Note: Descriptions are shown in the official language in which they were submitted.
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DELIVERY SYSTEM HAVING ENCAPSULATED POROUS CARRIER
LOADED WITH ADDITIVES, PARTICULARLY DETERGENT ADDITIVES
SUCH AS PERFUMES
FIELD OF THE INVENTION
The present invention relates to delivery particles, particularly to particles
for the
delivery of laundry additives, such as perfume agents, and detergent
compositions
including the delivery particles, especially granular detergents.
BACKGROUND OF THE INVENTION
Most consumers have come to expect scented laundry products and to expect that
fabrics
which have been laundered also have a pleasing fragrance. In many parts of the
world
handwashing is the predominant means of laundering fabrics. When handwashing
soiled
fabrics the user often comes in contact with the wash solution and is in close
proximity
to the detergent product used therein. Handwash solutions may also develop an
offensive
odor upon addition of soiled clothes. Therefore, it is desirable and
commercially
beneficial to add perfume materials to such products. Perfume additives make
laundry
compositions more aesthetically pleasing to the consumer, and in some cases
the
perfume imparts a pleasant fragrance to fabrics treated therewith. However,
the amount
of perfume carryover from an aqueous laundry bath onto fabrics is often
marginal.
Industry, therefore, has long searched for an effective perfume delivery
system for use in
detergent products which provides long-lasting, storage-stable fragrance to
the product,
as well as releases fragrance during use to mask wet solution odor and
delivers fragrance
to the laundered fabrics.
Further, after drying fabrics under the sun, fabrics obtain a "sun-dried type"
of odor.
Consumers often prefer this to a standard perfume odor. Also they often
consider
fabrics with these odors to be cleaner. Because consumers like the odor, they
like to dry
fabrics under the sun. In some countries, however, consumers cannot dry their
fabrics
outside because the air is not clean, or there is too much rain. As a result,
they have to
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dry their fabrics indoors and cannot expect to enjoy this benefit of having a
"sun-dried
type" of odor on their fabrics.
A detergent composition comprising a perfume which can provide a "sun-dried
type" of
odor has now been found.
Laundry and other fabric care compositions which contain perfume mixed with or
sprayed onto the compositions are well known from commercial practice. Because
perfumes are made of a combination of volatile compounds, perfume can be
continuously emitted from simple solutions and dry mixes to which the perfume
has been
added. Various techniques have been developed to hinder or delay the release
of
perfume from compositions so that they will remain aesthetically pleasing for
a longer
length of time. To date, however, few of the methods deliver significant
fabric odor
benefits after prolonged storage of the product.
Moreover, there has been a continuing search for methods and compositions
which will
effectively and efficiently deliver perfume from a laundry bath onto fabric
surfaces. As
can be seen from the following disclosures, various methods of perfume
delivery have
been developed involving protection of the perfume through the wash cycle,
with release
of the perfume onto fabrics. U.S. Pat. 4,096,072, Brock et al, issued June 20,
1978,
teaches a method for delivering fabric conditioning agents, including perfume,
through
the wash and dry cycle via a fatty quaternary ammonium salt. U.S. Pat.
4,402,856,
Schnoring et al, issued Sept. 6, 1983, teaches a microencapsulation technique
which
involves the formulation of a shell material which will allow for diffusion of
perfume out
of the capsule only at certain temperatures. U.S. Pat. 4,152,272, Young,
issued May 1,
1979, teaches incorporating perfume into waxy particles to protect the perfume
through
storage in dry compositions and through the laundry process. The perfume
assertedly
diffuses through the wax on the fabric in the dryer. U.S. Pat. 5,066,419,
Walley et al,
issued Nov. 19, 1991, teaches perfume dispersed with a water-insoluble
nonpolymeric
carrier material and encapsulated in a protective shell by coating with a
water-insoluble
friable coating material. U.S. Pat. 5,094,761, Trinh et al, issued Mar. 10,
1992, teaches a
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perfume/cyclodextrin complex protected by clay which provides perfume benefits
to at
least partially wetted fabrics.
Another method for delivery of perfume in the wash cycle involves combining
the
perfume with an emulsifier and water-soluble polymer, forming the mixture into
particles, and adding them to a laundry composition, as is described in U.S.
Pat.
4,209,417, Whyte, issued June 24, 1980; U.S. Pat. 4,339,356, Whyte, issued
July 13,
1982; and U.S. Pat. No. 3,576,760, Gould et al, issued April 27, 1971.
However, even
with the substantial work done by industry in this area, a need 'still exists
for a simple,
more efficient and effective perfume delivery system which can be mixed with
laundry
compositions to provide initial and lasting perfume benefits to fabrics which
have been
treated with the laundry product.
The perfume can also be adsorbed onto a porous carrier material, such as a
polymeric
material, as described in U.K. Pat. Pub. 2,066,839, Bares et al, published
July 15, 1981.
Perfumes have also been adsorbed onto a clay or zeolite material which is then
admixed
into particulate detergent compositions. Generally, the preferred zeolites
have been
Type A or 4A Zeolites with a nominal pore size of approximately 4 Angstrom
units. It is
now believed that with Zeolite A or 4A, the perfume is adsorbed onto the
zeolite surface
with relatively little of the perfume actually absorbing into the zeolite
pores. While the
adsorption of perfume onto zeolite or polymeric carriers may provide some
improvement
over the addition of neat perfume admixed with detergent compositions,
industry is still
searching for improvements in the length of storage time of the laundry
compositions
without loss of perfume characteristics, in the intensity or amount of
fragrance released
during the wash process and delivered to fabrics, and in the duration of the
perfume scent
on the treated fabric surfaces.
Combinations of perfumes generally with larger pore size zeolites X and Y are
also
taught in the art. East German Patent Publication No. 248,508, published
August 12,
1987 relates to perfume dispensers (e.g., an air freshener) containing a
faujasite-type
zeolite (e.g., zeolite X and Y) loaded with perfumes. The critical molecular
diameters of
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the perfume molecules are said to be between 2-8 Angstroms. Also, East German
Patent
Publication No. 137,599, published September 12, 1979 teaches compositions for
use in
powdered washing agents to provide thermoregulated release of perfume.
Zeolites A, X
and Y are taught for use in these compositions. These earlier teachings are
repeated in
the more recently filed European applications Publication No. 535,942,
published April
7, 1993, and Publication No. 536,942, published April 14, 1993, by Unilever
PLC, and
U.S. Patent 5,336,665, issued August 9, 1994 to Garner-Gray et al.
Effective perfume delivery compositions are taught by WO 94/28107, published
December 8, 1994 by The Procter & Gamble Company. These compositions comprise
zeolites having pore size of at least 6 Angstroms (e.g., Zeolite X or Y),
perfume
releaseably incorporated in the pores of the zeolite, and a matrix coated on
the perfumed
zeolite, the matrix comprising a water-soluble (wash removable) composition
comprising
from 0% to about 80%, by weight, of at least one solid polyol containing more
than 3
hydroxyl moieties and from about 20% to about 100%, by weight, of a fluid diol
or
polyol, in which the perfume is substantially insoluble and in which the solid
polyol is
substantially soluble.
Other perfume delivery systems are taught by WO 97/34982 and WO 98/41607,
published by The Procter & Gamble . WO 97/34982 discloses particles comprising
perfume loaded zeolite and a release barrier, which is an agent derived from a
wax and
having a size (i.e., a cross-sectional area) larger than the size of the pore
openings of the
zeolite Garner. WO 98/41607 discloses glassy particles comprising agents
useful for
laundry or cleaning compositions and a glass derived from one or more of at
least
partially-water-soluble hydroxylic compounds. A preferred agent is a perfume
in a
zeolite carrier.
Another problem that may occur in providing perfumed products is the excessive
odor
intensity associated with the products. A need therefore exists for a perfume
delivery
system which provides satisfactory perfume odor during use and thereafter from
the dry
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laundered fabric, but which also provides prolonged storage benefits and
reduced
product odor intensity.
By the present invention it has now been discovered that perfume loaded into
porous
carriers such as zeolite particles, can be effectively protected from
premature release of
perfume by coating said loaded carrier particles with a hydrophobic oil and
thereafter
encapsulating the oil-coated perfume-loaded Garner particles with a water-
soluble or
water-dispersible, but oil-insoluble, material, such as starch or modified
starch. The
porous carrier may be selected to be substantive to fabrics to be' able to
deposit enough
perfume on the fabrics to deliver a noticeable odor benefit even after the
fabrics are dry.
The present invention solves the long-standing need for a simple, effective,
storage-stable perfume delivery system which provides consumer-noticeable odor
benefits during and after the laundering process, and which has reduced
product odor
during storage of the composition. In particular, fabrics treated by the
present perfume
delivery system have higher scent intensity and remain scented for longer
periods of time
after laundering and drying.
The present invention also provides a delivery system for other additives,
which are
desirably protected from release until the product comprising the additive is
exposed to a
wet or moist environment.
SUMMARY OF THE INVENTION
The present invention relates to a delivery system for additives, which are
incorporated
in a variety of consumer products, including detergents and cleaning
compositions, room
deodorizers, insecticidal compositions, carpet cleaners and deodorizers
wherein the
additive is protected from release until exposed to a wet or moist
environment.
Specifically, the present additive delivery system is a particle comprising a
core of a
porous carrier material containing an additive, such as a perfume, in its
pores; a first
coating of a hydrophobic oil encapsulating said core, and a second coating of
a
water-soluble or water-dispersible, but oil-insoluble, material, such as
starch or modified
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starch, encapsulating the hydrophobic-oil coated core. The present delivery
particle can
be used to deliver laundry and cleaning agents either to or through the wash
cycle. A
laundry additive delivery particle according to the present invention
effectively delivers
perfume ingredients through the wash to a fabric surface.
In traditional perfume delivery systems more than 50% of the perfume material
is "lost"
due to diffusion of the volatile perfume materials from the product or by
dissolution in
the wash, and is not delivered to the fabric surface. In the present
invention, the coatings
effectively entrap the perfume material loaded into the carrier core. Thus,
the perfume
material is delivered to the fabric surface at a higher rate through the wash
than with
traditional perfume delivery systems.
The porous carrier material is typically selected from zeolites, macroporous
zeolites,
amorphous silicates, crystalline nonlayer silicates, layer silicates, calcium
carbonates,
calcium/sodium carbonate double salts, sodium carbonates, clays, sodalites,
alkali metal
phosphates, chitin microbeads, carboxyalkylcelluloses, carboxyalkylstarches,
cyclodextrins, porous starches, and mixtures thereof. Preferably the carrier
material is a
zeolites such as Zeolite X, Zeolite Y, and mixtures thereof.
Particularly preferred porous carriers are zeolite particles with a nominal
pore size of at
least about 6 Angstroms to effectively incorporate perfume into their pores.
Without
wishing to be limited by theory, it is believed that these zeolites provide a
channel or
cage-like structure in which the perfume molecules are trapped. Unfortunately,
such
perfumed zeolites are not sufficiently storage-stable for commercial use in
granular
fabric care products such as laundry detergents, particularly due to premature
release of
perfume upon moisture absorption. However, it has now been discovered that the
perfume-loaded zeolite can first be coated with a hydrophobic oil to protect
the zeolite
particles by forming a protective barrier to entrap and maintain the perfume
within the
zeolite's pores, and thereafter encapsulating the oil-coated particle with a
water-soluble
or water-dispersible, but oil-insoluble, material. Thus, the perfume
substantially remains
within the pores of the zeolite particles. It is also believed that since the
perfume is
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incorporated into the relatively large zeolite pores, it has better perfume
retention
through the laundry process than other smaller pore size zeolites in which the
perfume is
predominately adsorbed on the zeolite surface.
The hydrophobic oil coating can be a non-perfume oil but is preferably a
perfume which
can be the same as or different from the perfume oil loaded into the carrier.
It is believed
that when the present encapsulated particle is added to water, such as during
laundering,
the water-soluble or water-dispersible encapsulating material dissolves and
starts to
release the oil coating. When this oil coating is a perfume, ' the perfume
notes are
released from the wash solution, providing the wet odor benefit . The carrier
particles
loaded with perfume are released in the wash solution and deposit onto
fabrics. After the
fabrics are dried, perfume is released from the carrier as moisture in the
atmosphere
displaces the perfume contained in the pores of the carrier, providing the dry
odor
benefit.
The additive contained in the porous Garner core is preferably selected from
the group
consisting of perfumes, bleaches, bleach promoters, bleach activators, bleach
catalysts,
chelants, antiscalants, dye transfer inhibitors, photobleaches, enzymes,
catalytic
antibodies, brighteners, fabric-substantive dyes, antifungals, antimicrobials,
insect
repellents, soil release polymers, fabric softening agents, dye fixatives, pH
jump systems,
and mixtures thereof.
The preferred laundry additive to be loaded into the porous Garner material is
a perfume.
Preferably, the particle core is a perfume-loaded zeolite (PLZ).
The preferred encapsulating material is a starch, modified starch or starch
hydrolysate
while the preferred oil coating material is a perfume oil. The external
encapsulating
material may further include an ingredient selected from the group consisting
of
plasticizers, anti-agglomeration agents, and mixtures thereof.
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In a further embodiment of the present invention, a laundry or cleaning
detergent
composition is provided. The laundry or cleaning composition comprises from
about
0.001 % to about 50% by weight of the composition of the laundry additive
particle as
described above and from about 50% to about 99.999% by weight of the
composition of
laundry ingredients selected from the group consisting of detersive
surfactants, builders,
bleaching agents, enzymes, soil release polymers, dye transfer inhibitors,
fillers and
mixtures thereof. Preferably, the composition includes at least one detersive
surfactant
and at least one builder.
Accordingly, it is an object of the present invention to provide an additive
delivery
particle having a core loaded with an additive, preferably a laundry additive
such as a
perfume, and at least two surface coatings comprising an intermediate
hydrophobic oil
coating and an external encapsulating coating of a water-soluble or water-
dispersible
material. It is another object of the present invention to provide a laundry
and cleaning
composition having said laundry additive particle thereon. It is a further
object of the
present invention to provide a laundry additive particle which can provide
improved
fabric odor benefits, prolong storage life capabilities, and reduce product
odor intensity.
These and other objects, features and advantages of the present invention will
be
recognizable to one of ordinary skill in the art from the following
description and the
appended claims.
All percentages, ratios and proportions herein are on a weight basis unless
otherwise
indicated. All documents cited herein are hereby incorporated by reference.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 shows a SEM of an intact average sized laundry additive particle
comprising an
encapsulated perfume-loaded zeolite particle according to the present
invention.
Figure 2 shows a SEM of a cross-section of a particle according to the present
invention,
containing loaded zeolite particles inside a starch coating.
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DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention relates to a laundry additive particle and to laundry
and cleaning
compositions comprising the laundry additive particle, which is preferably a
perfume-
containing particle. Laundry and cleaning compositions include traditional
granular
laundry detergents as well as granular bleach, automatic dishwashing, hard
surface
cleaning, and fabric softening compositions. The laundry additive particle of
the present
invention provides superior through the wash perfume delivery capabilities as
well as
minimizes product odor due to evolving volatile perfume ingredients. While not
wishing
to be bound by theory, it is also believed that the specified coatings of the
particle of the
present invention increase the stability of the particle.
The preferred laundry particle of the present invention comprises a core of a
porous
carrier loaded with perfume, said loaded core being first coated with a
hydrophobic oil
material and thereafter encapsulated with an external coating of a water-
soluble or water-
dispersible, but oil-insoluble, material, such as starch or modified starch,
to form the
final particle.
Preferably, the laundry additive particles of the present invention have a
hygroscopicity
value of less than about 80%. The "hygroscopicity value", as used herein,
means the
level of moisture uptake by the particles, as measured by the percent increase
in weight
of the particles under the following test method. The hygroscopicity value
required for
the present invention particles is determined by placing 2 grams of particles
in an open
container petri dish under conditions of 90°F and 80% relative humidity
for a period of 4
weeks. The percent increase in weight of the particles at the end of this time
is the
particles' hygroscopicity value as used herein. Preferred particles of the
present
invention have a hygroscopicity value of less than about 50%, more preferably
less than
about 30%.
The laundry additive particles of the present invention typically comprise
from about 5%
to about 50% of the loaded central core particle which itself is about 60% to
about 99%
porous carrier and about 1 % to about 40% perfume or other laundry additive
material,
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from about 1% to about 40% of hydrophobic oil intermediate coating material,
and from
about 10% to about 94% external encapsulating material.
Loaded Central Core Particle
As already stated, the central core of the additive particle comprises a
porous carrier
material and a laundry additive loaded into said carrier material. The two
ingredients of
the central core may be mixed in a number of different ways.
At laboratory scale, basic equipment used for this purpose can vary from a 10-
20g coffee
grinder to a 100 - 500 g. food processor or even a 200-1000g kitchen mixer.
Procedure
consists of placing the carrier material particles (zeolite) in the equipment
and pouring
the laundry additive at the same time that mixing occurs. Mixing time is from
0.5 to 1 S
minutes. The loaded carrier material (zeolite) is then allowed to rest for a
period from
0.5 to 48 hours before further processing. During the loading process when
heating
occurs, cool jacketing may be used as an option. At pilot plant level,
suitable equipment
is a mixer of the Littleford type, which is a batch type mixer with plows and
chopper
blades that operate at high RPM's, to continuously mix the powder or mixture
of
powders while liquid perfume oil is being sprayed thereon.
Porous Carrier Material
The porous carrier material, as used herein, means any material capable of
supporting
(e.g., by adsorption into the pores) a deliverable agent such as a laundry or
cleaning
agent. Such materials include porous solids such as zeolites.
Preferred zeolites are selected from zeolite X, zeolite Y and mixtures
thereof. The term
"zeolite" used herein refers to a crystalline aluminosilicate material. The
structural
formula of a zeolite is based on the crystal unit cell, the smallest unit of
structure
represented by
Mm/n[(A102)m(Si02)y].xH20
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where n is the valence of the cation M, x is the number of water molecules per
unit cell,
m and y are the total number of tetrahedra per unit cell, and y/m is 1 to 100.
Most
preferably, y/m is 1 to 5. The cation M can be Group IA and Group IIA
elements, such
as sodium, potassium, magnesium, and calcium.
A zeolite useful herein is a faujasite-type zeolite, including Type X Zeolite
or Type Y
Zeolite, both with a pore size typically in the range of from about 4 to about
10
Angstrom units, preferably about 8 Angstrom units.
The aluminosilicate zeolite materials useful in the practice of this invention
are
commercially available. Methods for producing X and Y-type zeolites are well-
known
and available in standard texts. Preferred synthetic crystalline
aluminosilicate materials
useful herein are available under the designation Type X or Type Y.
For purposes of illustration and not by way of limitation, in a preferred
embodiment, the
crystalline aluminosilicate material is Type X and is selected from the
following:
(I) Na86[A102]86'(Si02)106].xH20 ,
(II) K86[A102]86.(Si02)106]~xH20 ,
(III) Ca40Na6[A102]86'(Si02)106].xH20 ,
(IV) Sr21Ba22[A102]86'(Si02)106]~xH2~'
and mixtures thereof, wherein x is from about 0 to about 276. Zeolites of
Formula (I)
and (II) have a nominal pore size or opening of 8.4 Angstroms units. Zeolites
of
Formula (III) and (IV) have a nominal pore size or opening of 8.0 Angstroms
units.
In another preferred embodiment, the crystalline aluminosilicate material is
Type Y and
is selected from the following:
(V) Na56[A102]56'(Si02)136~~xH20 ,
(VI) K56[A102]56'(Si02)136]~~2G
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and mixtures thereof, wherein x is from about 0 to about 276. Zeolites of
Formula (V)
and (VI) have a nominal pore size or opening of 8.0 Angstroms units.
In yet another embodiment, the class of zeolites known as, "Zeolite MAP" may
also be
employed in the present invention. Such zeolites are disclosed and described
in U.S.
Patent Application Serial No. 08/716,147 filed September 16, 1996 and
entitled, "Zeolite
MAP and Alcalase for Improved Fabric Care."
Zeolites used in the present invention are in particle form having an average
particle size
from about 0.5 microns to about 120 microns, preferably from about 0.5 microns
to
about 30 microns, as measured by standard particle size analysis technique.
The size of the zeolite particles allows them to be entrained in the fabrics
with which
they come in contact. Once established on the fabric surface (with the
coatings having
been washed away during the laundry process), the zeolites can begin to
release their
incorporated laundry agents, especially when subjected to heat or humid
conditions.
Intermediate Oil Coating Material
The intermediate oil coating material according to the present invention forms
a coating
on the central core particle. The intermediate coating provides a barner to
minimize
release or leakage of any deliverable agent, such as a perfume, incorporated
into the
porous carrier. The intermediate coating material comprises a hydrophobic oil
such as a
perfume oil which can be the same as or different from the perfume loaded into
the
carrier, or a non-perfume oil, such as mineral oil. The hydrophobic oil can be
one or a
mixture of organic compounds, preferably having a weighted average ClogP lower
than
the weighted average ClogP of the additive material or mixture loaded in the
pores of the
carrier. ClogP values are typically used to characterize perfume ingredients,
i.e., by their
octanol/water partition coefficient P. The octanol/water partition coefficient
of a
perfume ingredient is the ratio between its equilibrium concentration in
octanol and in
water. The more hydrophobic a material, the higher its ClogP. The intermediate
oil
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coating material is thus preferably less hydrophobic than the additive
material contained
in the porous Garner.
More preferably the highest CIogP of the material comprising the hydrophobic
oil
coating is lower than the lowest ClogP of the material comprising the additive
loaded in
the porous Garner. Even more preferably, there is a difference of at least one
unit and
most preferably, two units between the highest CIogP of the hydrophobic oil
coating
material and the lowest CIogP of the loaded additive material.
External Encapsulating Material
The external encapsulating material is coated on the intermediate coating
material which
is coated on the core particle and provides the outer layer of the final
particle. The
external coating material provides a substantially non-tacky or non-sticky
coating for the
final particle. Preferably, the external coating provides a particle which
will have a non-
tacky surface in high humidity conditions such as 80% relative humidity at 90
°F.
The external coating is a material derived from one or more at least partially
wash-
soluble or dispersible compounds. That is, the external coating will either be
soluble in
an aqueous wash environment or be dispersible in that aqueous wash
environment. The
compounds useful herein are preferably selected from the following classes of
materials.
1. Carbohydrates, which can be any or a mixture of i) Starches including
modified
starches and starch hydrolysates; ii) Oligosaccharides (defined as
carbohydrate
chains consisting of 2-35 monosaccharide molecules); iii) Polysaccharides
(defined
as carbohydrate chains consisting of at least 35 monosaccharide molecules);
and
iv) Simple sugars (or monosaccharides); and v) hydrogenates of i), ii), iii),
and iv).
Both linear and branched carbohydrate chains may be used. In addition
chemically
modified starches and poly-/oligo-saccharides may be used. Typical
modifications
include the addition of hydrophobic moieties of the form of alkyl, aryl, etc.
identical to
those found in surfactants to impart some surface activity to these compounds.
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2. All natural or synthetic gums such as alginate esters, carrageenin, agar-
agar, pectic
acid, and natural gums such as gum arabic, gum tragacanth and gum karaya.
3. Chitin and chitosan.
4. Cellulose and cellulose derivatives. Examples include: i) Cellulose acetate
and
Cellulose acetate phthalate (CAP); ii) Hydroxypropyl Methyl Cellulose (HPMC);
iii)Carboxymethylcellulose (CMC); iv) all enteric/aquater'ic coatings and
mixtures
thereof.
5. Silicates, Phosphates and Borates.
6. Water soluble polymers including polyacrylates, caprolactones, Polyvinyl
alcohol
(PVA) and Polyethylene glycol (PEG).
7. Waxes, including silicone waxes, paraffinic waxes, and microcrystalline
waxes.
8. Plasticizers.
9. Long Chain . (C 10-C35) fatty compounds including fatty acids, fatty
alcohols and
fatty esters.
10. Natural proteins including gelatin, casein and egg albumin.
Materials within these classes which are not at least partially wash soluble
or dispersible
are useful herein only when mixed in such amounts with the compounds useful
herein
such that the particle produced has the preferred hygroscopicity value of less
than about
80%. It is also preferred that these compounds be low temperature processable,
preferably within the range of from about 50 °C to about 200 °C,
and more preferably
within the range of from about 60 °C to about 180 °C.
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Preferred encapsulating materials are starches or modified starches such as
CAPSUI,TM
commercially available from National Starch, cellulose and cellulose
derivatives such as
hydroxy propyl methyl cellulose, other carbohydrates such as sucrose and
fructose,
natural polymers such as gum arabic and guar gum, natural proteins, and water-
soluble
polymers such as polyethylene glycol.
The external encapsulation coating may include optional additive ingredients
such as
plasticizers, anti-agglomeration agents, and mixtures thereof. The optional
plasticizers
include sorbitol, polyethylene glycol, propylene glycol, low molecular weight
carbohydrates and the like with a mixture of sorbitol and polyethylene glycol
and low
molecular weight polyols being the most preferred. The plasticizer is employed
at levels
of from about 0.01% to about 5%. The anti-agglomeration agents according to
the
present invention are preferably surfactants and are included at low levels of
less than
1% of the external coating. Suitable surfactants for use in the present
invention include
TWEENTM 80 commercially available from Imperial Chemicals, Inc. (ICI).
Laundry and Cleaning Additives
Laundry and cleaning additives or agents are included in the particle of the
present
invention. The agents are contained in the porous carrier material as
hereinbefore
described. As can be appreciated for the present invention, agents which are
incorporated
into the particles of the present invention may be the same as or different
from those
agents which are typically used to formulate the remainder of the laundry and
cleaning
compositions containing the particle. For example, the particle may comprise a
perfume
agent and (the same or different) perfume may also be blended into the final
composition
(such as by spray-on techniques) along with the perfume-containing particle.
These
agents are selected as desired for the type of composition being formulated,
such as
granular laundry detergent compositions, granular automatic dishwashing
compositions,
or hard surface cleaners.
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The laundry particle of the present invention may of course be included in a
composition
which may contain other ingredients. The compositions containing laundry
additive
particles 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.,
perfumes,
colorants, dyes, etc.).
Perfume
The preferred laundry or cleaning additive according to the present invention
is a
perfume material. As used herein the term "perfume" is used to indicate any
odoriferous
material which is subsequently released into the aqueous bath and/or onto
fabrics or
other surfaces contacted therewith. The perfume will most often be liquid at
ambient
temperatures. A wide variety of chemicals are known for perfume uses,
including
materials such as aldehydes, especially C6-C,4 aliphatic aldehydes, C6-C,4
acyclic
terpene aldehydes and mixtures thereof, ketones, alcohols and esters. More
commonly,
naturally occurring plant and animal oils and exudates comprising complex
mixtures of
various chemical components are known for use as perfumes. The perfumes herein
can
be relatively simple in their compositions or can comprise highly
sophisticated complex
mixtures of natural and synthetic chemical components, all chosen to provide
any
desired odor. Typical perfumes can comprise, for example, woody/earthy bases
containing exotic materials such as sandalwood, civet and patchouli oil. The
perfumes
can be of a light floral fragrance, e.g., rose extract, violet extract, and
lilac. The
perfumes can also be formulated to provide desirable fruity odors, e.g., lime,
lemon, and
orange. Any chemically compatible material which exudes a pleasant or
otherwise
desirable odor can be used in the perfumed compositions herein.
If "sun dried" odor is the preferred odor, the perfume component is selected
from
the group consisting of C6-C,.~ aliphatic aldehydes, C6-C,4 acyclic terpene
aldehyde and
mixtures thereof. Preferably, the perfume component is selected from C8-C1z
aliphatic
aldehydes, C8-C,2 acyclic terpene aldehydes and mixtures thereof. Most
preferably, the
perfume component is selected from the group consisting of citral; neral; iso-
citral;
dihydro citral; citronellal; octanal; nonanal; decanal; undecanal; dodecanal;
tridecanal; 2-
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methyl decanal; methyl nonyl acetaldehyde; 2-nonen-1-al; decanal; undecenal;
undecylenic aldehyde; 2, 6 dimethyl octanal; 2, 6, 10-trimethyl-9-undecen-1-
al; trimethyl
undecanal; dodecenal; melonal; 2-methyl octanal; 3, 5, 5, trimethyl hexanal
and mixtures
thereof. The preferable mixtures are, for example, a mixture comprising 30% by
weight
of 2-nonen-1-al, 40% by weight of undecylenic aldehyde and 30% by weight of
citral or
a mixture comprising 20% by weight of methyl nonyl acetaldehyde, 25% by weight
of
lauric aldehyde, 35% by weight of decanal and 20% by weight of 2-nonen-1-al.
By selecting a perfume component from among the foregoing, a "sun dried odor"
is
produced on the fabric even though the fabric is not actually dried in the
sun. The "sun
dried" odor is formed by selecting aldehydes such that at least one of them is
present
naturally in cotton fabrics after the fabric is dried in the sun and thus, are
a component of
the sun dried odor.
Perfumes also include pro-fragrances such as acetal pro-fragrances, ketal pro-
fragrances,
ester pro-fragrances (e.g., digeranyl succinate), hydrolyzable inorganic-
organic pro-
fragrances, and mixtures thereof. These pro-fragrances may release the perfume
material
as a result of simple hydrolysis, or may be pH-change-triggered pro-fragrances
(e.g., pH
drop) or may be enzymatically releasable pro-fragrances.
Preferred perfume. agents useful herein are defined as follows.
For purposes of the present invention, perfume agents are those which have the
ability to
be incorporated into the pores of the carrier, and hence their utility as
components for
delivery from the carrier through an aqueous environment. Commonly-owned WO
98/41607 describes the characteristic physical parameters of perfume molecules
which
affect their ability to be incorporated into the pores of a carrier, such as a
zeolite.
Obviously for the present invention compositions whereby perfume agents are
being
delivered by the compositions, sensory perception is also required for a
benefit to be
seen by the consumer. For the present invention perfume delivery particles,
the
preferred perfume agents have a threshold of noticeability (measured as odor
detection
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thresholds ("ODT") under carefully controlled GC conditions as described in
detail
hereinafter) less than or equal to 50 parts per billion ("ppb"). Agents with
ODTs above
50 ppb up to 1 part per million ("ppm") are less preferred. Agents with ODTs
above 1
ppm are preferably avoided. Laundry agent perfume mixtures useful for the
present
invention perfume delivery particles preferably comprise from about 0% to
about 80% of
deliverable agents with ODTs above 50 ppb up to 1 ppm, and from about 20% to
about
100% (preferably from about 30% to about 100%; more preferably from about 50%
to
about 100%) of deliverable agents with ODTs less than or equal to 50 ppb.
Also preferred are perfumes carried through the laundry process and thereafter
released
into the air around the dried fabrics (e.g., such as the space around the
fabric during
storage). This requires movement of the perfume out of the zeolite pores with
subsequent partitioning into the air around the fabric. Preferred perfume
agents are
therefore further identified on the basis of their volatility. Boiling point
is used herein as
a measure of volatility and preferred materials have a boiling point less than
300 °C.
Laundry agent perfume mixtures useful for the present invention laundry
particles
preferably comprise at least about 50% of deliverable agents with boiling
point less than
300 °C (preferably at least about 60%; more preferably at least about
70%).
In addition, preferred perfume delivery particles herein for use in laundry
detergents
comprise compositions wherein at least about 80%, and more preferably at least
about
90%, of the deliverable perfume agents have a weighted average ClogP value
ranging
from about 1.0 to 16, and more preferably from about 2.0 to about 8Ø Most
preferably,
the deliverable perfume agents or mixtures have a weighted average CIogP value
between 3 and 4.5. While not wishing to be bound by theory, it is believed
that perfume
materials having the preferred ClogP values are sufficiently hydrophobic to be
held
inside the pores of the zeolite Garner and deposited onto fabrics during the
wash, yet are
able to be released from the zeolite pores at a reasonable rate from dry
fabric to provide a
noticeable benefit. ClogP values are obtained as follows.
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Calculation of CIo~P:
These perfume ingredients are characterized by their octanol/water partition
coefficient
P. The octanol/water partition coefficient of a perfume ingredient is the
ratio between its
equilibrium concentration in octanol and in water. Since the partition
coefficients of
most perfume ingredients are large, they are more conveniently given in the
form of their
logarithm to the base 10, loge.
The loge of many perfume ingredients has been reported; for example, the
Pomona92
database, available from Daylight Chemical Information Systems, Inc. (Daylight
CIS),
contains many, along with citations to the original literature.
However, the loge values are most conveniently calculated by the "CLOGP"
program,
also available from Daylight CIS. This program also lists experimental IogP
values
when they are available in the Pomona92 database. The "calculated loge"
(ClogP) is
determined by the fragment approach of Hansch and Leo (cf., A. Leo, in
Comprehensive
Medicinal Chemistry, Vol. 4, C. Hansch, P.G. Sammens, J. B. Taylor and C. A.
Ramsden, Eds., p. 295, Pergamon Press, 1990). The fragment approach is based
on the
chemical structure of each perfume ingredient and takes into account the
numbers and
types of atoms, the atom connectivity, and chemical bonding. The ClogP values,
which
are the most reliable and widely used estimates for this physicochemical
property, can be
used instead of the experimental loge values in the selection of perfume
ingredients.
Determination of Odor Detection Thresholds:
The gas chromatograph is characterized to determine the exact volume of
material
injected by the syringe, the precise split ratio, and the hydrocarbon response
using a
hydrocarbon standard of known concentration and chain-length distribution. The
air
flow rate is accurately measured and, assuming the duration of a human
inhalation to last
0.2 minutes, the sampled volume is calculated. Since the precise concentration
at the
detector at any point in time is known, the mass per volume inhaled is known
and hence
the concentration of material. To determine whether a material has a threshold
below 10
ppb, solutions are delivered to the sniff port at the back-calculated
concentration. A
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panelist sniffs the GC effluent and identifies the retention time when odor is
noticed.
The average over all panelists determines the threshold of noticeability.
The necessary amount of analyte is injected onto the column to achieve a 10
ppb
concentration at the detector. Typical gas chromatograph parameters for
determining
odor detection thresholds are listed below.
GC: 5890 Series II with Fm detector
7673 Autosampler
Column: J&W Scientific DB-1
Length 30 meters ID 0.25 mm film thickness 1 micron
Method:
Split Injection: 17/1 split ratio
Autosampler: 1.13 microliters per injection
Column Flow: 1.10 mL/minute
Air Flow: 345 mL/minute
Inlet Temp. 245°C
Detector Temp. 285°C
Temperature Information
Initial Temperature: 50°C
Rate: 5 C/minute
Final Temperature: 280°C
Final Time: 6 minutes
Leading assumptions: (i) 0.02 minutes per sniff
(ii) GC air adds to sample dilution
Particularly preferred perfumes for use in the present invention are those
perfumes
referred to as high impact perfumes and characterized by having:
(1) a standard B.P. of about 275°C or lower at 760 mm Hg, and;
(2) a ClogP, or an experimental loge, of about 2 or higher, and;
(3) an ODT of less than or equal to SOppb and greater than 10 ppb,
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Perfume Fixative
Optionally, the perfume can be combined with a perfume fixative. The perfume
fixative
materials employed herein are characterized by several criteria which make
them
especially suitable in the practice of this invention. Dispersible,
toxicologically-acceptable, non-skin irntating, inert to the perfume,
degradable and/or
available from renewable resources, and relatively odorless additives are
used. Perfume
fixatives are believed to slow the evaporation of more volatile components of
the
perfume.
Examples of suitable fixatives include members selected from the group
consisting of
diethyl phthalate, musks, and mixtures thereof. If used, the perfume fixative
comprises
from about 10% to abut 50%, preferably from about 20% to about 40%, by weight,
of
the perfume.
Incorporation of Perfume in Preferred Zeolite Carrier
The Type X or Type Y Zeolites to be used as the preferred carrier herein
preferably
contain less than about 15% desorbable water, more preferably less than about
8%
desorbable water, and most preferably less than about 5% desorbable water.
Such
materials may be obtained by first activating/dehydrating by heating to about
150 to 350
°C, optionally with reduced pressure (from about 0.001 to about 20
Torr). After
activation, the agent is slowly and thoroughly mixed with the activated
zeolite and,
optionally, heated to about 60°C or up to about 2 hours to accelerate
absorption
equilibrium within the zeolite particles. The perfume/zeolite mixture is then
cooled to
room temperature and is in the form of a free-flowing powder.
The amount of perfume or other laundry additive incorporated into the zeolite
carrier is
typically from 1 % to 40%, preferably at least about 10%, more preferably at
least about
18.5%, by weight of the loaded particle, given the limits on the pore volume
of the
zeolite. It is to be recognized, however, that the present invention particles
may exceed
this level of laundry additive by weight of the particle, but recognizing that
excess levels
of laundry additives will not be incorporated into the zeolite, even if only
deliverable
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agents are used. Therefore, the present invention particles may comprise more
than 40%
by weight of laundry agents. Since any excess laundry agents (as well as any
non-
deliverable agents present) are not incorporated into the zeolite pores, these
materials are
likely to be immediately released to the wash solution upon contact with the
aqueous
wash medium.
Coating and Encapsulation of Loaded Zeolite Particles
In an embodiment of the present invention, perfume-loaded zeolite particles in
the form
of a free-flowing powder are thoroughly coated with a hydrophobic oil such as
mineral
oil or perfume oil. The hydrophobic-oil coated particles are mixed to a
solution of
modified starch (CAPSIJLT"", National Starch & Chemicals) and agitated to form
an
emulsion. The emulsion is then spray-dried using a spray dryer having a
spraying
system such as co-current with a spinning disk, with vaneless disk, with vaned
disk or
wheel or with two-fluid mist spray nozzle. Typical conditions involve an inlet
temperature of from about 120 °C to about 220 °C and an outlet
temperature of from
about 50 °C to about 220 °C.
The present laundry additive delivery particles are discrete particles having
particle size
of from about 3 to about 100 microns as measured by standard particle size
analysis
technique. Figure 1 shows a SEM of an intact average sized encapsulated
perfume-
loaded zeolite particle according to the present invention. Figure 2 shows a
cross-section
of a particle according to the present invention, containing loaded zeolite
particles inside
a starch coating.
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Stability Testing of Encapsulated Perfume-Loaded Zeolite Particles
Samples of encapsulated perfume-loaded zeolite particles are kept in open jars
at 80 °F
and 70% Relative Humidity and in sealed plastic bags at 120 °F for ten
days. After that
period the samples are taken out and evaluated organoleptically. Particles are
homogenized and dosed according to regional real washing conditions. They are
mixed
with odorless base granule, previously approved for this kind of test.
Original particles
(which are not subjected to stability testing conditions) are included as
reference.
Perfume intensity scores for the particles are registered in terms of Dry
Fabric Odor.
Particles with perfume loaded zeolite are able to provide between 5 points to
20 points
of advantage, in a perfume intensity scale, compared against control with
sprayed on
perfume alone.
Adiunct Laundry or Cleaning Ingredients
Adjunct ingredients useful in the laundry or cleaning compositions according
to the
present invention include surfactants, builders, and agents such as those
which are
incorporated into the present delivery particles. The various types of agents
useful in
laundry and cleaning compositions are described hereinafter. The compositions
containing particulate compositions 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.
Detersive Surfactant
The granules and/or the agglomerates include surfactants at the levels stated
previously.
The detersive surfactant can be selected from the group consisting of anionic
surfactants,
nonionic surfactants, cationic surfactants, zwitterionic surfactants and
mixtures.
Nonlimiting examples of surfactants useful herein include the conventional C
11-C 18
alkyl benzene sulfonates ("LAS") and primary, branched-chain and random C 10-
C20
alkyl sulfates ("AS"), the C 10-C 1 g secondary (2,3) alkyl sulfates of the
formula
CH3(CH2)x(CHOS03-M+) CH3 and CH3 (CH2)y(CHOS03-M+) CH2CH3 where x
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and (y + 1 ) are integers of at least about 7, preferably at least about 9,
and M is a
water-solubilizing cation, especially sodium, unsaturated sulfates such as
oleyl sulfate,
the C 10-C 1 g alkyl alkoxy sulfates ("AEXS"; especially EO 1-7 ethoxy
sulfates),
C 10-C 1 g alkyl alkoxy carboxylates (especially the EO 1-5
ethoxycarboxylates), the C 10-
1 g glycerol ethers, the C 10-C 1 g alkyl polyglycosides and their
corresponding sulfated
polyglycosides, and C 12-C 1 g alpha-sulfonated fatty acid esters. If desired,
the
conventional nonionic and amphoteric surfactants such as the C 12-C 1 g alkyl
ethoxylates
("AE") including the so-called narrow peaked alkyl ethoxylates and C6-C 12
alkyl phenol
alkoxylates (especially ethoxylates and mixed ethoxy/propoxy); C 12-C 1 g
betaines and
sulfobetaines ("sultaines"), C 10-C 1 g amine oxides, and the like, can also
be included in
the overall compositions. The C 10-C 1 g N-alkyl polyhydroxy fatty acid amides
can also
be used. Typical examples include the C 12-C 1 g N-methylglucamides. See WO
9,206,154. Other sugar-derived surfactants include the N-alkoxy polyhydroxy
fatty acid
amides, such as C 10-C 1 g N-(3-methoxypropyl) glucamide. The N-propyl through
N-
hexyl C 12-C 1 g glucamides can be used for low sudsing. C 10-C20 conventional
soaps
may also be used. If high sudsing is desired, the branched-chain C 1 p-C 16
soaps may be
used. Mixtures of anionic and nonionic surfactants are especially useful.
Other
conventional useful surfactants are listed in standard texts.
The C 10-C 1 g alkyl alkoxy sulfates ("AEXS"; especially EO 1-7 ethoxy
sulfates) and
C 12-C 1 g alkyl ethoxylates ("AE") are the most preferred for the cellulase-
containing
detergents described herein.
Detersive Builder
The granules and agglomerates preferably include a builder at the previously
stated
levels. To that end, inorganic as well as organic builders can be used. Also,
crystalline
as well as amorphous builder materials can be used. Builders are typically
used in fabric
laundering compositions to assist in the removal of particulate soils and to
eliminate
water hardness.
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Inorganic or P-containing detergent builders include, but are not limited to,
the alkali
metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by
the
tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates),
phosphonates, phytic acid, silicates, carbonates (including bicarbonates and
sesquicarbonates), sulphates, and aluminosilicates. However, non-phosphate
builders
are required in some locales. Importantly, the compositions herein function
surprisingly
well even _ in the presence of the so-called "weak" builders (as compared with
phosphates) such as citrate, or in the so-called "under built" situation that
may occur with
zeolite or layered silicate builders.
Examples of silicate builders are the alkali metal silicates, particularly
those having a
Si02:Na20 ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the
layered
sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to H.
P. Rieck.
NaSKS-6 is the trademark for a crystalline layered silicate marketed by
Hoechst
(commonly abbreviated herein as "SKS-6"). Unlike zeolite builders, the Na SKS-
6
silicate builder does not contain aluminum. NaSKS-6 has the delta-Na2Si05
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'YH20 wherein M is sodium or hydrogen, x is a
number
from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 can
be used
herein. Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7
and
NaSKS-11, as the alpha, beta and gamma forms. As noted above, the delta-
Na2Si05
(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 stabilizing 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 15,
1973.
As mentioned previously, aluminosilicate builders are useful builders in the
present
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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:
Mz(zA102)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 about 0.5, and x is an integer from about 1 S to about 264.
Useful aluminosilicate ion exchange materials are commercially available.
These
aluminosilicates can be crystalline or amorphous 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,
Krummel,
et al, issued October 12, 1976. Preferred synthetic crystalline
aluminosilicate ion
exchange materials useful herein are available under the designations Zeolite
A, Zeolite
P (B), Zeolite MAP and Zeolite X. In an especially preferred embodiment, the
crystalline aluminosilicate ion exchange material has the formula:
NaI2~(A102)12(Si02)12]'~20
wherein x is from about 20 to about 30, especially about 27. This material is
known as
Zeolite A. Dehydrated zeolites (x = 0 - 10) may also be used herein.
Preferably, the
aluminosilicate has a particle size of about 0.1-10 microns in diameter.
Organic 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,
"polycarboxylate" refers to compounds having a plurality of carboxylate
groups,
preferably at least 3 carboxylates. Polycarboxylate builder can generally be
added to the
composition in acid form, but can also be added in the form of a neutralized
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 polycarboxylate builders encompasses the
ether
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polycarboxylates, including oxydisuccinate, as disclosed in Berg, U.S. Patent
3,128,287,
issued April 7, 1964, and Lamberti et al, U.S. Patent 3,635,830, issued
January 18, 1972.
See also "TMS/TDS" builders of U.S. Patent 4,663,071, issued to Bush et al, on
May 5,
1987. Suitable ether polycarboxylates also include cyclic compounds,
particularly
alicyclic compounds, such as those described in U.S. Patents 3,923,679;
3,835,163;
4,1 S 8,635; 4,120,874 and 4,102,903.
Other useful detergency builders include the ether hydroxypolycarboxylates,
copolymers
of malefic anhydride with ethylene or vinyl methyl ether, 1, 3, S-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, oxydisuccinic 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 detergent compositions of 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, Bush, issued January 28, 1986. Useful succinic acid builders
include the CS-
C20 alkyl and alkenyl succinic acids and salts thereof. A particularly
preferred
compound 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 European Patent
Application 86200690.5/0,200,263, published November 5, 1986.
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Other suitable polycarboxylates are disclosed in U.S. Patent 4,144,226,
Crutchfield et al,
issued March 13, 1979 and in U.S. Patent 3,308,067, Diehl, issued March 7,
1967. See
also Diehl U.S. Patent 3,723,322.
Fatty acids, e.g., C 12-C 1 g monocarboxylic acids, can also be incorporated
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.
Other Adjunct Ingredients
The composition of the present invention may also include enzymes, enzyme
stabilizers,
brighteners, polymeric dispersing agents (i.e. polyacrylates), carriers,
hydrotropes, suds
boosters or suppressors, soil release agents, dye transfer inhibitors, and
processing aids.
Granular Compositions
The laundry and cleaning compositions of the present invention can be used in
both low
density (below 550 grams/liter) and high density granular compositions in
which the
density of the granule is at least 550 grams/liter. Granular compositions are
typically
designed to provide an in the wash pH of from about 7.5 to about 11.5, more
preferably
from about 9.5 to about 10.5. Low density compositions can be prepared by
standard
spray-drying processes. Various means and equipment are available to prepare
high
density compositions. Current commercial practice in the field employs spray-
drying
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towers to manufacture compositions which have a density less than about 500
g/1.
Accordingly, if spray-drying is used as part of the overall process, the
resulting spray-
dried particles must be further densified using the means and equipment
described
hereinafter. In the alternative, the formulator can eliminate spray-drying by
using
mixing, densifying and granulating equipment that is commercially available.
The
following is a nonlimiting description of such equipment suitable for use
herein.
Various means and equipment are available to prepare high density (i.e.,
greater than
about 550, preferably greater than about 650, grams/liter or "g/I"), high
solubility, free-
flowing, granular detergent compositions according to the present invention.
Current
commercial practice in the field employs spray-drying towers to manufacture
granular
laundry detergents which often have a density less than about 500 g/I. In this
procedure,
an aqueous slurry of various heat-stable ingredients in the final detergent
composition
are formed into homogeneous granules by passage through a spray-drying tower,
using
conventional techniques, at temperatures of about 175°C to about
225°C. However, if
spray drying is used as part of the overall process herein, additional process
steps as
described hereinafter must be used to obtain the level of density (i.e., > 650
g/1) required
by modern compact, low dosage detergent products.
For example, spray-dried granules from a tower can be densified further by
loading a
liquid such as water or a nonionic surfactant into the pores of the granules
and/or
subjecting them to one or more high speed mixer/densifiers. A suitable high
speed
mixer/densifier for this process is a device marketed under the tradename
"Lodige CB
30" or "Lodige CB 30 Recycler" which comprises a static cylindrical mixing
drum
having a central rotating shaft with mixing/cutting blades mounted thereon. In
use, the
ingredients for the detergent composition are introduced into the drum and the
shaft/blade assembly is rotated at speeds in the range of 100-2500 rpm to
provide
thorough mixing/densification. See Jacobs et al, U.S. Patent 5,149,455, issued
September 22, 1992. The preferred residence time in the high speed
mixer/densifier is
from about 1 to 60 seconds. Other such apparatus includes the devices marketed
under
the tradename "Shugi Granulator" and under the tradename "Drais K-TTP 80).
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Another process step which can be used to densify further spray-dried granules
involves
grinding and agglomerating or deforming the spray-dried granules in a moderate
speed
mixer/densifier so as to obtain particles having lower intraparticle porosity.
Equipment
such as that marketed under the tradename "Lodige KM" (Series 300 or 600) or
"Lodige
Ploughshare" mixer/densifiers are suitable for this process step. Such
equipment is
typically operated at 40-160 rpm. The residence time of the detergent
ingredients in the
moderate speed mixer/densifier is from about 0.1 to 12 minutes. Other useful
equipment
includes the device which is available under the tradename "Drais K-T 160".
This
process step which employs a moderate speed mixer/densifier (e.g. Lodige KM)
can be
used by itself or sequentially with the aforementioned high speed
mixer/densifier (e.g.
Lodige CB) to achieve the desired density. Other types of granules
manufacturing
apparatus useful herein include the apparatus disclosed in U.S. Patent
2,306,898, to G. L.
Heller, December 29, 1942.
While it may be more suitable to use the high speed mixer/densifier followed
by the low
speed mixer/densifier, the reverse sequential mixer/densifier configuration is
also
contemplated by the invention. One or a combination of various parameters
including
residence times in the mixer/densifiers, operating temperatures of the
equipment,
temperature and/or composition of the granules, the use of adjunct ingredients
such as
liquid binders and flow aids, can be used to optimize densification of the
spray-dried
granules in the process of the invention. By way of example, see the processes
in Appel
et al, U.S. Patent 5,133,924, issued July 28, 1992 (granules are brought into
a deformable
state prior to densification); Delwel et al, U.S. Patent 4,637,891, issued
January 20, 1987
(granulating spray-dried granules with a liquid binder and aluminosilicate);
Kruse et al,
U.S. Patent 4,726,908, issued February 23, 1988 (granulating spray-dried
granules with a
liquid binder and aluminosilicate); and, Bortolotti et al, U.S. Patent
5,160,657, issued
November 3, 1992 (coating densified granules with a liquid binder and
aluminosilicate).
In those situations in which particularly heat sensitive or highly volatile
detergent
ingredients are to be incorporated into the final detergent composition,
processes which
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31
do not include spray drying towers are preferred. The formulator can eliminate
the
spray-drying step by feeding, in either a continuous or batch mode, starting
detergent
ingredients directly into mixing/densifying equipment that is commercially
available.
One particularly preferred embodiment involves charging a surfactant paste and
an
anhydrous builder material into a high speed mixer/densifier (e.g. Lodige CB)
followed
by a moderate speed mixer/densifier (e.g. Lodige KM) to form high density
detergent
agglomerates. See Capeci et al, U.S. Patent 5,366,652, issued November 22,
1994 and
Capeci et al, U.S. Patent 5,486,303, issued January 23, 1996. Optionally, the
liquid/solids ratio of the starting detergent ingredients in such a process
can be selected
to obtain high density agglomerates that are more free flowing and crisp.
Optionally, the process may include one or more recycle streams of undersized
particles
produced by the process which are fed back to the mixer/densifiers for further
agglomeration or build-up. The oversized particles produced by this process
can be sent
to grinding apparatus and then fed back to the mixing/densifying equipment.
These
additional recycle process steps facilitate build-up agglomeration of the
starting
detergent ingredients resulting in a finished composition having a uniform
distribution of
the desired particle size (400-700 microns) and density (> 550 g/1). See
Capeci et al,
U.S. Patent 5,516,448, issued May 14, 1996 and Capeci et al, U.S. Patent
5,489,392,
issued February 6, 1996. Other suitable processes which do not call for the
use of spray-
drying towers are described by Bollier et al, U.S. Patent 4,828,721, issued
May 9, 1989;
Beerse et al, U.S. Patent 5,108,646, issued April 28, 1992; and, Jolicoeur,
U.S. Patent
5,178,798, issued January 12, 1993.
In yet another embodiment, the high density detergent composition of the
invention can
be produced using a fluidized bed mixer. In this process, the various
ingredients of the
finished composition are combined in an aqueous slurry (typically 80% solids
content)
and sprayed into a fluidized bed to provide the finished detergent granules.
Prior to the
fluidized bed, this process can optionally include the step of mixing the
slurry using the
aforementioned Lodige CB mixer/densifier or a "Flexomix 160" mixer/densifier,
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available from Shugi. Fluidized bed or moving beds of the type available under
the
tradename "Escher Wyss" can be used in such processes.
Another suitable process which can be used herein involves feeding a liquid
acid
precursor of an anionic surfactant, an alkaline inorganic material (e.g.
sodium carbonate)
and optionally other detergent ingredients into a high speed mixer/densifier
(residence
time 5-30 seconds) so as to form agglomerates containing a partially or
totally
neutralized anionic surfactant salt and the other starting detergent
ingredients.
Optionally, the contents in the high speed mixer/densifier cari be sent to a
moderate
speed mixer/densifier (e.g. Lodige KM) for further agglomeration resulting in
the
finished high density detergent composition. See Appel et al, U.S. Patent
5,164,108,
issued November 17, 1992.
Optionally, high density detergent compositions according to the invention can
be
produced by blending conventional or densified spray-dried detergent granules
with
detergent agglomerates in various proportions (e.g. a 60:40 weight ratio of
granules to
agglomerates) produced by one or a combination of the processes discussed
herein.
Additional adjunct ingredients such as enzymes, perfumes, brighteners and the
like can
be sprayed or admixed with the agglomerates, granules or mixtures thereof
produced by
the processes discussed herein. Bleaching compositions in granular form
typically limit
water content, for example, to less than about 7% free water, for best storage
stability.
Deposition of Perfume onto Fabric Surfaces
The method of washing fabrics and depositing perfume thereto comprises
contacting said
fabrics with an aqueous wash liquor comprising at least about 100 ppm of
conventional
detersive ingredients described hereinabove, as well as at least about 0.1 ppm
of the
above-disclosed laundry additive particle. Preferably, said aqueous liquor
comprises
from about 500 ppm to about 20,000 ppm of the conventional detersive
ingredients and
from about 10 ppm to about 200 ppm of the laundry additive particle.
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The laundry additive particle works under all circumstances, but is
particularly useful for
providing odor benefits during the laundering process and on wet and dry
fabrics. The
method comprises contacting fabrics with an aqueous liquor containing at least
about
100 ppm of conventional detersive ingredients and at least about 1 ppm of the
laundry
additive particle such that the perfumed zeolite particles are entrained on
the fabrics,
storing line-dried fabrics under ambient conditions with humidity of at least
20%, drying
the fabric in a conventional automatic dryer, or applying heat to fabrics
which have been
line-dried or machine dried at low heat (less than about 50°C) by
conventional ironing
means (preferably with steam or pre-wetting).
The following nonlimiting examples illustrate the parameters of and
compositions
employed within the invention. All percentages, parts and ratios are by weight
unless
otherwise indicated.
EXAMPLE I
Perfume-loaded zeolite ("PLZ") is prepared by mixing Zeolite 13X and perfume
at a
85/15 weight ratio. The PLZ is thoroughly mixed with the intermediate coating
oil
(ICO) in a proportion of 1:0.5 to 1:1 PLZ:ICO. The mixture is then poured into
a
solution about 4 fold the weight of the mixture and containing about 25% solid
starch.
During the entire process, this second mixture is kept with agitation using a
mixer or a
high-speed homogenizer such as a tissue homogenizer. The mixture is then
pumped into
a spray dryer at 180 °C to 220 °C. The process yields a fine
powder, which is suitable for
use as a laundry additive in a detergent composition. The perfume loaded in
the zeolite
has following composition:
Material Name
Violiff 2.5
Frutene 15.0
Methyl Iso Butenyl Tetrahydro7.5
Pyran
Cymal 10.0
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Florhydral 15.0
Delta Damascone 15.0
Ionone Beta 25.0
P.T. Bucinal 10.0
The particles formed unexpectedly have a superior "Neat Product Odor" ("NPO")
and
emit only minimal detectable odors over the base product odor as observed by a
statistically significant number of panelist graders. This provides strong
evidence of the
lack of perfume displacement from the carrier particles.
EYAMPLE II
Several detergent compositions are exemplified below incorporating the perfume
particle
prepared in Example I.
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Base Granule A B C
Aluminosilicate 18.0 22.0 24.0
Sodium Sulfate 10.0 19.0 6.0
Sodium Polyacrylate Polymer 3.0 2.0 4.0
PolyethyleneGlycol (MW=400) 2.0 1.0 --
012-13 Linear Alkylbenzene 6.0 7.0 8.0
Sulfonate, Na
014-16 Secondary Alkyl Sulfate,3.0 3.0 --
Na
014-15 Alkyl Ethoxylated Sulfate,3.0 9.0 --
Na
Sodium Silicate 1.0 2.0 3.0
Brightener 24/471 0.3 0.3 0.3
Sodium Carbonate 7.0 26.0
Carboxymethyl Cellulose -- -- 1.0
DTPMPA~ -- -- 0.5
DTPA3 __ __
0.5
Admixed Agglomerates
014-15 Alkyl Sulfate, Na S.0 -- --
012-13 Linear Alkylbenzene 2.0 -- --
Sulfonate, Na
Sodium Carbonate 4.0 -- --
Polyethylene Glycol (MW=4000) 1.0 -- --
Admix
Sodium Carbonate -- -- 13.0
012-15 Alkyl Ethoxylate (E0=7)2.0 0.5 2.0
CI2-15 Alkyl Ethoxylate (E0=3)-- -- 2.0
Perfume Spray-On 0.3 0.4 0.3
Perfume Particles' 0.5 0.5 0.5
Polyvinylpyrrolidone 0.5 -- --
Polyvinylpyridine N-oxide 0.5 -- --
Polyvinylpyrrolidone-polyvinylimidazole0.5 -- --
Distearylamine & Cumene Sulfonic2.0 -- --
Acid
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Soil Release Polymers 0.5 -- --
Lipolase Lipase (100.000 LU/I)60.5 -- 0.5
Termamyl Amylase (60 KNIJ/g)6 0.3 -- 0.3
CAREZYME~ Cellulase (1000 CEVL1/g)60.3 -- --
Protease (40mg/g)7 0.5 0.5 0.5
NOBSB __ __
5.0
TAED9 __ __
3.0
Sodium Percarbonate 12.0 -- --
Sodium Perborate Monohydrate -- -- 22.0
Polydimethylsiloxane 0.3 -- 3.0
Sodium Sulfate -- -- 3.0
Miscellaneous (water, etc.) balance balance balance
Total 100 100 100
1. Purchased from Cuba-Cieigy
2. Diethylene Triamine PentaMethylene Phosophonic Acid
3. Diethylene Triamine Pentaacetic Acid
4. From Example I
5. Made according to U.S. Patent 5,415,807, issued May 16, 1995 to Gosselink,
et al.
6. Purchased from Novo Nordisk A/S
7. Purchased from Genencor
8. Nonanoyloxybenzenesulfonate
9. Tetra Acetyl Ethylene Diamine
EXAMPLE III
The following detergent compositions according to the invention are suitable
for
machine and handwashing operations. The base granule is prepared by a
conventional
spray drying process in which the starting ingredients are formed into a
slurry and passed
through a spray drying tower having a counter current stream of hot air (200-
400 C)
resulting in the formation of porous granules. The remaining adjunct detergent
ingredients are sprayed on or added dry.
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Base Granule A B C
12-13 Alkylbenzene Sulfonate,19.0 18.0 19.0
Na
Cationic Surfactant) 0.5 0.5 --
DTPMPA~ 0.3 -- --
DTPA -- 0.3 --
Sodium Tripolyphosphate 25.0 19.0 29.0
Acrylic/Maleic Co-polymer 1.0 0.6 --
Carboxymethylcellulose 0.3 0.2 0.3
Brightener 49/15/33 0.2 0.2 0.2
Sodium Sulfate 28.0 39.0 15.0
Sodium Silicate (2.0R) 7.5 -- --
Sodium Silicate (1.6R) -- 7.5 6.0
Admix
Quantum (zinc phthalocyanine 2.0 2.0 2.0
sulfonate)
Sodium Carbonate 5.0 6.0 20.0
C12-13 Alkly Ethoxylate (E0=7)0.4 -- 1.2
Savinase5 Protease (4KNPY/g) 0.6 -- 1.0
Termamyls Amylase (60KNU/g) 0.4 -- --
Lipolases Lipase ( 100,000 0.1 0.1 0.1
LU/I)
SavBans (6 KNPU/100 KNU/g) -- 0.3 --
CAREZYME~5 Cellulase (1000 -- 0.1 --
CEVLJ/g)
Soil Release Polymer6 0.1 0.1 0.3
Perfume Spray-On 0.4 0.4 0.4
Perfume Panicles ~ 1.5 1.5 2.0
Miscellaneous (water, etc.) balance balance balance
Total 100. 100. 100.
0 0 0
1. C12-l4Dimethyl Hydroxyethyl Quaternary Ammonium Compound
2. Diethylene Triamine Pentamethylenephosphoric Acid
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3. Diethylene Triamine Pentaacetic Acid
4. Purchased from Ciba-Geigy
S. Purchased from Novo Nordisk A/S
6. Made according to U.S. patent 5,415,807 issued May 16, 1995 to Gosselink
et al
7. From Example I
EXAMPLE IV
The following detergent composition invention is in the
according to the form of a
laundry bar which is particularly
suitable for handwashing operations.
Weight
Coconut Fatty Alkyl Sulfate 30.0
Sodium Tripolyphosphate 5.0
Tetrasodium Pyrophosphate 5.0
Sodium Carbonate 20.0
Sodium Sulfate 5.0
Calcium Carbonate 5.0
Na1,9K0.1Ca(C03)2 15.0
Aluminosilicate 2.0
Coconut Fatty Alcohol 2.0
Perfume Particle 1 1.0
Perfume Spray-On 1.0
Miscellaneous (water, etc.) Balance
Total 100.0
1. From Example I.
Having thus described the invention in detail, it will be clear to those
skilled in the art
that various changes may be made without departing from the scope of the
invention and
the invention is not to be considered limited to what is described in the
specification
