Note: Descriptions are shown in the official language in which they were submitted.
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PERFUMED BLEACHING COMPOSITIONS
Field of the invention
The invention relates to perfumed bleaching compositions. More
specifically, it relates to bleaching co;mpositions comprising a
bleach system and a stabilised perfume composition.
Background of the invention
Perfumes are an important and desirable part of detergent
compositions. They are used to cover up the chemical odours of
the cleaning ingredients and provide an aesthetic benefit to the
wash process and, preferably the cleaned fabrics. EP 430315,
which discloses the use of a laundry detergent composition
containing a lipase and a perfume having specific fragrance
materials, exemplifies such use. In said patent, the perfume
composition is said to counteract the problem of the residual
malodour of lipase treated laundry.
However, perfumes generally are volatile and many perfume
ingredients can be destroyed or damaged by contact with
cleaning ingredients, especially alkali and bleaches. To minimise
direct contact between perfume and bleach components in
granular compositions, bleaches are sometimes admixed after
perfume spray-on. Even this does not avoid oxidation of
perfumes by bleaches, especially bleach activator/bleaching agent
combinations, at least partly because of perfume mobility in the
compositions.
One solution to this problem is encapsulation of the perfume.
This increases the expense and complexity of formulation and
~ does not always provide sufficient protection. EP 332259
teaches the use of a liquid detergent composition containing
peroxyacid bleach and perfumed silica particles which protect the
perfurne from oxidation by the bleach.
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Despite the above disclosures, there is a continuing need for the
development or identification of perfumes suitable for use in
bleaching compositions containing a bleach system selected frorn
a perhydrate in combination with a bleach activator and a
preformed peracid.
Coating the bleaching agent in order to stabilise it has been
extensively disclosed in the patent literature, an example being
WO 94/01521 which describes the use of a detergent
composition comprising a bleach activator, a coated alkali metal
percarbonate bleach wherein the coating material is a mixed salt
of an alkali metal carbonate and alkali rnetal sulphate, a chelant
(EDDS) and a perfume.
It has now been found that coating the source of active oxygen
such as the perhydrate and/or the preformed peracid allows the
use of new perfume compositions.
It has also been found that the further coating of the bleach
activa~or allows the use of such new perfume compositions.
Therefore, it is an object of the invention to provide a perfume
composition comprising aroma chemicals selected from primary
and secondary alcohols, aliphatic aldehydes, hydrocinnamic
aldehydes, esters excluding salicylates and unsaturated ketones
in a bl~aching cornposition containing a bleaching system,
selected from a perhydrate in combination with a bleach activator
and a preformed peracid wherein said perhydrate and/or said
preformed peracid are coated, which gives an excellent perfume
fragrance on fabrics as well as an excellent perfume stability in
presence of the bleaching ingredient in the wash liquor and in the
product during storage.
For the purpose of the present invention, a perfumed bleaching
composition consists of a bleaching composition and a perfume
composition, both as defined hereinafter, wherein said perfume is
incorporated by any rneans in a composition selected from:
i)-the bleaching composition as a finished product,
ii)-the bleaching composition during its making process,
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or any mixtures thereof.
Processes for incorporating the perfume in the bleaching
composition are not critical to the present invention. This can be
done by spray-on, admixture with one or more component of the
bleaching composition or other means known to the man skilled
in the art. A preferred process, for cost and practibility reasons,
is a spray-on process.
Sumrnary of the invention
The present invention relates to a perfumed bleaching
composition containing:
a-a bleaching system selected from
i)-a perhydrate in amount of from 0.1% to 60% by weight
and combined with a bleach activator in amount of from 0.1 ~~6
to 60% by weight,
ii)-a preformed peracid in amount of from 0.1% 1:o 60% by
weight,
and any mixtures thereof,
wherein said perhydrate and/or said preformed peracid are
coated; and
b-a perfume in amount from 0.05% to 2% by weight which
comprises aroma chemicals selected from: primary and secondary
alcohols, aliphatic aldehydes, hydrocinnamic aldehydes, esters
excluding salicylates, unsaturated ketones and mixtures thereof,
wherein the total sum of the weight of said aroma chemicals in
the perfume is at least 30% by weight of the perfume.
In preferred embodiments of the invention, the bleaching
~ composition may comprise a coated bleach activator and/or a
chelant such as EDDS which further enhances the storage
stability of the perfume.
Detailed description of the invention
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The present invention contemplates bleaching compositions
havin3 an excellent perfume fragrance as well as an excellent
perfume stability.
More particularly, it relates to a perfumed bleaching composition
containing:
a-a bleaching system selected from
i)-a perhydrate in amount of from 0.1% to 60% by weight
and combined with a bleach activator in amount of from 0.1 %
to 60% by weight,
ii)-a preformed peracid in amount of from 0.1% to 60% by
weight,
and any mixtures thereof,
wherein said perhydrate and/or said preformed peracid are
coated; and
b-a perfume in amount from 0.05% to 2% by weight which
comprises aroma chemicals selected from: prirnary and secondary
alcohols, aliphatic aldehydes, hydrocinnamic aldehydes, esters
excluding salicylates, unsaturated ketones and rnixtures thereof,
wherein the total sum of the weight of said aroma chemicals in
the perfume is at least 30% by weight of the perfume.
~2le~ching System
The compositions according to the present invention herein
contain bleaching agents or bleaching compositions containing a
bleaching system, selected from a perhydrate in combination
with one or more bleach activators and one or more preformed
peracids wherein said perhydrate and/or said preformed peracid
are coated. When present, bleaching agents will typically be at
levels of from 0.1% to 60%, more typically from 1% to 30%,
and nnore preferably from 5% to 20% of the bleaching
composition, especially for fabric laundering.
The bleaching agents used herein can be any of the
bleaching agents useful for detergent compositions in textile
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cleaning, hard surface cleaning, or other cleaning purposes that
are now known or become known. The bleaching agent, source
of alkaline hydrogen peroxide in the wash liquor, is an inorganic
perhydrate bleach or a preformed peracid.
The perhydrate may be any of the alkali inorganic salts such as
perborate monohydrate or tetrahydrate, percarbonate,
perphosphate and persilicate salts, but is conventionally an alkali
metal perborate or percarbonate.
Sodium percarbonate, which is the preferred perhydrate, is an
addition compound having a formula corresponding to
2Na2C03.3H202, and is available commercially as a crystalline
solid. Most commercially available material includes a low level of
a heavy metal sequestrant such as EDTA, 1-hydroxyethylene
1,1-diphosphonic acid (HEDP) or an aminophosphonate, that is
incorporated during the manufacture process.
Another category of bleaching agent that can be used in place of
or in combination with the mixture of a coated perhydrate and a
bleach activator encompasses the preformed peracid bleachir3g
agents and salts thereof. Suitable examples of this class of
agents include (6-octylamino)-6-oxo-caproic acid, (6-nonylamino)-
6-oxo-caproic acid, (6-decylamino)-6-oxo-caproic acid,
magnesium monoperoxyphthalate hexahydrate, the magnesium
salt of metachloro perbenzoic acid, 4-nonylamino-4-
oxoperoxybutyric acid and diperoxydodecanedioic acid. Such
bleaching agents are disclosed in U.S. Patent 4,483,781, U.S.
Patent 4,634,551, EP 0,133,354, U.S. Patent 4,412,934 and
EP 0,1 70,386.
Mixtures of bleaching agents can also be used.
~ An essential component of the invention is a coating for the
bleaching agent which prevents the source of damage (hydrogen
~ peroxide (H202) and/or peroxide anion ) from diffusion such that less than 5% of the peroxide source is diffused upon storage.
Thereby, the present invention provides an enhancement in the
perfume stability after a minimum of 24 hours storage of at least
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1 panel grade, preferably 2 panel grades, after grading conducted
by an expert panel. The stability grade is given versus a
labora1:ory prepared standard product (grade 10.0) on a 1 to 10
scale. The bleach agent coating material can be selected from
mixtures of alkali metal sulphate and carbonate, sodium silicate,
borate and water-soluble surfactant. The bleaching agent is
preferably percarbonate. The most preferred coating material
comprïses mixed salt of an alkali and/or alkaline earth metal
sulphate and carbonate.
Such coatings together with coating processes have previously
been described in GB-1,466,799. The weight ratio of the mixed
salt coating material to the bleaching agent lies in the range from
1: 200 to 1: 4, more preferably from 1: 99 to 1: 9, and most
preferably from 1 : 49 to 1 :19. Preferably, the mixed salt is of
sodium sulphate and sodium carbonate which has the general
formula Na2S04.n.Na2C03 wherein n is from 0.1 to 3,
preferably n is from 0.3 to 1.0 and most preferably n is from 0.2
to 0.5.
Another suitable coating material is sodium silicate of SiO2:
Na20 ratio from 1.6: 1 to 3.4: 1, preferably 2.8: 1, applied as
an aqueous solution to give a level of from 2% to 10%, (normally
from 3% to 5%) of silicate solids by weight of the bleaching
agent. Magnesium silicate can also be included in the coating.
Also useful as bleaching agent coating materials are sodium
citrat~, borats or water-soluble surfactants such as linear alkyl
benzelle sulphonate and alkyl ether sulphate. A useful coating
material for the percarbonate bleaching agent is a solid inorganic
coating material consisting of a mixture of sodium carbonate and
sodiurn chloride disclosed in EP-A-592969.
Preferred peroxygen bleaching agents selected from alkali
metal perborates tetrahydrates and monohydrates and
percarbonates, etc., are combined with bleach activators, which
lead to the in situ production in aqueous solution (i.e., during the
washing process) of the peroxy acid corresponding to the bleach
activator.
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The amount of bleach activator will typically be from 0.1% to
60%, more typically from 0.5% to 40% by weight of the
bleaching composition.
These activators preferably contain one or more N- or O-acyl
groups and may be selected from a wide range of classes.
Various nonlimiting examples of activators are disclosed in U.S.
Patent 4,915,854 and U.S. Patent 4,412,934. The
nonanoyloxybenzene sulfonate (NOBS), isononanoyloxybenzene
sulfonate (ISONOBS) and tetraacetyl ethylene diamine (TAED)
activators are typical, and mixtures thereof can also be used.
Highly preferred amido-derived bleach activators are those
of the formulae:
R1 N(R5)C(o)R2C(o)L or R1 C(o)N(R5)R2C~o)L
wherein R1 is an alkyl group containing from 6 to 12 carbon
atoms, R2 is an alkylene containing from 1 to 6 carbon a~oms,
R5 is H or alkyl, aryl, or alkaryl containing from 1 to 10 carbon
atoms, and L is any suitable leaving group. A leaving ~roup is
any group that is displaced from the bleach activator as a
consequence of the nucleophilic attack on the bleach activator by
the perhydrolysis anion. A preferred leaving group is phenyl
s~slfonate.
Preferred examples of bleach activators of the above
formulae include (6-octanamido-caproyl)oxybenzenesulfonate, (6-
nonanamidocaproyl)oxybenzenesulfonate, (6-decanamido-
caproyl)oxybenzene- sulfonate, and mixtures thereof as described
in U.S. Patent 4,634,551.
Another class of bleach activators comprises the
benzoxazin-type activators disclosed in U.S. Patent 4,966,723.
A highly preferred activator of the benzoxazin-type is:
ll
'o
Still another class of preferred bleach activators includes
the acyl lactam activators, especially acyl caprolactams and acyl
valerolactams of the formulae:
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O O
~ I--CH2--CH2~ 0 I--CH2--CH2
R6--C--N~ ,C H2 R6--C--N
CH2--CH2 CH2--CH2
wherein R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group
containing from 1 to 12 carbon atoms. Highly preferred lactam
activa1:ors include benzoyl caprolactam, octanoyl caprolactam,
3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam,
decanoyl caprolactam, undecenoyl caprolactam, benzoyl
valerolactam, octanoyl valerolactam, decanoyl valerolactam,
undec~noyl valerolactam, nonanoyl valerolactam, 3,5,5-
trimethylhexanoyl valerolactam and mixtures thereof. See also
U.S. Patent 4,545,784, which discloses acyl caprolactams,
including benzoyl caprolactam, adsorbed into sodium perborate.
Another class of preferred bleach activators include the cationic
bleach activators, derived from the valerolactam and acyl
caprolactam compounds, of forrnula:
+
R~ R'
\ 11
\ / 2
CH2--CH2
wherein x is 0 or 1, substituents R, R' and R" are each C1-C10
alkyl or C2-C4 hydroxy alkyl groups, or [(CyH2y)0]n~R"' wherein
y=2-4, n= 1-20 and R"' is a C1-C4 alkyl group or hydrogen and
X is an anion.
Mixture of any of the bleach activators hereinbefore described
may be used.
In a preferred embodiment, the bleach activator component is in
a coa1:ed form. The coating rnaterial is selected frorn a mixture of
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alkali metal Cg-C22 fatty acid salts in admixture with the
corresponding fatty acids (disclosed in GB 1507312), a coating
of C14-C1g fatty acid mixtures (disclosed in GB 1381121), a
mixture of C12-C14 fatty acids and C1o-C20 aliphatic alcohols
(disclosed in GB 1441416) and an organic acid coating (disclosed in
WO 92/13798).
Bleaching agents other than oxygen bleaching agents are
also known in the art and can optionally be utilized herein. One
type of non-oxygen bleaching agent of particular interest includes
photoactivated bleaching agents such as the sulfonated zinc
and/or aluminium phthalocyanines. See U.S. Patent 4,033,718.
If used, bleaching compositions will typically contain from
0.025% to 1.25%, by weight, of such bleaches, especially
sulfonate zinc phthalocyanine.
If desired, the bleaching compounds can be catalysed by
means of a manganese compound. Such compounds are well
known in the art and include, for example, the manganese-based
catalysts disclosed in U.S. Pat. 5,246,621, U.S. Pat. 5,244,594;
U.S. Pat. 5,194,416; U.S. Pat. 5,114,606; and EP 549,271A1,
549,272A1, 544,440A2, and 544,490A1; Preferred examples
of these catalysts include MnlV2~u-0)3(1,4,7-trimethyl-1,4,7-
triazacyclononane)2(PF6)2, Mnlll2(u-O) 1 (u-OAc)2(1,4,7-
trimethyl-1,4,7-triazacyclononane)2 (ClO4)2, MnlV4(u-o)6(1,4,7-
triazacyclononane)4(CI04)4, MnlllMnlV4(u-O)l(u-OAc)2 (1,4,7-
trimethyl-1,4,7-triazacyclononane)2(C104)3, MnlV(1,4,7-
trimethyl-1,4,7-triazacyclononane)- (OCH3)3(PF6), and mixtures
thereof. Other metal-based bleach catalysts include those
disclosed in U.S. Pat. 4,430,243 and U.S. Pat. 5,114,611. The
use of manganese with various complex ligands to enhance
bleaching is also reported in the following United States Patents:
4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,117;
5,274,147; 5,153,161; 5,227,084.
The other essential component of the invention is a perfume
connposition comprising aroma chemicals selected from primary
and secondary alcohols, aliphatic aldehydes, hydrocinnamic
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aldehydes, esters excluding salicylates, unsaturated ketones and
mixtures thereof.
Primary alcohols suitable for the purpose of the invention
are 3,7-dimethyl-6-octen-1-ol, 3,7-dimethyl-2,6-octadien-1-ol,
phenyl ethyl alcohol, 1-pentanol, 3-methyl-5-phenyl and
cyclohexyl ethyl alcohol. Preferred primary alcohols are 3,7-
dimethlyl-6-octen-1-ol, 3,7-dimethyl-2,6-octadien-1-ol and phenyl
ethyl alcohol.
Secondary alcohols suitable for use in the perfume composition
are cyclohexanol,2-tertiary butyl, 4-methyl-3-decen-5-ol,
cyclohexanol,4-tertiary butyl and 4-iso propyl cyclohexanol.
Preferred secondary alcohols are cyclohexanol,2-tertiary butyl
and 4-methyl-3-decen-5-ol. When used such alcohols compounds
will be at a level of from 1% to 50%, preferabiy at a level of
from 20% to 45% and more preferably from 25% to 35% by
weigh1: of the perfume composition.
Qliphatic aldehydes suitable for the purpose of the invention
are octanal, nonanal, decanal, undecanal, dodecanal, 10-
undec~nal, 2-methyl undecanal and 2-methyl decanal.
Hydrocinnamic aldehydes suitable for tlhe purpose of the
invention are 2-methyl-3-(4-tertiary butyl phenyl) propanal and 2-
methyl-3-~4-iso propyl phenyl) propanal. When used such
aliphal:ic and hydrocinnamic aldehydes will be at a level of up to
30%, preferably at a level of up to 20% and more preferably up
to 10~,6 by weight of the perfume composition.
Esters, excluding salicylates, suitable for the purpose of the
invention are benzyl acetate, benzyl propionate, phenyl ethyl
acetate, citronellyl acetate, geranyl acetate, 2-methyl-3-phenyl-
propan-2-yl acetate, 4-tertiary butyl cyclohexyl acetate, 2-tertiary
butyl cyclohexyl acetate, hexahydro-4,7-methano-inden-5-yl
acetate, hexahydro-4,7-methano-inden-6-yl acetate, hexahydro-
4,7-methano-inden-5-yl propionate, hexahydro-4,7-methano-
inden-6-yl propionate and methyl benzoate. Preferred esters,
excluding salicylates, are 2-methyl-3-phenyl-propan-2-yl acetate,
2-tertiary butyl cyclohexyl acetate, hexahydro-4,7-methano-
inden-5-yl acetate, hexahydro-4,7-methano-inden-6-yl acetate,
hexahydro-4,7-methano-inden-5-yl propionate, hexahydro-4,7-
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methano-inden-6-yl propinate and methyl benzoate. When used
such esters excluding salicylates will be at a level of from 5% to
50%, preferably at a level of from 10% to 40% and more
preferably from 25% to 35% by weight of the perfume
composition.
Unsaturated ketones suitable for the purpose of the
invention are 7-acetyl 1 ,2,3,4,5,6,7,8-octanhydro 1,1,6,7 tetra
methyl naphtalene, 3-buten-2-one 3-methyl-4-(2,6,6, trimethyl-2-
cyclohexen-1-yl), 3-buten-2-one 4-(2,6,6-trimethyl-1-cyclohexen-
1-yl), 3-buten-2-one 4-(2,6,6-trimethyl-2-cyclohexen-1-yl) and
ketone cedr-8-enyl methyl. When used such unsaturated ketones
will be at a level of from up to 30%, preferably at a level of up to
25~h by weight of the perfume composition.
The total sum of the weight of said aroma chemicals, described
herein before, present in the perfume composition is at least
30~~6, preferably at least 50% and more preferably at least 80%
by weight of the perfume.
The perfume composition is incorporated in the bleaching
composition of the invention at a level of from 0.05% to 2% by
weight, preferably from 0.01% to 1% of the bleaching
composition.
The incorporation of other ingredients additional to the bleaching
system and perfume can be advantageous in enhancing the
stability of the perfume. In particular, the bleaching composition
may comprise one or more iron and/or manganese chelating
agents which further enhances the storage stability of the
perfume.
Chelating Agents - Such chelating agents can be selected
from the group consisting of amino carboxylates, amino
phosphonates, polyfunctionally-substituted aromatic chelating
agents and mixtures therein, all as hereinafter defined. Without
intending to be bound by theory, it is believed that the benefit of
these materials is due in part to their exceptional ability to
remove iron and manganese ions from washing solutions by
formation of soluble chelates.
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Amino carboxylates useful as optional chelating agents
include ethylenediaminetetracetates, N-
hydroxyethylethylenediaminetriacetates, nitrilotriacetates,
ethylenediamine tetraproprionates, triethylenetetraamine-
hexac:etates, diethylenetriaminepentaacetates, and ethanoldi-
glycines, alkali metal, ammonium, and substituted ammonium
salts therein and mixtures therein.
Preferred biodegradable non-phosphorus chelants for use herein
are ethylenediamine disuccinate (nEDDS"), especially the [S,Sl
isomer as described in U.S. Patent 4,704,233, ethylenediamine-
N,N'-diglutamate (EDDG) and 2-hydroxypropylene-diamine-N,N'-
disuccinate (HPDDS) compounds.
Amino phosphonates are also suitable for use as chelating
agents in the compositions of the invention when at least low
levels of total phosphorus are permitted in detergent
compositions, and include ethylenediaminetetrakis
~methylenephosphonates) available under the trademark
DEQUEST from Monsanto. Preferably, these amino
phosphonates do not contain alkyl or alkenyl groups with more
than 6 carbon atoms.
Polyfunctionally-substituted aromatic chelating agents are
also useful in the compositions herein. See U.S. Patent
3,812,044. Preferred compounds of this type in acid form are
dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-
disulfobenzene .
If utilized, these chelating agents will generally comprise
from 0.1% to 10% by weight of the bleaching compositions
herein. More preferably, if utilized, the che!ating agents will
complrise from 0.1% to 3.0% by weight of such compositions.
Additional detergent comr~onents
The bleaching compositions of the invention may also contain
additional detergent components. 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 cleaning operation for which it is to be used.
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The compositions of the invention may, for example, be
formulated as hand and machine laundry detergent compositions,
including laundry additive compositions and compositions suitable
for use in the pretreatment of stained fabrics and machine
dishwashing compositions.
When incorporated in compositions suitable for use in a machine
washing method, eg: machine laundry and machine dishwashing
methods, the compositions of the invention preferably contain
one or more additional detersive components.
For the purpose of the invention, when said bleaching
composition comprises additional detergent components, as
described herein after, the terms 'bleaching composition' and
'detergent composition' will be used herein after as synonymous.
Detersive Surfactants - Nonlimiting exarnples of surfactants
useful herein typically at levels from 1% to 55%, by weight,
include the conventional C1 1-C18 alkyl benzene sulfonates
(nLASn) and primary, branched-chain and random C10-C20 alkyl
sulfates ("ASn), the C1 0-C1 8 secondary (2,3) alkyl sulfates of
the formula CH3(CH2)x(CHOSO3-M + ) CH3 and CH3
(CH2)y(CHOS03~M + ) CH2CH3 where x and (y + 1 ) are integers
of at least 7, preferably at least 9, and M is a water-solubilizing
cation, especially sodium, unsaturated sulfates such as oleyl
sulfate, the C10-C1g alkyl alkoxy sulfates ("AEXS"; especially E0
1-7 ethoxy sulfates), C1 0-C1 8 alkyl alkoxy carboxylates
(especially the E0 1-5 ethoxycarboxylates), the C1 0-1~3 glycerol
ethers, the C 1 o-C 1 8 alkyl polyglycosides and their corresponding
sulfated polyglycosides, and C 1 2-C 1 8 alpha-sulfonated fatty acid
esters. If desired, the conventional nonionic and amphoteric
surfactants such as the C1 2-C1 8 alkyl ethoxylates ("AE")
including the so-called narrow peaked alkyl ethoxylates and C6-
C12 alkyl phenol alkoxylates (especially ethoxylates and mixed
ethoxy/propoxy), C 1 2-C 1 8 betaines and sulfobetaines
(nsultainesn), C1 o-C1 8 amine oxides, and the like, can also be
included in the overall compositions. The C1 o-C1 8 N-alkyl
polyhydroxy fatty acid amides can also be used. Typical
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14
examples include the C 1 2-C1 8 N-methylglucamides. See WO
9,206,154. Other sugar-derived surfactants include the N-aikoxy
polyhydroxy fatty acid amides, such as C10-C1g N (3-
methoxypropyl) glucamide. The N-propyl through N-hexyl C12-
C18 glucamides can be used for low sudsing. C10-c20
conventional soaps may also be used. If high sudsing is desired,
the branched-chain C1 o-C1 6 soaps may be used. Mixtures of
anionic and nonionic surfactants are especially useful. Other
conventional useful surfactants are listed in standard texts.
Adjunct Ingredients
The compositions herein can optionally include one or more
other detergent adjunct materials or other materials for assisting
or enhancing cleaning performance, treatment of the substrate to
be cleaned, or to modify the aesthetics of the detergent
composition (e.g., colorants, dyes, etc.). The following are
illustrative examples of such adjunct materials.
Ruilders - Detergent builders can optionally be included in
the compositions herein to assist in controlling mineral hardness.
Inorganic as well as organic builders can be used. Builders are
typically used in fabric laundering compositions to assist in the
removal of particulate soils.
The level of builder can vary widely depending upon the end
use of the composition and its desired physical form. When
present, the compositions will typically comprise at least 1%
builder. Granular formulations typically comprise from 10% to
80%~ more typically from 15% to 50% by weight, of the
deteraent builder. Lower or higher levels of builder, however, are
not meant to be excluded.
Inorganic or phosphate-containing detergent builders
inclutle, but are not limited to, the alkali metal, ammonium and
alkanolammonium salts of polyphosphates (exemplified by the
tripolyphosphates, pyrophosphates, and glassy polymeric meta-
phosphates).
Non-phosphate builders may also be used. These can include, but
are not restricted to phytic acid, silicates, alkali metal carbonates
(including bicarbonates and sesquicarbonates), sulphates,
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1 5
aluminosilicates, monomeric poiycarboxylates, homo or
copolymeric polycarboxylic acids or their salts in which the
polycarboxylic acid comprises at least two carboxylic radicals
separated from each other by not more than two carbon atoms,
organic phosphonates and aminoalkylene poly (alkylene
phosphonates).
The compositions herein also function in the presence of the so-
called "weak" builders (as compared with phosphates) such as
citrate, or in the so-called "underbuilt" situation that may occur
with zeolite or layered silicate builders.
Examples of silicate builders are the so called 'amorphous'
alkali metal silicates, particularly those having a SiO2:Na2O ratio
in the range 1.6:1 to 3.2:1 and crystalline layered silicates, such
as the layered sodium silicates described in U.S. Patent
4,664,839. NaSKS-6 is the trademark for a crystalline la~,cered
silicate marketed by Hoechst (commonly abbreviated herein as
"SKS-6n). Unlike zeolite builders, the Na SKS-6 silicate builder
does not contain aluminum. NaSKS-6 has the delta-Na2Si2Os
morphology form of layered silicate. It can be prepared by
methods such as those described in German DE-A-3,417,649
and DE-A-3,742,043. SKS-6 is a highly preferred layered silicate
for use herein, but other such layered silicates, such as those
having the general formula NaMSix02x+ 1 ~YH2O wherein Nl is
sodiurn or hydrogen, x is a number from 1.9 to 4, preferably 2,
and y is a number from 0 to 20, preferably O can be used herein.
Various other layered silicates from Hoechst include l\laSKS-5,
NaSKS-7 and NaSKS-1 1, as the alpha, beta and gamma forms.
As noted above, the delta-Na2Si2Os (NaSKS-6 form) is most
preferred for use herein. Other silicates may also be useful such
as for example magnesium silicate, which can serve as a
crispening agent in granular formulations, as a stabilising agent
for oxygen bleaches, and as a component of suds control
systems.
Examples of carbonate builders are the alkaline earth and
alkali metal carbonates as disclosed in German Patent Application
No. 2,321 ,001 published on November 1 5, 1 973.
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16
Aluminosilicate builders are useful in the present invention.
Aluminosilicate builders are of great importance in most currently
marketed heavy duty granular detergent compositions, and can
also be a significant builder ingredient in liquid detergent
formulations. Aluminosilicate builders include those having the
empirical formula:
Naz[(Alo2)z(sio2)y] ~XH20
wherein z and y are integers of at least 6, the molar ratio of z to
y is in the range from 1.0 to 0.5, and x is an integer from 15 to
264.
Useful aluminosilicate ion exchange materials are
commercially available. These aluminosilicates can be crystalline
or annorphous in structure and can be naturally-occurring
aluminosilicates or synthetically derived. A method for producing
aluminosilicate ion exchange materials is disclosed in U.S. Patent
3,985,669. Preferred synthetic crystalline aluminosilicate ion
exchange materials useful herein are available under the
desi~nations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X.
In an especially preferred embodiment, the crystalline
aluminosilicate ion exchange material has the formula:
Na1 2[(A1~2)1 2(sio2)1 2] xH20
wherein x is from 20 to 30, especially 27. This material is
known as Zeolite A. Dehydrated zeolites (x = O - 10) may also
be used herein. Preferably, the aluminosilicate has a particle size
of 0.1-10 microns in diameter.
Or~anic detergent builders suitable for the purposes of the
present invention include, but are not restricted to, a wide variety
of polycarboxylate compounds. As used herein, "poly-
carboxylate" refers to compounds having a plurality of
carboxylate groups, preferably at least 3 carboxylates.
Polycarboxylate builder can generally be added to the
cornposition in acid form, but can also be added in the form of a
neutralised salt. When utilized in salt form, alkali metals, such as
sodium, potassium, and lithium, or alkanolammonium salts are
preferred.
Included among the polycarboxylate builders are a variety of
categories of useful materials. One important category of
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polycarboxylate builders encompasses the ether polycarboxy-
lates, including oxydisuccinate, as disclosed in U.S. Patent
3,128,287 and U.S. Patent 3,635,830. See also "TMS/TDS"
builders of U.S. Patent 4,663,071. Suitable ether
polycarboxylates also include cyclic compounds, particularly
alicyclic compounds, such as those described in U.S. Patents
3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.
Other useful detergency builders include the ether
hydroxypolycarboxylates, copolymers of maleic anhydride with
ethylene or vinyl methyl ether, or acrylic acid, 1, 3, 5-trihydroxy
benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic
acid, the various alkali metal, ammonium and substituted
ammonium salts of polyacetic acids such as ethylenediamine
tetraacetic acid and nitrilotriacetic acid, as well as
polycarboxylates such as mellitic acid, succinic acid, oxy-
disuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid,
carboxymethyloxysuccinic acid, and soluble salts thereof.
Citrate builders, e.g., citric acid and soluble salts thereof
(particularly sodium salt), are polycarboxylate builders of
particular importance for heavy duty liquid detergent formulations
due to their availability from renewable resources and their
biodegradability. Citrates can also be used in granular
compositions, especially in combination with zeolite and/or
layered silicate builders. Oxydisuccinates are also especially
useful in such compositions and combinations.
Also suitable in the compositions containing the present
invention are the 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the
related compounds disclosed in U.S. Patent 4,566,984. Useful
succinic acid builders include the Cs-C20 alkyl and alkenyl
succinic acids and salts thereof. A particularly preferred
cornpound of this type is dodecenylsuccinic acid. Specific
examples of succinate builders include: laurylsuccinate,
myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate
(preferred), 2-pentadecenylsuccinate, and the like.
Laurylsuccinates are the preferred builders of this group, and are
described in EP 0,200,263.
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18
Other suitable polycarboxylates are disclosed in U.S. Patent
4,144,226 and in U.S. Patent 3,308,067. See also U.S. Pat.
3,723,322.
Fatty acids, e .9 ., C 1 2-C 1 8 monocarboxylic acids, can also
be inc:orporated into the compositions alone, or in combination
with the aforesaid builders, especially citrate and/or the succinate
builders, to provide additional builder activity. Such use of fatty
acids will generally result in a diminution of sudsing, which
should be taken into account by the formulator.
In situations where phosphorus-based builders can be used,
and especially in the formulation of bars used for hand-laundering
operations, the various alkali metal phosphates such as the well-
known sodium tripolyphosphates, sodium pyrophosphate and
sodium orthophosphate can be used. Phosphonate builders such
as ethane-1-hydroxy-1,1-diphosphonate and other known
phosphonates (see, for example, U.S. Patents 3,159,581;
3,213,030; 3,422,021; 3,400,148 and 3,422,137) can also be
used.
En7ymes - Enzymes can be included in the formulations
herein for a wide variety of fabric laundering purposes, including
removal of protein-based, carbohydrate-based, or triglyceride-
based stains, for example, and for the prevention of fugitive dye
translFer, and for fabric restoration. The enzymes to be
incorporated include proteases, amylases, lipases, cellulases, and
peroxidases, as well as mixtures thereof. Other types of
enzymes may also be included. They may be of any suitable
origin, such as vegetable, animal, bacterial, fungal and yeast
origin. However, their choice is governed by several factors such
as pH-activity and/or stability optima, thermostabiiity and
stability versus active detergents and builders. In this respect
bacterial or fungal enzymes are preferred, such as bacterial
amylases and proteases, and fungal cellulases.
Enzymes are normally incorporated at levels sufficient to
provi~e up to 5 mg by weight, more typically 0.01 mg to 3 mg,
of active enzyme per gram of the composition. Stated
otherwise, the compositions herein will typically comprise from
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19
0.001 % to 5%, preferably 0.01 %-1 % by weight of a
commercial enzyme preparation.
Suitable examples of proteases are the subtilisins which are
obtained from particular strains of B. subtilis and B. licheniforms.
Another suitable protease is obtained from a strain of Bacillus,
having maximum activity throughout the pH range of 8-12,
developed and sold by Novo Industries A/S under the registered
trade name ESPERASE. The preparation of this enzyme and
analogous enzymes is described in GB 1,243,784 of Novo.
Proteolytic enzymes suitable for removing protein-based stains
that are commercially available include those sold under the
tradenames ALCALASE and SAVINASE by Novo Industries A/S
(Denmark) and MAXATASE by International Bio-Synthetics, Inc.
(The Netherlands). Other proteases include Protease A (see EP
130,756) and Protease B (see EP257189).
Amylases include, for example, a-amylases described in GB
1,296,839 (Novo), RAPIDASE, International Bio-Synthetics, Inc.
and TERMAMYL, Novo Industries. Fungamyl (Novo) is especially
useful.
The cellulases usable in the present invention include both
bacterial or fungal cellulase. Preferably, they will have a pH
optimum of between 5 and 9.5. Suitable cellulases are disclosed
in U.S. Patent 4,435,307, which discloses fungal cellulase
produced from Humicola insolens and Humicola strain DSM1800
or a cellulase 212-producing fungus belonging to the genus
Aeromonas, and cellulase extracted from the hepatopancreas of a
marine mollusk (Dolabella Auricula Solander). suitable cellulases
are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-
OS-2.247.832. ENDO A, CAREZYME both from Novo Industries
A/S are especially useful.
Suitable lipase enzymes for detergent usage include those
produced by microorganisms of the Pseudomonas group, such as
Pseudomonas stutzeri ATCC 19.154, as disclosed in GB
- 1,372,034. See also lipases in Japanese Patent Application
53,20487, laid open to public inspection on February 24, 1978.
This lipase is available from Amano Pharmaceutical Co. Ltd.,
Nagoya, Japan, under the trade name Lipase P "Arnano,"
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hereinafter referred to as "Amano-P." Other commerciai lipases
include Amano-CES, lipases ex Chromobacter viscosum, e.g.
Chromobacter viscosum var. Iipolyticum NRRLB 3673,
cornmercially available from Toyo Jozo Co., Tagata, Japan; and
furth0r Chromobacter viscosum lipases from U.S. Biochemical
Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex
Pseudomonas gladioli. The LIPOLASE enzyme derived from
Humicola lanuginosa and commercially available from Novo (see
also E~P 341,947) is a preferred lipase for use herein.
Peroxidase enzymes are used in combination with oxygen
sources, e.g., percarbonate, perborate, persulfate, hydrogen
peroxide, etc. They are used for "solution bleaching," i.e. to
prevent trans~er of dyes or pigments removed from substrates
during wash operations to other substrates in the wash solution.
Peroxidase enzymes are known in the art, and include, for
example, horseradish peroxidase, ligninase, and haloperoxidase
such as chloro- and bromo-peroxidase. Peroxidase-containing
detergent compositions are disclosed, for example, in PCT
International Application WO 89/099813, published October 19,
1989, by O. Kirk, assigned to Novo Industries A/S.
A wide range of enzyme materials and means for their
incorporation into synthetic detergent compositions are also
disclosed in U.S. Patent 3,553,139. Enzymes are further
disclosed in U.S. Patent 4,101,457 and in U.S. Patent
4,507,219. Enzyme materials useful for liquid detergent
formulations, and their incorporation into such formulations, are
disclosed in U.S. Patent 4,261,868. Enzymes for use in
deter~ents can be stabilized by various techniques. Enzyme
stabilisation techniques are disclosed and exemplified in U.S.
Patent 3,600,31 9 and EP 0 1 99 405. Enzyme stabilisation
systems are also described, for example, in U.S. Patent
3,5 1 9,570.
Fn~yme Stabilisers - The enzymes employed herein are
stabilized by the presence of water-soluble sources of calcium
and/or magnesium ions in the finished compositions which
provide such ions to the enzymes. (Calcium ions are generally
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somewhat more effective than magnesium ions and are preferred
herein if only one type of cation is being used.) Additional
stability can be provided by the presence of various other art-
disclosed stabilisers, especially borate species: see Severson,
U.S. 4,537,706. Typical detergents, especially liquids, will
comprise from 1 to 30, preferably from 2 to 20, more preferably
frorn 5 to 15, and most preferably from 8 to 12, millimoles of
calcium ion per liter of finished composition. This can vary
somewhat, depending on the amount of enzyme present and its
response to the calcium or magnesiurn ions. The level of calcium
or magnesium ions should be selected so that there is always
some minimum level available for the enzyme, after allowing for
complexation with builders, fatty acids, etc., in the composition.
Any water-soluble calcium or magnesium salt can be used as the
source of calcium or magnesium ions, including, but not limited
to, calcium chloride, calcium sulfate, calcium malate, calcium
maleate, calcium hydroxide, calcium formate, and calcium
acetate, and the corresponding magnesium salts. A small
amount of calcium ion, generally from 0.05 to 0.4 millimoles per
liter, is often also present in the composition due to calcium in
the enzyme slurry and formula water. In solid detergent
compositions the formulation may include a sufficient quantity of
a water-soluble calcium ion source to provide such amounts in
the laundry liquor. In the alternative, natural water hardness may
suffice.
It is to be understood that the foregoing levels of calcium
and/or magnesium ions are sufficient to provide enzyme stability.
More calcium and/or magnesium ions can be added to the
compositions to provide an additional measure of grease removal
performance. Accordingly, as a general proposition the
compositions herein will typically comprise from 0.05% to 2%
by weight of a water-soluble source of calcium or magnesium
ions, or both. The amount can vary, of course, with the amount
~ and type of enzyme employed in the composition.
The compositions herein may also optionally, but
preferably, contain various additional stabilizers, especially
borate-type stabilizers. Typically, such stabilizers will be used at
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levels in the compositions from 0.25% to 10%, preferably from
0.5% to 5%, more preferably from 0.75% to 3%, by weight of
boric acid or other borate compound capable of forming boric
acid in the composition (calculated on the basis of boric acid).
Boric acid is preferred, although other compounds such as boric
oxider borax and other alkali metal borates (e.g., sodium ortho-,
meta- and pyroborate, and sodium pentaborate) are suitable.
Substituted boric acids (e.g., phenylboronic acid, butane boronic
acid, and p-bromo phenylboronic acid) can also be used in place
of boric acid.
t'lay Soil Removal/Anti-redeposition Agents - The
compositions according to the present invention can also
optionally contain water-soluble ethoxylated amines having cla
soil removal and antiredeposition properties. Granular detergent
cornpositions which contain these compounds typically contain
from 0.01 % to 10.0% by weight of the water-soluble
ethoxylates amines; liquid detergent compositions typically
contain 0.01 % to 5%.
The most preferred soil release and anti-redeposition agent
is ethoxylated tetraethylenepentamine. Exemplary ethoxylated
amines are further described in U.S. Patent 4,597,898,
Vand~erMeer, issued July 1, 1986. Another group of preferred
clay soil removal-antiredeposition agents are the cationic
compounds disclosed in EP 111,965. Other clay soil
removal/antiredeposition agents which can be used include the
ethoxylated amine polymers disclosed in EP 111,984; the
zwitterionic polymers disclosed in EP 112,592; and the amine
oxides disclosed in U.S. Patent 4,548,744. Other clay soil
removal and/or anti redeposition agents known in the art can also
be utilized in the compositions herein. Another type of preferred
antire:deposition agent includes the carboxy rnethyl cellulose
(CMC:) materials. These materials are well known in the art.
Polynneric Soil Release Agent - Any polymeric soil release agent
known to those skilled in the art can optionally be employed in
the compositions and processes of this invention. Polymeric soil
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release agents are characterized by having both hydrophilic
segments, to hydrophilize the surface of hydrophobic fibers, such
as polyester and nylon, and hydrophobic segments, to deposit
upon hydrophobic fibers and remain adhered thereto through
completion of washing and rinsing cycles and, thus, serve as an
anchor for the hydrophilic segments. This can enable stains
occurring subsequent to treatment with the soil release agent to
be more easily cleaned in later washing procedures.
Soil release agents characterized by poly(vinyl ester)
hydrophobe segments include graft copolymers of poly(vinyl
ester), e.g., C1-C6 vinyl esters, preferably poly(vinyl acetate)
grafted onto polyalkylene oxide backbones, such as polyethylene
oxide backbones (see EP 0 219 048). Commercially available
soil release agents of this kind include the SOKALAN type of
material, e.g., SOKALAN HP-22, available from BASF (West
Germany).
One type of preferred soil release agent is a copolymer
having random blocks of ethylene terephthalate and polyethylene
oxide (PEO) terephthalate. The molecular weight of this
polymeric soil release agent is in the range of from 25,000 to
55,000. See U.S. Patent 3,959,230 to Hays and U.S. Patent
3,893,929.
Another preferred polymeric soil release agent is a polyester
with repeat units of ethylene terephthalate units contains 10-
15% by weight of ethylene terephthalate units together with 90-
80% by weight of polyoxyethylene terephthalate units, derived
from a polyoxyethylene glycol of average molecular weight 300-
5,000. Exa~ples of this polymer include the commercially
available material ZELCON 5126 (from Dupont) and MILEASE T
(from ICI). See also U.S. Patent 4,702,857.
Another preferred polymeric soil release agent is a
sulfonated product of a substantially linear ester oligomer
comprised of an oligomeric ester backbone of terephthaloyl and
~ oxyalkyleneoxy repeat units and terminal moieties covalently
attached to the backbone. These soil release agents are
described fully in U.S. Patent 4,968,451. Other suitable
polymeric soil release agents include the terephthalate polyesters
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24
of U.S. Patent 4,711,730, the anionic end-capped oligomeric
esters of U.S. Patent 4,721,580 and the block polyester
oligomeric compounds of U.S. Patent 4,702,857.
Preferred polymeric soil release agents also include the soil
release agents of U.S. Patent 4,877,896, which discloses
anionic, especially sulfoarolyl, end-capped terephthalate esters.
11F utilized, soil release agents wili generally comprise from
0.01 % to 10.0%, by weight, of the compositions herein,
typically from 0.1% to 5%, preferably from 0.2% to 3.0%.
Still another preferred soil release agent is an oligomer with
repeat units of terephthaloyl units, sulfoisoterephthaloyl units,
oxyethyleneoxy and oxy-1,2-propylene units. The repeat units
form the backbone of the oligomer and are preferably terminated
with modified isethionate end-caps. A particularly preferred soil
release agent of this type comprises one sulfoisophthaloyl unit, 5
terephthaloyl units, oxyethyleneoxy and oxy-1,2-propyleneoxy
units in a ratio of from 1.7 to 1.8, and two end-cap units of
sodium 2-(2-hydroxyethoxy)-ethanesulfonate. Said soil release
agent also comprises from 0.5% to 20%, by weight of the
oligomer, of a crystalline-reducing stabilizer, preferably selected
from xylene sulfonate, cumene sulfonate, toluene sulfonate, and
mixtures thereof.
Dye Transfer Inhibiting Agents
The compositions according to the present invention may also
include one or more materials effective for inhibiting the transfer
of dyes from one fabric to another during the cleaning process.
Generally, such dye transfer inhibiting agents include polyvinyl
pyrrolidone polymers, polyamine N-oxide polymers, copolymers of
N-vinylpyrrolidone and N-vinylimidazole, manganese
phthalocyanine, peroxidases, and mixtures thereof. If used, these
agents typically comprise from 0.01 % to 10% by weight of the
composition, preferably from 0.01% to 5%, and more preferably
from 0.05% to 2%.
~ Aore specifically, the polyamine N-oxide polymers preferred
for use herein contain units having the following structural
formuDa: R-AX-P; wherein P is a polymerizable unit to which an N-
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0 group can be attached or the N-0 group can form part of the
polymerizable unit or the N-0 group can be attached to both
uni~s; A is one of the following structures: -NC(0)-, -C(0)0-, -S-, -
0-, -N=; x is 0 or 1; and R is aliphatic, ethoxylated aliphatics,
aromatics, heterocyclic or alicyclic groups or any combination
thereof to which the nitrogen of the N-0 group can be attached
or the N-0 group is part of these groups. Preferred polyamine N-
oxides are those wherein R is a heterocyclic group such as
pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives
thereof.
The N-0 group can be represented by the following general
structures:
(R2)y; N~ hC
~ R3k
wherein R 1, R2, R3 are aliphatic, aromatic, heterocyclic or
alicyclic groups or combinations thereof; x, y and z are 0 or 1;
and the nitrogen of the N-0 group can be attached or form part of
any of the aforementioned groups. The amine oxide unit of the
polyamine N-oxides has a pKa ~ 10, preferably pKa < 7, more
preferred pKa < 6.
Any polymer backbone can be used as long as the amine
oxide polyrner formed is water-soluble and has dye transfer
inhibiting properties. Examples of suitable polymeric backbones
are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide,
polyimides, polyacrylates and mixtures thereof. These polymers
include random or block copolymers where one monomer type is
an amine N-oxide and the other monomer type is an N-oxide. The
amine N-oxide polymers typically have a ratio of amine to the
amine N-oxide of 10:1 to 1:1,000,000. However, the number of
amine oxide groups present in the polyamine oxide polymer can
be varied by appropriate copolymerization or by an appropriate
degree of N-oxidation. The polyamine oxides can be obtained in
almost any degree of polymerization. Typically, the average
molecular weight is within the range of 500 to 1,000,000; more
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26
preferred 1,000 to 500,000; most preferred 5,000 to 100,000.
This preferred class of materials can be referred to as "PVN0".
The most preferred polyamine N-oxide useful in the
compositions herein is poly(4-vinylpyridine-N-oxide) which as an
average molecular weight of 50,000 and an amine to amine N-
oxide ratio of 1:4.
Copolymers of N-vinylpyrrolidone and N-vinylimidazole
polymers (referred to as a class as "PVPVI") are also preferred for
use herein. Preferably the PVPVI has an average molecular
weight range from 5,000 to 1,000,000, more preferably from
5,000 to 200,000, and most preferably from 10,000 to 20,000.
(The average molecular weight range is determined by light
scattering as described in Barth, et al., Chemical Analysis, Vol
1 1 3 . n Modern Methods of Polymer Characterization " . ) The
PVPVI copolymers typically have a molar ratio of N-vinylimidazole
to N-vinylpyrrolidone from 1:1 to 0.2:1, more preferably from
0.8 1 tO 0.3 1~ most preferably from 0.6:1 to 0.4:1. These
copol~/mers can be either linear or branched.
The present invention compositions also may employ a poly-
vinylpyrrolidone ("PVP") having an average molecular weight of
from 5,000 to 400,000, preferably from 5,000 to 200,000, and
more preferably from 5,000 to 50,000. PVP's are known to
persons skilled in the detergent field; see, for example, EP-A-
262,897 and EP-A-256,696. Compositions containing PVP can
also contain polyethylene glycol ("PEGn) having an average
molec:ular weight frorn 500 to 100,000, preferably from 1,000
to 10,000. Preferably, the ratio of PEG to PVP on a ppm basis
deliv~red in wash solutions is from 2:1 to 50:1, and more
preferably from 3:1 to 10:1.
The detergent compositions herein may also optionally
contain from 0.005 % to 5 % by weight of certain types of
hydrophilic optical brighteners which also provide a dye transfer
inhibi~ion action. If used, the compositions herein will preferably
comprise from 0.0 1% to 1% by weight of such optical
brigh~:eners.
The hydrophilic optical brighteners useful in the present
invention are those having the structural formula:
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N~ HI Hl ~NH~NN~
R2 SO3M So3M R~
wherein R 1 is selected from anilino, N-2-bis-hydroxyethyl and
NH-2-hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-
2-hydroxyethyl-N-methylamino, morphilino, chloro and amino; and
M is a salt-forming cation such as sodium or potassium.
When in the above formula, R1 is anilino, R2 is N-2-bis-
hydroxyethyl and M is a cation such as sodium, the brightener is
4,4' ,-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-
2,2'-stilbenedisulfonic acid and disodium salt. This particular
brightener species is commercially marketed under the tradename
Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX
is the preferred hydrophilic optical brightener useful in the
compositions herein.
When in the above formula, R1 is anilino, R2 is N-2-
hydroxyethyl-N-2-methylamino and M is a cation such as sodium,
the brightener is 4,4'-bis[(4-anilino-6-(N-2-hydroxyethyl-N-
methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid
disodium salt. This particular brightener species is commercially
marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy
Corporation.
When in the above formula, R1 is anilino, R2 is morphilino
and M is a cation such as sodium, the brightener is 4,4'-bis[(4-
anilino-6-morphilino-s-triazine-2-yl)amino]2,2'-stilbenedlisulfonic
acid, sodium salt. This particular brightener species is
commercially marketed under the tradename Tinopal AMS-GX by
Ciba Geigy Corporation.
Other specific optical brightener species which may be used
in the present invention provide especially effective dye transfer
inhibition performance benefits when used in combination with
the selected polymeric dye transfer inhibiting agents hereinbefore
described. The combination of such selected polymeric materials
(e.g., PVNO and/or PVPVI) with such selected optical brighteners
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28
(e.g., Tinopal UNPA-GX, Tinopal 5BM-GX and/or Tinopal AMS-
GX) provides significantly better dye transfer inhibition in aqueous
wash solutions than does either of these two detergent
composition components when used alone. Without being bound
by theory, it is believed that such brighteners work this way
because they have high affinity for fabrics in the wash solution
and thlerefore deposit relatively quick on these fabrics. The
extent to which brighteners deposit on fabrics in the wash
solution can be defined by a parameter called the "exhaustion
coefficient". The exhaustion coefficient is in general as the ratio
of a) the brightener material deposited on fabric to b) the initial
brightener concentration in the wash liquor. Brighteners with
relatively high exhaustion coefficients are the most suitable for
inhibiting dye transfer in the context of the present invention.
Of course, it will be appreciated that other, conventional
optical brightener types of compounds can optionally be used in
the present compositions to provide conventional fabric
"brightness" benefits, rather than a true dye transfer inhibiting
effect. Such usage is conventional and well-known to detergent
formulations.
~ Conventional optical brighteners or other brightening or
whitening agents known in the art can be incorporated at levels
typically from 0.05% to 1.2%, by weight, into the detergent
compositions herein. Commercial optical brighteners which may
be useful in the present invention can be classified into
subgroups, which include, but are not necessarily limited to,
derivatives of stilbene, pyrazoline, coumarin, carboxylic acid,
methinecyanines, dibenzothiphene-5,5-dioxide, azoles, 5- and 6-
membered-ring heterocycles, and other miscellaneous agents.
Examples of such brighteners are disclosed in "The Production
and Application of Fluorescent Brightening Agents", M.
Zahradnik, Published by John Wiley & Sons, New York (1982).
Specific exarnples of optical brighteners which are useful in
the present compositions are those identified in U.S. Patent
4,79(),856. These brighteners include the PHORWHITE series of
brighteners from Verona. Other brighteners disclosed in this
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29
reference include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM;
available from Ciba-Geigy; Artic White CC and Artic White CWD,
available from Hilton-Davis, located in Italy; the 2-(4-stryl-
phenyl)-2H-napthol[1,2-dltriazoles; 4,4'-bis- (1,2,3-triazol-2-yl)-
stil- benes; 4,4'-bis(stryl)bisphenyls; and the aminocoumarins.
Specific examples of these brighteners include 4-methyl-7-
diethyl- amino coumarin; 1,2-bis(-venzimidazol-2-yl)ethylene; 1,3-
diphenyl-phrazolines; 2,5-bis(benzoxazol-2-yl)thiophene; 2-stryl-
napth-l 1 ,2-d]oxazole; and 2-(stilbene-4-yl)-2H-naphtho- l 1 ,2-
dltriazole. See also U.S. Patent 3,646,015. Anionic brighteners
are preferred herein.
Suds Suppressors - Compounds for reducing or suppressing the
formation of suds can be incorporated into the compositions of
the present invention. Suds suppression can be of particular
importance in the so-called "high concentration cleaning process"
and in front-loading European-style washing machines.
A wide variety of materials may be used as suds
suppressors, and suds suppressors are well known to those
skilled in the art. See, for example, Kirk Othmer Encyclopedia of
Chemical Technology, Third Edition, Volume 7, pages 430-447
(John Wiley & Sons, Inc., 1979). One category of suds
suppressor of particular interest encompasses monocarboxylic
fatty acid and soluble salts therein. See U.S. Patent 2,954,347.
The rnonocarboxylic fatty acids and salts thereof used as suds
suppressor typically have hydrocarbyl chains of 10 to 24 carbon
atoms, preferably 12 to 18 carbon atoms. Suitable salts include
the alkali metal salts such as sodium, potassium, and lithium
salts, and amrnonium and alkanolammonium salts.
The bleaching compositions herein may also contain non-
surfactant suds suppressors. These include, for example: high
molecular weight hydrocarbons such as paraffin, fatty acid esters
(e.g., fatty acid triglycerides), fatty acid esters of monovalent
alcohols, aliphatic C1 g-C40 ketones (e.g., stearone), etc. Other
suds inhibitors include N-alkylated amino triazines such as ltri- to
hexa-alkylmelamines or di- to tetra-alkyldiamine chlortriazines
formed as products of cyanuric chloride with two or three moles
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of a primary or secondary amine containing 1 to 24 carbon
atoms, propylene oxide, and monostearyl phosphates such as
monosltearyl alcohol phosphate ester and monostearyl di-alkali
metal ~e.g., K, Na, and Li) phosphates and phosphate esters. The
hydrocarbons such as paraffin and haloparaffin can be utilized in
liquid form. The liquid hydrocarbons will be liquid at room
temperature and atmospheric pressure, and will have a pour point
in the range of -40~C and 50~C, and a minimum boiling point
not less than 110~C (atmospheric pressure). It is also known to
utilize waxy hydrocarbons, preferably having a melting point
below 100~C. The hydrocarbons constitute a preferred category
of suds suppressor for detergent compositions. Hydrocarbon
suds suppressors are described, for example, in U.S. Patent
4,265,779. The hydrocarbons, thus, include aliphatic, alicyclic,
aromatic, and heterocyclic saturated or unsaturated hydrocarbons
having from 12 to 70 carbon atoms. The term "paraffin," as
used in this suds suppressor discussion, is intended to include
mixtures of true paraffins and cyclic hydrocarbons.
Another preferred category of non-surfactant suds
suppressors cornprises silicone suds suppressors. This category
includ~s the use of polyorganosiloxane oils, such as polydimethyl-
siloxar~e, dispersions or emulsions of polyorganosiloxane oils or
resins, and combinations of polyorganosiloxane with silica
particles wherein the polyorganosiloxane is chemisorbed or fused
onto tlle silica. Silicone suds suppressors are well known in the
art and are, for example, disclosed in U.S. Patent 4,265,779 and
EP 35~01 6.
Other silicone suds suppressors are disclosed in U.S. Patent
3,455,839 which relates to compositions and processes for
defoanning aqueous solutions by incorporating therein small
amounts of polydimethylsiloxane fluids.
I\Jlixtures of silicone and silanated silica are described, for
instance, in German Patent Application DOS 2,124,526. Silicone
defoarners and suds controlling agents in granular detergent
compositions are disclosed in U.S. Patent 3,933,672 and in U.S.
Patent 4,652,392.
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An exemplary silicone based suds suppressor for use herein
is a suds suppressing amount of a suds controlling agent
consisting essentially of:
(i) polydimethylsiloxane fluid having a viscosity of from 20
cs. to 1,500 cs. at 25~C;
(ii) from 5 to 50 parts per 100 parts by weight of (i) of
siloxane resin composed of (CH3)3SiO1/2 units of SiO2
units in a ratio of from (CH3)3 SiO1 /2 units and to
SiO2 units of from 0.6:1 to 1.2:1: and
(iii) from 1 to 20 parts per 100 parts by weight of (i) of a
solid silica gel.
In the preferred silicone suds suppressor used herein, the
solvent for a continuous phase is made up of certain polyethylene
glycols or polyethylene-polypropylene glycol copolymers or
mixtures thereof (preferred), or polypropylene glycol. The
primary silicone suds suppressor is branched/crosslinked and
preferably not linear.
To illustrate this point further, typical liquid laundry
detergent compositions with controlled suds will optionally
comprise from t).001 to 1, preferably from 0.01 to 0.7, most
preferably from 0.05 to 0.5, weight % of said silicone suds
suppressor, which cornprises (1) a nonaqueous emulsion of a
primary antifoam agent which is a mixture of (a) a
polyorganosiloxane, (b) a resinous siloxane or a silicone resin-
producing silicone compound, (c) a finely divided filler material,
and (d) a catalyst to promote the reaction of mixture components
(a), (b) and (c), to form silanolates; (2) at least one nonionic
silicone surfactant; and (3) polyethylene glycol or a copolymer of
polyethylene-polypropylene glycol having a solubility in water at
room temperature of more than 2 weight %; and without
polypropylene glycol. Similar amounts can be used in granular
compositions, gels, etc. See also U.S. Patents 4,978,471 and
4,983,31 6; 5,288,431 and U.S. Patents 4,639,489 and
- 4,749,740, Aizawa et al at column 1, line 46 through column 4,
line 35.
The silicone suds suppressor herein preferably comprises
polyethylene glycol and a copolymer of polyethylene
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glycol/polypropylene glycol, all having an average molecular
weight of less than 1,000, preferably between 100 and 800.
The polyethylene glycol and polyethylene/polypropylene
copolyuners herein have a solubility in water at room temperature
of more than 2 weight %, preferably more than 5 weight %.
The preferred solvent herein is polyethylene glycol having
an average molecular weight of less than 1,000, more preferably
between 100 and 800, most preferably between 200 and 400,
and a copolymer of polyethylene glycol/polypropylene glycol,
preferably PPG 200/PEG 300. Preferred is a weight ratio of
between 1 :1 and 1 :10, most preferably between 1 :3 and 1 :6, of
polyethylene glycol :copolyrner of polyethylene-polypropylene
glycol.
The preferred silicone suds suppressors used herein do not
contain polypropylene glycol, particularly of 4,000 molecular
weight. They also preferably do not contain block copolymers of
ethylene oxide and propylene oxide, like PLURONIC L101.
Other suds suppressors useful herein comprise the
secondary alcohols (e.g., 2-alkyl alkanols) and mixtures of such
alcohols with silicone oils, such as the silicones disclosed in U.S.
4,798,679, 4,075,1 18 and EP 150,872. The secondary
alcohols include the C6-C1 6 alkyl alcohols having a C1-C1 6
chain. A preferred alcohol is 2-butyl octanol, which is available
from ~ondea under the trademark ISOFOL 12. Mixtures of
secondary alcohols are available under the trademark ISALCHEM
123 frorn Enichem. Mixed suds suppressors typically comprise
mi~ctures of alcohol + silicone at a weight ratio of 1:5 to 5:1.
For any detergent compositions to be used in automatic
laundry washing machines, suds should not form to the extent
that tlhey overflow the washing rnachine. Suds suppressors,
when utilized, are preferably present in a "suds suppressing
amount. By "suds suppressing amount" is meant that the
formulator of the composition can select an amount of this suds
controlling agent that will sufficiently control the suds to result in
a low-sudsing laundry detergent for use in automatic laundry
washing machines.
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The compositions herein will generally comprise from 0% to
5% of suds suppressor. When utilized as suds suppressors,
monocarboxylic fatty acids, and salts therein, will be present
typically in amounts up to 5%, by weight, of the detergent
composition. Preferably, from 0.5% to 3% of fatty
monocarboxylate suds suppressor is utilized. Silicone suds
suppressors are typically utilized in amounts up to 2.0%, by
weight, of the detergent composition, although higher amounts
may be used. This upper limit is practical in nature, due primarily
to concern with keeping costs minimized and effectiveness of
lower amounts for effectively controlling sudsing. Preferably
from 0.01% to 1% of silicone suds suppressor is used, more
preferably from 0.25% to 0.5%. As used herein, these weight
percentage values include any silica that may be utilized in
combination with polyorganosiloxane, as well as any adjunct
materials that may be utilized. Monostearyl phosphate suds
suppressors are generally utilized in amounts ranging from 0.1 ~/0
to 2%, by weight, of the composition. Hydrocarbon suds
suppressors are typically utilized in amounts ranging frorn 0.01%
to 5.0%, although higher levels can be used. The alcohol suds
suppressors are typically used at 0.2%-3% by weight of the
finished compositions.
Fabric Softeners - Various through-the-wash fabric
softeners, especially the impalpable smectite clays of U.S. Patent
4,062,647, as well as other softener clays known in the art, can
optionally be used typically at levels of from 0.5% to 10% by
weight in the present compositions to provide fabric softener
benefits concurrently with fabric cleaning. Clay softeners can be
used in combination with amine and cationic softeners as
disclosed, for example, in U.S. Patent 4,375,416 and U.S.
Patent 4,291,071.
Other Ingredients - A wide variety of other functional ingredients
useful in detergent compositions can be included in the
compositions herein, including other active ingredients, carriers,
hydrotropes, processing aids, dyes or pigments, solvents for
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34
liquid formulations, solid fillers for bar compositions, etc. If high
sudsing is desired, suds boosters such as the C1 o-C1 6
alkanolamides can be incorporated into the compositions,
typically at 1 %-10% levels. The C1 0-C1 4 monoethanol and
diethanol amides illustrate a typical class of such suds boosters.
Use of such suds boosters with high sudsing adjunct surfactants
such as the amine oxides, betaines and sultaines noted above is
also advantageous. If desired, soluble magnesium salts such as
MgCI2, MgS04, and the like, can be added at levels of, typically,
0. 1%-2 % , to provide additional suds and to enhance grease
removal perforn ance.
Various detersive ingredients employed in the present
compositions optionally can be further stabilized by absorbing
said ingredients onto a porous hydrophobic substrate, then
coating said substrate with a hydrophobic coating. Preferably,
the detersive ingredient is admixed with a surfactant before being
absorbed into the porous substrate. In use, the detersive
ingredient is released from the substrate into the aqueous
washing liquor, where it performs its intended detersive function.
lro illustrate this technique in more detail, a porous
hydrophobic silica (trademark SIPERNAT D10, DeGussa) is
admixed with a proteolytic enzyme solution containing 3%-5% of
C13-15 ethoxylated alcohol (E0 7) nonionic surfactant.
Typicalfy, the enzyme/surfactant solution is 2.5 X the weight of
silica. The resulting powder is dispersed with stirring in silicone
oil (various silicone oil viscosities in the range of 500-12,500 can
be used). The resulting silicone oil dispersion is emulsified or
otherwise added to the final detergent matrix. By this means,
ingredients such as the aforementioned enzymes, bleaches,
bleach activators, bleach catalysts, photoactivators, dyes,
fluorescers, fabric conditioners and hydrolyzable surfactants can
be "protected" for use in detergents.
The detergent compositions herein will preferably be
formulated such that, during use in aqueous cleaning operations,
the w;ash water will have a pH of between 6.5 and 11,
preferably between 7 . 5 and 1 0 . 5 . Laundry products are typically
at pH 9-11. Techniques for controlling pH at recommended usage
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levels include the use of buffers, alkalis, acids, etc., and are well
known to those skilled in the art.
The bulk density of granular bleaching compositions (so-called
granular detergent compositions) is typically at least 450 g/litre,
more usually at least 600 g/litre and more preferably from 650
g/litre to 1000 g/litre.
The invention is illustrated in the following non limiting examples,
in which all percentages are on a weight basis unless otherwise
stated.
In the bleaching compositions of the invention, ~e abbreviated component
i-lentifications have the following me~nin~.c:
LAS : Sodium linear C12 aLkyl benzene sulphonate
TAS : Sodium tallow allyl slllrh~te
XYAS : Sodium Clx - Cly alkyl slllrh~te
25EY : AC12 lspredomin~ntlylinearprimaryalcohol
condensed with an average of Y moles of
ethylene oxide
45EY : A C14 - Cls predomin~ntly linear primary
alcohol condensed with an average of Y moles of
e~ylene oxide
XYEZS : ClX - Cly sodium alkyl sulphate conden~e~
with an average of Z moles of ethylene oxide per
mole
polyhydroxy fatty : N-Lauroyl N-Methyl Glllc~mine
acid amide
TFAA : C 1 6-C 1 8 alkyl N-methyl glucamide.
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36
NaSKS~6 : Crystalline layered silicate of formula ~-
Na2Si205
Carbonate : Anhydrous sodiumcarbonate
Silicate : Amorphous sodium silicate (SiO2:Na20 ratio
normally follows)
MA/AA. : Copolymer of 1:4 maleic/acrylic acid, average
molecular weight about 80,000
Zeolite A : Hydrated Sodium Aluminosilicate of for~nula
Nal2(A102SiO2)12. 27H20 having a ~ m~y
particle size in the range from 1 to 10
micrometers
Photobleach : Tetra sulphonatedzincphthalocyanine
Ci~ate : Tri-sodiumcitrate dihydrate
Citric acid : Anhydrous Citric Acid
PBl : Sodium perborate monohydrate bleach of nomin~l
formula NaBo2.H2o2
PB4 : Sodium perborate tetrahydrate bleach of norninz~l
formula NaBo2.H2o2-3H2o
Pel~l,,onate : Anhydrous sodium perc~l,onate bleach of
empirical formula 2Na2CO3.3H2O2 coated with
a mixed salt of formula Na2S04.n.Na2C03
where n is 0.29 and where the weight ratio of
percarbonate to mixed salt is 39:1
TAED : Tetraacetyl ethylene ~ mine
Savinase : Proteolytic enzyme activity 4 KNPU/g
Lipolase : Lipolytic enzyme activity 100 KLU/g
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Cellulase : Cellulosic enzyme activity of 1 000
CEVU/g
Endo A : Cellulytic enzyme activity 5000 SCEVU/g
Termamyl 60T : Amylolytic enzyme activity of 300 KNU/g
all sold by NOVO ~n~ tries AtS
PVNO : Polyvinyl pyridine N-oxide polymer of molecular
weight 10,000
MgS04 : Anhydrous ~esillm Sulphate
SRP : modified aI~ionic polyester Soil Release Polymer
CMC : Sodium carboxymethyl cellulose
EDDS : Ethylenediamine -N, N'- disuccinic acid,
[S,S] isomer in the form of the sodium
salt.
Brightener : Disodium 4,4'-bis-(2-sulphostyryl)-
biphenyl.
DETPMP : Diethylenetriamine penta (Methylene
phosphonic acid) marketed by Monsanto
under the Trade name Dequest 2060.
Mixed Suds : 25 % paraffin wax Mpt 50 ~ C, 1 7 %
suppressor hydrophobic silica, 58% paraffin oil.
Fxamr)le 1
The following perfume formulations were prepared
Perfume 1 ~
Hexyl cinnamic aldehyde 10
Hexyl salicylate 20
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Phenyl ethyl alcohol 20
Citronellol 1 2
Geraniol 8
2-Methyl-3-(4-tertiary butyl phenyl) propanal 10
Phenyl ethyl acetate 2
Benzyl acetate 5
4-tertiary butyl cyclohexyl acetate 5
3-Buten-2-one, 4-(2,6,6-trimethyl-1- 3
cyclohexen- 1 -yl)
10-undecenal (10% in DPG) 5
Perfume 2 %
Benzyl salicylate 5
Hexyl salicylate 10
Phenyl ethyl alcohol 1 5
4-lso propyl cyclohexanol 5
Citronellol 1 0
3-Buten-2-one, 4-(2,6,6-trimethyl-1- 1 5
cyclohexen- 1 -yl)
Heliotropine 4
7-Acetyl, 1, 2, 3, 4, 5, 6, 7, 8-octahydro 1, 1, 5
6, 7 tetra methyl naphtalene
Benzyl acetate 7
4-tertiary butyl cyclohexyl acetate 20
2-Methyl-3-phenyl propan-2-yl acetate 4
Storage stability of said l-erfume compositions in term of grade
stability
Method for measuring the perfume grade stability
Perfume samples are at least 24 hours old. The samples are
coded to preserve anonymity and the results are recorded on
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39
individual sheets. The panel is held in an odour-free room. The
detergent is poured into a clean plastic cup and covered
immediately with a plastic lid. 1% solutions are then made by
adding hot water (50~CJ to a beaker along with the product. This
is covered immediately with a watch glass.
Panel odour grading is carried out by a minimum of three expert
judges. In this instance, expert is defined as a person having at
least 6 months training with demonstrated evidence of olfactive
sensitivity. All grades for this work were given versus a
laboratory prepared standard product (grade 10.0) on a 1-10
scale. The individual ~rades are only averaged when the highest
and lowest grades do not differ by more than 2 panel grades.
Where differences are greater, that product is repanelled as soon
as possible on a subsequent panel.
For each perfume formulations sprayed onto the bleaching
composition at least 1 stability grade enhancement was
recorded.
Exam,~le ~
The following perfumed bleaching compositions were prepared
(parts by weight). Compositions A, B, C, D are in accordance
with the present invention, wherein the perfume is selected from
one of those defined in Example 1 and sprayed onto the finished
detergent product.
A B C D
LAS - - - 6.92
TAS - - - 2.05
45AS/25AS - - 9.1
(3: 1 )
45AS 6.86 6.86 - -
35AE3S 2.3
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C25E3S 1.71 1.71 - 0.16
C45E7 - - - 4.0
C25E5 2.21 2.21
C24E5 4.5
C25E3 1.16 1.16
polyhyldroxy 1.45 1.45
fatty acid amide
TFAA - - 2.0
Zeolite A 10.2 10.2 10.2 20.2
Citrate - - 5.5
Citric 2.5 2.3
SKS-6 9.2 8.5
Na SKS-6/citric - - 10.6
acid ~79:21)
Carbonate 5.8 9.8 7.6 15.4
Silicat~ (2.0 - - 0.15 3.0
ratio)
Bicarbonate - - 0.28
Sulphate - 8.0 0.27
MA/A,A 3.85 3.0 3.1 4.0
CMC 0.30 0.30 0.4 0.31
SRP 0.20 0.15 0.20 0.30
PVPV~ - - - O .0 1
PVN0 0.02 - 0.03 0.01
Savinase 0.41 0.25 0.55 1.4
Lipolase 0.11 0.07 0.15 0.36
Cellulase 0.12 - 0.28
Endo A 0.08 0.12 - 0.13
Termamyl 60T - - 0.27
PB4 - - - 11.64
PB1 - - - 8.7
TAED 4.7 1.6 5.0 5.0
DETPMP - - 0.5 0.38
MgSC)4 0.38 0.38 0.38 0.40
Percarbonate 16.9 10.0 22.5
EDDS 0.21 0.21
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41
Brightener 0.22 0.18 0.22 0.19
Photoactivated 0.002 0.002 0.002 0.002
r bleach
Suds suppressor 2.75 2.75 1.5 0.85
perfumes 0.3(1 ) 0.3(2) 0.3(1 ) 0.3(2)
Water minors and miscellaneous to balance
(1 ) perfume formulation 1
(2) perfume formulation 2
The compositions in accordance with the invention were all seen
having an enhanced perfume stability o~ at least 1 grade.
