1
Random graft copolymerl 0.1 0.2 0.0 0.0 0.05 0.0
Carboxymethyl cellulose 1 0.3 1 1 1 1
Stainzyme (20 mg active/g) 0.1 0.2 0.1 0.2 0.1 0.1
Protease (Savinase , 32.89 nrq
active/g) 0.1 0.1 0.1 0.1 0.1
Amylase - Natalase (8.65 mg
active/g) 0.1 0.0 0.1 0.0 0.1 0.1
Lipase - Lipex (18 mg active
/g) 0.03 0.07 0.3 0.1 0.07 0.4
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Fluorescent Brightener 1 0.06 0.0 0.06 0.18 0.06 0.06
Fluorescent Brightener 2 0.1 0.06 0.1 0.0 0.1 0.1
DTPA 0.6 0.8 0.6 0.25 0.6 0.6
MgSO4 1 1 1 0.5 1 1
Sodium Percarbonate 0.0 5.2 0.1 0.0 0.0 0.0
Sodium Perborate
Monohydrate 4.4 0.0 3.85 2.09 0.78 3.63
NOBS 1.9 0.0 1.66 0.0 0.33 0.75
TAED 0.58 1.2 0.51 0.0 0.015 0.28
Sulphonated zinc
phthalocyanine 0.0030 0.0 0.0012 0.0030 0.0021 0.0
S-ACMC 0.1 0.0 0.0 0.0 0.06 0.0
Direct Violet Dye (DV9 or
DV99 or DV66) 0.0 0.0 0.0003 0.0001 0.0001 0.0
Additional Neat Perfume (1) 0.5 0.5 0.5 0.5 0.5 0.5
Microcapsules (2) 0.7 1.0 2.3 0.5 1.2 0.8
Sulfate/Moisture Balance
(1) Optional.
(2) Microcapsules of the present invention comprising a core that comprise
perfume.
11.2 Granular laundry detergent compositions typically for front-loading
automatic washing
machines. The typical pH is about 10
A E F
(wt B C D (wt%) (wt%)
%) (wt%) (wt%) (wt%)
Linear alkylbenzenesulfonate 8 7.1 7 6.5 7.5 7.5
AE3S 0 4.8 1.0 5.2 4 4
C12-14 Alkylsulfate 1 0 1 0 0 0
AE7 2.2 0 2.2 0 0 0
C10-12 Dimethyl 0 0
hydroxyethylammonium chloride 0.75 0.94 0.98 0.98
Crystalline layered silicate (8- 0 0
Na2Si205) 4.1 0 4.8 0
Zeolite A 5 0 5 0 2 2
Citric Acid 3 5 3 4 2.5 3
Sodium Carbonate 15 20 14 20 23 23
Silicate 2R (5i02:Na20 at ratio 2:1) 0.08 0 0.11 0 0 0
Soil release agent 0.75 0.72 0.71 0.72 0 0
Acrylic Acid/Maleic Acid 2.6 3.8
Copolymer 1.1 3.7 1.0 3.7
Carboxymethylcellulose 0.15 1.4 0.2 1.4 1 0.5
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Protease - Purafect (84 mg
active/g) 0.2 0.2 0.3 0.15 0.12 0.13
Amylase - Stainzyme Plus (20 mg 0.15 0.15
active/g) 0.2 0.15 0.2 0.3
Lipase - Lipex (18.00 mg active/g) 0.05 0.15 0.1 0 0 0
Amylase - Natalase (8.65 mg 0.15 0.15
active/g) 0.1 0.2 0 0
Cellulase - CellucleanTM (15.6 mg 0.1 0.1
active/g) 0 0 0 0
TAED 3.6 4.0 3.6 4.0 2.2 1.4
Percarbonate 13 13.2 13 13.2 16 14
Na salt of Ethylenediamine-N,N'- 0.2 0.2
disuccinic acid, (S,S) isomer (EDDS) 0.2 0.2 0.2 0.2
Hydroxyethane di phosphonate 0.2 0.2
(HEDP) 0.2 0.2 0.2 0.2
MgSO4 0.42 0.42 0.42 0.42 0.4 0.4
Perfume 0.5 0.6 0.5 0.6 0.6 0.6
Suds suppressor agglomerate 0.05 0.1 0.05 0.1 0.06 0.05
Soap 0.45 0.45 0.45 0.45 0 0
Sulphonated zinc phthalocyanine 0.00 0 0
(active) 07 0.0012 0.0007 0
S-ACMC 0.01 0.01 0 0.01 0 0
Direct Violet 9 (active) 0 0 0.0001 0.0001 0 0
Additional Neat Perfume (1) 0.5 0.5 0.5 0.5 0.5 0.5
Perfume Microcapsules (2) 2.0 1.5 0.9 2.2 1.5 0.8
Sulfate/ Water & Miscellaneous Balance
(1) Optional.
(2) Microcapsules of the present invention comprising a core that comprise
perfume.
11.3 Heavy Duty Liquid laundry detergent compositions
A B C D E F G
(wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%)
AES C12-15 alkyl ethoxy (1.8)
sulfate 11 10 4 6.32 0 0 0
AE3S 0 0 0 0 2.4 0 0
Linear alkyl benzene
sulfonate/sulfonic acid 1.4 4 8 3.3 5 8 19
HSAS 3 5.1 3 0 0 0 0
Sodium formate 1.6 0.09 1.2 0.04 1.6 1.2
0.2
Sodium hydroxide 2.3 3.8 1.7 1.9 1.7 2.5
2.3
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To pH
Monoethanolamine 1.4 1.49 1.0 0.7 0 0 8.2
Diethylene glycol 5.5 0.0 4.1 0.0 0 0 0
AE9 0.4 0.6 0.3 0.3 0 0 0
AE8 0 0 0 0 0 0 20.0
AE7 0 0 0 0 2.4 6 0
Chelant (HEDP) 0.15 0.15 0.11 0.07 0.5 0.11
0.8
Citric Acid 2.5 3.96 1.88 1.98 0.9 2.5 0.6
C12-14 dimethyl Amine Oxide 0.3 0.73 0.23 0.37 0 0 0
C12-18 Fatty Acid 0.8 1.9 0.6 0.99 1.2 0 15.0
4-formyl-phenylboronic acid 0 0 0 0 0.05 0.02 0.01
Borax 1.43 1.5 1.1 0.75 0 1.07 0
Ethanol 1.54 1.77 1.15 0.89 0 3 7
A compound having the following
general structure:
bis((C2H50)(C2H40)n)(CH3)-N+-
CM2x-N -(CH3)-
bis((C2H50)(C2H40)n), wherein n
= from 20 to 30, and x = from 3 to
8, or sulphated or sulphonated
variants thereof 0.1 0 0 0 0 0 2.0
Ethoxylated (E015) tetraethylene
pentamine 0.3 0.33 0.23 0.17 0.0 0.0 0
Ethoxylated Polyethylenimine 0 0 0 0 0 0 0.8
Ethoxylated hexamethylene
diamine 0.8 0.81 0.6 0.4 1 1
1,2-Propanediol 0.0 6.6 0.0 3.3 0.5 2 8.0
Fluorescent Brightener 0.2 0.1 0.05 0.3 0.15 0.3 0.2
Hydrogenated castor oil derivative 0.1 0.1
structurant 0 0 0 0 0
Perfume 1.6 1.1 1.0 0.8 0.9 1.5 1.6
Protease (40.6 mg active/g) 0.8 0.6 0.7 0.9 0.7 0.6 1.5
Mannanase: Mannaway@ (25 mg
active/g) 0.07 0.05 0.045 0.06 0.04 0.045 0.1
Amylase: Stainzyme@ (15 mg
active/g) 0.3 0 0.3 0.1 0 0.4 0.1
Amylase: Natalase@ (29 mg
active/g) 0 0.2 0.1 0.15 0.07 0 0.1
Xyloglucanase (Whitezyme@, 0.2
20mg active/g) 0.2 0.1 0 0 0.05 0.05
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Lipex (18 mg active/g) 0.4 0.2 0.3 0.1 0.2 0 0
Additional Neat Perfume (1) 0.5 0.5 0.5 0.5 0.5 0.5
0.5
Perfume Microcapsules (2) 0.25 3.2 2.5 4.0 2.5 1.4
0.8
*Water, dyes & minors Balance
* Based on total cleaning and/or treatment composition weight, a total of no
more than 12%
water
(1) Optional.
(2) Microcapsules of the present invention comprising a core that comprise
perfume.
Examples 11.4 Unit Dose Compositions
Example of Unit Dose detergents A B
C14_ 15 alkyl poly ethoxylate (8) 12 -
C12 - 14 alkyl poly ethoxylate (7) 1 14
C12 - 14 alkyl poly ethoxylate (3) sulfate Mono
8.4 9
EthanolAmine salt
Linear Alkylbenzene sulfonic acid 15 16
Citric Acid 0.6 0.5
C1218 Fatty Acid 15 17
Enzymes 1.5 1.2
PEI 600 E020 4 -
Diethylene triamine penta methylene
1.3 _
phosphonic acid or HEDP
Fluorescent brightener 0.2 0.3
Hydrogenated Castor Oil 0.2 0.2
1, 2 propanediol 16 12
Glycerol 6.2 8.5
Sodium hydroxide - 1
Mono Ethanol Amine 7.9 6.1
Dye Present Present
PDMS - 2.7
Potassium sulphite 0.2 0.2
Perfume Microcapsules (1) 1.5 0.9
Up to Up to
Water
100p 100
(1) Microcapsules of the present invention comprising a core that comprise
perfume.
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Raw Materials and Notes For Composition Examples
LAS is linear alkylbenzenesulfonate having an average aliphatic carbon chain
length C9-
C15 supplied by Stepan, Northfield, Illinois, USA or Huntsman Corp. (HLAS is
acid form).
C12-14 Dimethylhydroxyethyl ammonium chloride, supplied by Clariant GmbH,
Germany
5 AE3S is C12-15 alkyl ethoxy (3) sulfate supplied by Stepan, Northfield,
Illinois, USA
AE7 is C12-15 alcohol ethoxylate, with an average degree of ethoxylation of 7,
supplied by
Huntsman, Salt Lake City, Utah, USA
AES is C10-18 alkyl ethoxy sulfate supplied by Shell Chemicals.
AE9 is C12-13 alcohol ethoxylate, with an average degree of ethoxylation of 9,
supplied by
10 Huntsman, Salt Lake City, Utah, USA
HSAS or HC1617HSAS is a mid-branched primary alkyl sulfate with average carbon
chain length of about 16-17
Sodium tripolyphosphate is supplied by Rhodia, Paris, France
Zeolite A is supplied by Industrial Zeolite (UK) Ltd, Grays, Essex, UK
15 1.6R Silicate is supplied by Koma, Nestemica, Czech Republic
Sodium Carbonate is supplied by Solvay, Houston, Texas, USA
Polyacrylate MW 4500 is supplied by BASF, Ludwigshafen, Germany
Carboxymethyl cellulose is Finnfix V supplied by CP Kelco, Arnhem,
Netherlands
Suitable chelants are, for example, diethylenetetraamine pentaacetic acid
(DTPA)
20 supplied by Dow Chemical, Midland, Michigan, USA or Hydroxyethane di
phosphonate (HEDP)
supplied by Solutia, St Louis, Missouri, USA Bagsvaerd, Denmark
Savinase , Natalase , Stainzyme , Lipex , CellucleanTM, Mannaway and
Whitezyme are all products of Novozymes, Bagsvaerd, Denmark.
Proteases may be supplied by Genencor International, Palo Alto, California,
USA (e.g.
25 Purafect Prime(D) or by Novozymes, Bagsvaerd, Denmark (e.g. Liquanase ,
Coronase ).
Fluorescent Brightener 1 is Tinopal AMS, Fluorescent Brightener 2 is Tinopal
CBS-
X, Sulphonated zinc phthalocyanine and Direct Violet 9 is Pergasol Violet BN-
Z all supplied
by Ciba Specialty Chemicals, Basel, Switzerland
Sodium percarbonate supplied by Solvay, Houston, Texas, USA
30 Sodium perborate is supplied by Degussa, Hanau, Germany
NOBS is sodium nonanoyloxybenzenesulfonate, supplied by Future Fuels,
Batesville,
USA
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TAED is tetraacetylethylenediamine, supplied under the Peractive brand name
by
Clariant GmbH, Sulzbach, Germany
S-ACMC is carboxymethylcellulose conjugated with C.I. Reactive Blue 19, sold
by
Megazyme, Wicklow, Ireland under the product name AZO-CM-CELLULOSE, product
code S-
ACMC.
Soil release agent is Repel-o-tex PF, supplied by Rhodia, Paris, France
Acrylic Acid/Maleic Acid Copolymer is molecular weight 70,000 and
acrylate:maleate
ratio 70:30, supplied by BASF, Ludwigshafen, Germany
Na salt of Ethylenediamine-N,N'-disuccinic acid, (S,S) isomer (EDDS) is
supplied by
Octel, Ellesmere Port, UK
Hydroxyethane di phosphonate (HEDP) is supplied by Dow Chemical, Midland,
Michigan, USA
Suds suppressor agglomerate is supplied by Dow Corning, Midland, Michigan, USA
HSAS is mid-branched alkyl sulfate as disclosed in US 6,020,303 and US
6,060,443
C12_14 dimethyl Amine Oxide is supplied by Procter & Gamble Chemicals,
Cincinnati,
USA
Random graft copolymer is a polyvinyl acetate grafted polyethylene oxide
copolymer having
a polyethylene oxide backbone and multiple polyvinyl acetate side chains. The
molecular
weight of the polyethylene oxide backbone is about 6000 and the weight ratio
of the
polyethylene oxide to polyvinyl acetate is about 40:60 and no more than 1
grafting point per
50 ethylene oxide units.
Ethoxylated polyethyleneimine is polyethyleneimine (MW = 600) with 20
ethoxylate groups
per -NH.
Cationic cellulose polymer is LK400, LR400 and/or JR3OM from Amerchol
Corporation,
Edgewater NJ
Note: all enzyme levels are expressed as % enzyme raw material
EXAMPLE 5. Microcapsules in Shampoo
A subset of the capsules from the above examples is formulated into a rinse-
off Shampoo
formulation as follows: to 90.0 grams of shampoo formulation (with a typical
formulation given
below) is added an appropriate amount of microcapsule slurry to deliver a
fragrance usage level
of 0.5wt%. The microcapsules and water are added on top of the shampoo
formulation, then the
contents are mixed using a SpeedMixer by Hauschild DAC 400FVZ mixer, at 1850
RPM for 1
minute.
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Typical composition of shampoo formulations are given in the examples below.
EXAMPLE COMPOSITION I II III
- =
In
Water q.s. q.s. q.s.
Polyquaternium 76' 2.50
Guar, Hydroxylpropyl
0.25
Trimonium Chloride
Polyquaterium 6 3 0.79
Sodium Laureth Sulfate 21.4 21.4
(SLE3S) 4 3 3 21.43
Sodium Lauryl Sulfate (SLS) 20.6 20.6
20.69
9 9
Silicone 6 0.75 1.00 0.5
Cocoamidopropyl Betaine 7 3.33 3.33 3.33
Cocoamide MEA 8 1.0 1.0 1.0
Ethylene Glycol Distearate 9 1.50 1.50 1.50
Sodium Chloride 1 0.25 0.25 0.25
Fragrance 0.70 0.70 0.70
Fragrance Microcapsule 1.2 1.2 1.2
Up Up
Up to
Preservatives, pH adjusters to to
1%
1% 1%
1 Mirapol AT-1, Copolymer of Acrylamide(AM) and TRIQUAT, MW=1,000,000;
CD= 1.6 meq./gram; 10% active ; Supplier Rhodia
2 Jaguar C500, MW - 500,000, CD=0.7, supplier Rhodia
3 Mirapol 100S, 31.5% active, supplier Rhodia
4 Sodium Laureth Sulfate, 28% active, supplier: P&G
5 Sodium Lauryl Sulfate, 29% active supplier: P&G
6 Glycidol Silicone VC2231-193C
7 Tegobetaine F-B, 30% active supplier: Goldschmidt Chemicals
8 Monamid CMA, 85% active, supplier Goldschmidt Chemical
9 Ethylene Glycol Distearate, EGDS Pure, supplier Goldschmidt Chemical
Sodium Chloride USP (food grade), supplier Morton; note that salt is an
adjustable
ingredient, higher or lower levels may be added to achieve target viscosity.
EXAMPLE COMPOSITION IV V VI
Ingredient
Water q.s. q.s. q.s.
Silicone A 1 1.0
Silicone B 2 0.5
Silicone C 3 0.5
Cyclopentasiloxane 4 0.61 1.5
Behenyl trimethyl
2.25 2.25 2.25
ammonium chloride 5
Isopropyl alcohol 0.60 0.60 0.60
Cetyl alcohol 6 1.86 1.86 1.86
Stearyl alcohol 7 4.64 4.64 4.64
Disodium EDTA 0.13 0.13 0.13
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NaOH 0.01 0.01 0.01
Benzyl alcohol 0.40 0.40 0.40
Methylchloroisothiazolinone/ 0.000 0.000
0.0005 5
Methylisothiazolinone 8 5
Panthenol 9 0.10 0.10 0.10
Panthenyl ethyl ether 1 0.05 0.05 0.05
Fragrance 0.35 0.35 0.35
Fragrance Microcapsules 1.2 1.2 1.2
1 Glycidol Silicone VC2231-193
2 Glycidol Silicone VC2231-193F
3 Glycidol Silicone VC2231-193A
4 Cyclopentasiloxane: SF1202 available from Momentive Performance Chemicals
Behenyl trimethyl ammonium chloride/Isopropyl alcohol: Genamin ril \II KMP
available from Clariant
6 Cetyl alcohol: Konol ril \II series available from Shin Nihon Rika
7 Stearyl alcohol: Konol TM series available from Shin Nihon Rika
8 Methylchloroisothiazolinone/Methylisothiazolinone: Kathon TM CG available
from
Rohm & Haas
9 Panthenol: Available from Roche
Panthenyl ethyl ether: Available from Roche
EXAMPLE COMPOSITION VII VIII
Ingredient
Sodium Laureth Sulfate 10.00 10.00
Sodium Lauryl Sulfate 1.50 1.50
Cocamidopropyl betaine 2.00 2.00
Guar Hydroxypropyl trimonium chloride (1) 0.40
Guar Hydroxypropyl trimonium chloride (2) 0.40
Dimethicone (3) 2.00 2.00
Gel Network (4) 27.27
Ethylene Glycol Distearate 1.50 1.50
5-Chloro-2-methyl-4-isothiazolin-3-one, Kathon 0.0005 0.0005
CG
Sodium Benzoate 0.25 0.25
Disodium EDTA 0.13 0.13
Perfume 0.70 0.70
Fragrance Microcapsules of Example 3 1.0 1.0
Citric Acid/ Sodium Citrate Dihydrate pH QS pH QS
Sodium Chloride/ Ammonium Xylene Sulfonate Visc. Visc.
QS QS
Water QS QS
(1) Jaguar C17 available from Rhodia
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(2) N-Hance 3269 (with Mol. W. of -500,000 and 0.8meq/g) available from
Aqulaon/Hercules
(3) Viscasil 330M available from General Electric Silicones
(4) Gel Networks; See Composition below. The water is heated to about 74 C
and the Cetyl
Alcohol, Stearyl Alcohol, and the SLES Surfactant are added to it. After
incorporation, this
mixture is passed through a heat exchanger where it is cooled to about 35 C.
As a result of this
cooling step, the Fatty Alcohols and surfactant crystallized to form a
crystalline gel network.
Ingredient Wt. %
Water 86.14%
Cetyl Alcohol 3.46%
Steary Alcohol 6.44%
Sodium laureth-3 sulfate (28% Active) 3.93%
5-Chloro-2-methyl-4-isothiazolin-3-one, Kathon CG 0.03%
EXAMPLE 6. Microcapsules in Lotion
Example I II III
PHASE A
DC-9040 1 8.60 3.00 5.00
Dimethicone 4.09 4.00 4.00
Polymethylsilsesquioxane 2 4.09 4.00 4.00
Cyclomethicone 11.43 0.50 11.33
KSG-210 3 5.37 5.25 5.40
Polyethylene wax 4 3.54 2.05
DC-2503 Cosmetic Wax 5 7.08 10.00 3.77
Hydrophobic TiO2 0.50
Iron oxide coated Mica 0.65
TiO2 Coated Mica 1.00 1.00
Fragrance Particles 1.00 1.00 1.00
PHASE B
Glycerin 10.00 10.00 10.00
Dexpanthenol 0.50 0.50 0.50
Pentylene Glycol 3.00 3.00 3.00
Hexamidine Diisethionate 6 0.10 0.10 0.10
Niacinamide 7 5.00 5.00 5.00
Methylparaben 0.20 0.20 0.20
Ethylparaben 0.05 0.05 0.05
Sodium Citrate 0.20 0.20 0.20
Citric Acid 0.03 0.03 0.03
Sodium Benzoate 0.05 0.05 0.05
Sodium Chloride 0.50 0.50 0.50
FD&C Red #40 (1%) 0.05 0.05 0.05
q.s to q.s to q.s to
Water 100 100 100
Hardness at 21 C (g) 33.3 15.4 14.2
Hardness at 33 C (g) 6.4 0.7 4.0
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1. 12.5% Dimethicone Crosspolymer in Cyclopentasiloxane. Available from Dow
CorningTM.
2. E.g., TospearlTm 145A or Tospearl 2000. Available from GE Toshiba
SiliconeTM.
3. 25% Dimethicone PEG-10/15 Crosspolymer in Dimethicone. Available from
Shin-EtsijTM.
4. JeenateTm 3H polyethylene wax from JeenTM
5 5. Stearyl Dimethicone. Available from Dow Corning.
6. Hexamidine diisethionate, available from Laboratoires Serobiologiques.
7. Additionally or alternatively, the composition may comprise one or more
other skin care actives, their salts and
derivatives, as disclosed herein, in amounts also disclosed herein as would be
deemed suitable by one of skill
in the art.
For the examples above, in a suitable container, combine the ingredients of
Phase A. In a
separate suitable container, combine the ingredients of Phase B. Heat each
phase to 73 C-78 C
while mixing each phase using a suitable mixer (e.g., Anchor blade, propeller
blade, or IKA T25)
until each reaches a substantially constant desired temperature and is
homogenous. Slowly add
Phase B to Phase A while continuing to mix Phase A. Continue mixing until
batch is uniform.
Pour product into suitable containers at 73-78 C and store at room
temperature. Alternatively,
continuing to stir the mixture as temperature decreases results in lower
observed hardness values
at 21 and 33 C.
Example 7
di-Aldehyde functional diazobenzene synthesis
a) 4,4' -dibromoazobenzene synthesis
50 g. of p-bromoaniline (available from Sigma-Aldrich) and 1 liter of
anhydrous benzene is
added to a round bottom flask with stirring. 258 grams of finely powdered lead
tetraacetate
is added slowly over 3 hours. After one additional hour the lead diacetate is
filtered off and
the filtrate is washed thoroughly with 3 liters of water. After separating the
benzene and
aqueous layers, the benzene solution is concentrated to a volume of 100 ml.
The
concentrate on cooling in ice yields 31 g. of a solid material that on
sublimation in vacuum
(0.001 mm.) within the temperature range of 200-250" (air-bath) gives 20 grams
of 4,4'-
dibromoazobenzene. The product is recrystallized from chloroform.
b) di-Aldehyde functional diazobenzene synthesis
A solution of 10 grams of 4,4' -dibromo-azobenzene from the example above and
50 ml of
diethyl ether (available from Sigma-Aldrich) is added dropwise to a dispersion
of 2 grams
of magnesium (available from Sigma-Aldrich) in 25m1 of diethyl ether in a
round bottom
flask equipped with nitrogen gas. After 3 hours at 25C, a solution of 3 grams
of
paraformaldehyde (available from Sigma-Aldrich) dissolved in 30 ml of diethyl
ether is
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added dropwise over a 30 minute period. After stirring for an additional 8
hours, the
solution is acidified with an aqueous solution of 0.1N HC1 (available from
Sigma-Aldrich).
The ether solution is filtered from the solids and extracted with 0.1N sodium
bicarbonate
solution, followed by extractions with water. The ether layer is vacuum dried
and 2 grams
of the product is dissolved into 50m1 of acetonitrile. A solution of 5 grams
of sodium
periodate (NaI04) in 10 milliliters of water and this is added to the product
from the
previous step dissolved in acetonitrile. The reaction mixture is diluted with
200 mL of
methylene chloride and filtered. The resin is thoroughly washed with methylene
chloride
and combined washings and filtrates are purified on silica-gel plates or
silica-gel column.
IR and 1H NMR spectral data confirm the identity of the product.
c) Re s orcin capsule
In a 400 mL beaker, 5.5 g resorcin are dissolved in water while stirring
(stirring speed:
approximately 1,500 rpm) and then mixed with 2.0 g sodium carbonate solution
(20 wt %), upon
which the pH is 7.9. The solution is heated to a temperature of approximately
52 C. 20 g
glutardialdehyde are then added.
The mixture is stirred for approximately an additional 10 minutes at a
stirring speed of
approximately 1,500 rpm and a temperature of approximately 52 C (pre-
condensation time).
Afterward, approximately 20 g water are added and approximately 2 minutes
later, 1 g of one of
the protective colloids (a) copolymer 1.1a, (b) copolymer 1.1b and (c) poly-
AMPS (AMPS
homopolymer) is added and approximately another 2 minutes later 55 g butyl
phenylacetate
(CAS No. 122-43-0; aromatic substance with a honey-like aroma) and 5.5 g of di-
Aldehyde
functional diazobenzene are added. Immediately afterward, the stirring speed
is increased to
approximately 4,000 rpm and at approximately the same time, 20.0 g sodium
carbonate solution
(20 wt %) are added. Afterward the pH of the mixture is approximately 9.7.
Subsequently, the
viscosity and the volume of the mixture increase. Stirring is continued at a
stirring speed of
approximately 4,000 rpm until the viscosity drops again. Only then is the
stirring speed reduced
to approximately 1,500 rpm. The preparation is stirred for an additional
approximately 60
minutes at a temperature of approximately 52 C and at a roughly constant
stirring speed. This
phase is also called the dwell phase. The mixture is then heated to
approximately 80 C and the
capsules are hardened at this temperature for a period of 3 hours.
Capsule size distribution ¨ D (90) 5 to 10 pm; encapsulation efficiency
approx. 90%;
Drying yield > 90%; solids of the slurry approximately 40 wt %.
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The capsules produced are formaldehyde-free and can be processed without any
problems from
the aqueous slurry into a dry, free-flowing powder as stable core/shell
microcapsules.
The capsules can also be loaded with other gaseous, liquid or solid
hydrophobic materials and
substance classes instead of with butyl phenyl acetate, in particular with
aromatic substances
and/or perfume oils. One aliquot of capsules are subjected to pressure and a
second aliquot are
subjected to electromagnetic radiation both aliquots demonstrate trigger
release of their core
materials.
The dimensions and values disclosed herein are not to be understood as being
strictly limited to
the exact numerical values recited. Instead, unless otherwise specified, each
such dimension is
intended to mean both the recited value and a functionally equivalent range
surrounding that
value. For example, a dimension disclosed as "40 mm" is intended to mean
"about 40 mm."
Every document cited herein, including any cross referenced or related patent
or application and
any patent application or patent to which this application claims priority or
benefit thereof, is
hereby incorporated herein by reference in its entirety unless expressly
excluded or otherwise
limited. The citation of any document is not an admission that it is prior art
with respect to any
invention disclosed or claimed herein or that it alone, or in any combination
with any other
reference or references, teaches, suggests or discloses any such invention.
Further, to the extent
that any meaning or definition of a term in this document conflicts with any
meaning or
definition of the same term in a document incorporated by reference, the
meaning or definition
assigned to that term in this document shall govern.
While particular embodiments of the present invention have been illustrated
and described, it
would be obvious to those skilled in the art that various other changes and
modifications can be
made without departing from the spirit and scope of the invention. It is
therefore intended to
cover in the appended claims all such changes and modifications that are
within the scope of this
invention.
