U.S. patent application number 15/412312 was filed with the patent office on 2017-06-01 for composition comprising microcapsules.
The applicant listed for this patent is The Procter & Gamble Company. Invention is credited to Karl Ghislain BRAECKMAN, Karel Jozef Maria DEPOOT, Johan SMETS, Tim Roger Michel VAN PACHTENBEKE.
Application Number | 20170152464 15/412312 |
Document ID | / |
Family ID | 40361665 |
Filed Date | 2017-06-01 |
United States Patent
Application |
20170152464 |
Kind Code |
A1 |
BRAECKMAN; Karl Ghislain ;
et al. |
June 1, 2017 |
Composition Comprising Microcapsules
Abstract
A liquid composition having a microcapsule, the microcapsule
having an aldehyde-containing resin, and one or more formaldehyde
scavenger which reacts with formaldehyde to achieve more than about
60% reaction completeness in about 15 minutes time at pH 8 and at
about 21.degree. C. A liquid composition having a microcapsule, the
microcapsule having an aldehyde-containing resin, one or more
sulfur-based formaldehyde scavenger and optionally a
non-sulfur-based formaldehyde scavenger.
Inventors: |
BRAECKMAN; Karl Ghislain;
(Gerpinnes, BE) ; DEPOOT; Karel Jozef Maria;
(Anzegem-Vichte, BE) ; VAN PACHTENBEKE; Tim Roger
Michel; (Puurs, BE) ; SMETS; Johan; (Lubbeek,
BE) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
The Procter & Gamble Company |
Cincinnati |
OH |
US |
|
|
Family ID: |
40361665 |
Appl. No.: |
15/412312 |
Filed: |
January 23, 2017 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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14162862 |
Mar 10, 2014 |
9580673 |
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15412312 |
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12569026 |
Sep 29, 2009 |
8664174 |
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14162862 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C11D 3/505 20130101;
C11D 3/046 20130101; C11D 17/0039 20130101; C11D 3/32 20130101 |
International
Class: |
C11D 17/00 20060101
C11D017/00; C11D 3/50 20060101 C11D003/50 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 30, 2008 |
EP |
08 165 469.1 |
Claims
1. A liquid composition comprising a microcapsule, said
microcapsule comprising an aldehyde-containing resin, and one or
more formaldehyde scavenger which reacts with formaldehyde to
achieve more than about 60% reaction completeness in about 15
minutes time at pH 8 and at about 21.degree. C.
2. The liquid composition according to claim 1, wherein said
microcapsule further comprises one or more sulfur-based
formaldehyde scavenger.
3. The liquid composition according to claim 2, wherein said
microcapsule further comprises a non-sulfur-based formaldehyde
scavenger.
4. The liquid composition according to claim 1, wherein said
composition comprises a pre-made slurry which comprises said
microcapsule and one or more non-sulfur based formaldehyde
scavenger.
5. The composition according to claim 3, wherein the composition
comprises from about 0.0001% to about 1%, by weight of said
composition, of said one or more non-sulfur-based formaldehyde
scavenger.
6. The composition according to claim 3, wherein said one or more
non-sulfur-based formaldehyde scavenger comprises
acetoacetamide.
7. The composition according to claim 2, wherein the composition
comprises from about 0.001% to about 2.0%, by weight of said
composition, of said one or more sulfur-based formaldehyde
scavenger.
8. The composition according to claim 2, wherein said microcapsule
comprises microcapsule wall material having a ratio, by weight, of
said one or more sulfur-based formaldehyde scavenger to said
microcapsule wall material of from about 0.05:1 to about 10:1.
9. The composition according to claim 2, wherein said microcapsule
comprises microcapsule wall material having a ratio, by weight, of
said one or more sulfur-based formaldehyde scavenger to said
microcapsule wall material of from about 0.1:1 to about 6:1.
10. The composition according to claim 3, said composition having a
ratio, by weight, of said non-sulfur-based formaldehyde scavenger
to said one or more sulfur-based scavenger of from about 0.001:1 to
about 5:1.
11. The composition according to claim 3, said composition having a
ratio, by weight, of said non-sulfur-based scavenger to said one or
more sulfur-based scavenger of from about 0.01:1 to about 1:1.
12. The composition according to claim 1, wherein said microcapsule
is a core in shell microcapsule comprising a substance selected
from the group consisting of perfume raw materials, silicone oils,
waxes, hydrocarbons, higher fatty acids, essential oils, lipids,
skin coolants, vitamins, sunscreens, antioxidants, glycerine,
catalysts, bleach particles, silicon dioxide particles, malodor
reducing agents, dyes, brighteners, antibacterial actives,
antiperspirant actives, cationic polymers and mixtures thereof.
13. The composition according to claim 3, wherein said
non-sulfur-based formaldehyde scavenger is selected from the group
consisting of urea, ethylene urea, lysine, glycine, serine,
carnosine, histidine, 3,4-diaminobenzoic acid, allantoin,
glycouril, anthranilic acid, methyl anthranilate, methyl
4-aminobenzoate, ethyl acetoacetate, acetoacetamide, malonamide,
ascorbic acid, 1,3-dihydroxyacetone dimer, biuret, oxamide,
benzoguanamine, pyroglutamic acid, pyrogallol, methyl gallate,
ethyl gallate, propyl gallate, triethanol amine, succinamide,
benzotriazol, triazole, indoline, oxamide, sorbitol, glucose,
cellulose, poly(vinyl alcohol), partially hydrolyzed
poly(vinylformamide), poly(vinyl amine), poly(ethylene imine),
poly(oxyalkyleneamine), poly(vinyl alcohol)-co-poly(vinyl amine),
poly(4-aminostyrene), poly(l-lysine), chitosan, hexane diol,
ethylenediamine-N,N'-bisacetoacetamide,
N-(2-ethylhexyl)acetoacetamide, 2-benzoylacetoacetamide,
N-(3-phenylpropyl) acetoacetamide, lilial, helional, melonal,
triplal, 5,5-dimethyl-1,3-cyclohexanedione,
2,4-dimethyl-3-cyclohexenecarboxformaldehyde,
2,2-dimethyl-1,3-dioxan-4,6-dione, 2-pentanone, dibutyl amine,
triethylenetetramine, ammonium hydroxide, benzylamine,
hydroxycitronellol, cyclohexanone, 2-butanone, pentane dione,
dehydroacetic acid, ammonium hydroxide or a mixture thereof.
14. The composition according to claim 2 wherein said one or more
sulfur-based formaldehyde scavenger is selected from the group
consisting of alkali or alkali earth metal dithionites,
pyrosulfites, sulfites, bisulfite, metasulfite, monoalkyl sulphite,
dialkyl sulphite, dialkylene sulphite, sulfides, thiosulfates and
thiocyanates, mercaptans, such as thioglycolic acid,
mercaptoethanol, 4-hydroxy-2-mercapto-6-methylpyrimidine,
mercaptothiazoline, thiodialkanoic acids, such as thiodipropionic
acid, dithiodialkanoic acids, such as 3,3'-dithiodipropionic acid,
sulfinates, such as sodium formaldehydesulfoxylate or
formamidinosulfinic acid and thiourea and mixtures thereof.
15. A liquid composition comprising a microcapsule, said
microcapsule comprising an aldehyde-containing resin, one or more
sulfur-based formaldehyde scavenger and optionally a
non-sulfur-based formaldehyde scavenger.
16. The composition according to claim 15, wherein the microcapsule
is a core in shell microcapsule comprising a substance selected
from the group consisting of perfume raw materials, silicone oils,
waxes, hydrocarbons, higher fatty acids, essential oils, lipids,
skin coolants, vitamins, sunscreens, antioxidants, glycerine,
catalysts, bleach particles, silicon dioxide particles, malodor
reducing agents, dyes, brighteners, antibacterial actives,
antiperspirant actives, cationic polymers and mixtures thereof.
17. The composition according to claim 15, wherein the one or more
sulfur-based formaldehyde scavenger is selected from the group
consisting of alkali or alkali earth metal dithionites,
pyrosulfites, sulfites, bisulfite, metasulfite, monoalkyl sulphite,
dialkyl sulphite, dialkylene sulphite, sulfides, thiosulfates and
thiocyanates, mercaptans, such as thioglycolic acid,
mercaptoethanol, 4-hydroxy-2-mercapto-6-methylpyrimidine,
mercaptothiazoline, thiodialkanoic acids, such as thiodipropionic
acid, dithiodialkanoic acids, such as 3,3'-dithiodipropionic acid,
sulfinates, such as sodium formaldehydesulfoxylate or
formamidinosulfinic acid and thiourea and mixtures thereof.
18. The composition according to claim 15, wherein the
non-sulfur-based formaldehyde scavenger is selected from the group
consisting of urea, ethylene urea, lysine, glycine, serine,
carnosine, histidine, 3,4-diaminobenzoic acid, allantoin,
glycouril, anthranilic acid, methyl anthranilate, methyl
4-aminobenzoate, ethyl acetoacetate, acetoacetamide, malonamide,
ascorbic acid, 1,3-dihydroxyacetone dimer, biuret, oxamide,
benzoguanamine, pyroglutamic acid, pyrogallol, methyl gallate,
ethyl gallate, propyl gallate, triethanol amine, succinamide,
benzotriazol, triazole, indoline, oxamide, sorbitol, glucose,
cellulose, poly(vinyl alcohol), partially hydrolyzed
poly(vinylformamide), poly(vinyl amine), poly(ethylene imine),
poly(oxyalkyleneamine), poly(vinyl alcohol)-co-poly(vinyl amine),
poly(4-aminostyrene), poly(l-lysine), chitosan, hexane diol,
ethylenediamine-N, N'-bisacetoacetamide,
N-(2-ethylhexyl)acetoacetamide, 2-benzoylacetoacetamide,
N-(3-phenylpropyl) acetoacetamide, lilial, helional, melonal,
triplal, 5,5-dimethyl-1,3-cyclohexanedione,
2,4-dimethyl-3-cyclohexenecarboxformaldehyde,
2,2-dimethyl-1,3-dioxan-4,6-dione, 2-pentanone, dibutyl amine,
triethylenetetramine, ammonium hydroxide, benzylamine,
hydroxycitronellol, cyclohexanone, 2-butanone, pentane dione,
dehydroacetic acid, ammonium hydroxide or a mixture thereof.
19. A process of preparing a composition comprising the steps of:
i) preparing a slurry of microcapsules comprising an
aldehyde-containing resin and optionally one or more formaldehyde
scavenger; and then ii) adding said slurry to a substance
comprising one or more sulfur-based formaldehyde scavenger.
20. The process according to claim 19, wherein said one or more
formaldehyde scavenger of step i) comprises a non-sulfur-based
formaldehyde scavenger.
Description
FIELD OF THE INVENTION
[0001] The present invention relates to a liquid composition
comprising microcapsules, said microcapsules comprising a
formaldehyde-containing resin, and a formaldehyde scavenger with
fast reaction kinetics. More preferably the scavenger is a
sulfur-based formaldehyde scavenger. The composition preferably
additionally comprises at least one further formaldehyde scavenger
present in the premix slurry of the microcapsule, which is added to
a final product liquid composition. Said further formaldehyde
scavenger added via the slurry, may be sulfur-based, but is
preferably non-sulfur based.
BACKGROUND TO THE INVENTION
[0002] Benefit agents, such as perfumes, silicones, waxes, flavors,
vitamins and fabric softening agents, are expensive and generally
less cost effective when employed at high levels in personal care
compositions, cleaning compositions, and fabric care compositions.
As a result, there is a desire to maximize the effectiveness of
such benefit agents. One method of achieving such objective is to
improve the delivery efficiency and active lifetime of the benefit
agent. This can be achieved by providing the benefit agent as a
component of a microcapsule.
[0003] Microcapsules are made either by supporting the benefit
agent on a water-insoluble porous carrier or by encapsulating the
benefit agent in a water-insoluble shell. In the latter category
microencapsulates are made by precipitation and deposition of
polymers at the interface, such as in coacervates, for example as
disclosed in GB-A-O 751 600, U.S. Pat. No. 3,341,466 and EP-A-0 385
534, or other polymerisation routes such as interfacial
condensation U.S. Pat. No. 3,577,515, US-A-2003/0125222, U.S. Pat.
No. 6,020,066, WO2003/101606, U.S. Pat. No. 5,066,419. A
particularly useful means of encapsulation is using the
melamine/urea--formaldehyde condensation reaction as described in
U.S. Pat. No. 3,516,941, U.S. Pat. No. 5,066,419 and U.S. Pat. No.
5,154,842. Such capsules are made by first emulsifying a benefit
agent in small droplets in a pre-condensate medium obtained by the
reaction of melamine/urea and formaldehyde and then allowing the
polymerisation reaction to proceed along with precipitation at the
oil-water interface. The encapsulates ranging in size from a few
micrometer to a millimeter are then obtained in a suspension form
in an aqueous medium.
[0004] Microcapsules provide several benefits. They have the
benefit of protecting the benefit agent from physical or chemical
reactions with incompatible ingredients in the composition,
volatilization or evaporation. Microcapsules have the further
advantage in that they can deliver the benefit agent to the
substrate and can be designed to rupture under desired conditions,
such as when a fabric becomes dry. Microcapsules can be
particularly effective in the delivery and preservation of
perfumes. Perfumes can be delivered to and retained within the
fabric by a microcapsule that only ruptures, and therefore releases
the perfume, when the fabric is dry.
[0005] Preferred microcapsules have a core-in-shell architecture
and comprise a shell of formaldehyde-containing resin. The
Applicants have found, however, that when such microcapsules are
formulated into a composition, regardless of the content of the
core of the microcapsule, the composition containing said
microcapsule becomes discoloured. Particularly problematic is a
blue product discolouring to green. This is particularly
problematic when the product is packaged in a transparent or
translucent container. Discoloration appears to be dependent on
microcapsule level and storage temperature. Higher storage
temperature and/or higher concentration of microcapsule results in
a product that discolours faster and with more colour depth.
SUMMARY OF THE INVENTION
[0006] According to the present invention there is provided a
liquid composition comprising a microcapsule, comprising an
aldehyde-containing resin, and one or more formaldehyde scavenger
which reacts with formaldehyde to achieve more then 60% reaction
completeness in 15 minutes time at pH 8 and at 21.degree. C.
[0007] According to the present invention there is further provided
a liquid composition comprising a microcapsule comprising an
aldehyde-containing resin, one or more sulfur-based formaldehyde
scavenger and optionally one or more non-sulfur based formaldehyde
scavenger.
[0008] According to the present invention there is also provided a
process of preparing the composition comprising the steps of:
i) preparing a slurry of microcapsules comprising an
aldehyde-containing resin and optionally one or more formaldehyde
scavenger; ii) adding said slurry to a composition comprising one
or more sulfur-based formaldehyde scavenger.
BRIEF DESCRIPTION OF THE DRAWINGS
[0009] The present disclosure may be more readily understood with
reference to the appended drawing FIGURES where:
[0010] FIG. 1 is a plot showing formaldehyde scavenger
kinetics.
DETAILED DESCRIPTION OF THE INVENTION
[0011] The liquid compositions of the present invention are
preferably suitable for use as laundry or hard surface cleaning
treatment compositions.
[0012] The term liquid is meant to include viscous or fluid liquids
with newtonian or non-Newtonian rheology and gels. Said composition
may be packaged in a container or as an encapsulated unitized dose.
The latter form is described in more detail below. Liquid
compositions may be aqueous or non-aqueous. Where the composition
is aqueous it may comprise from 20% to 90% water, more preferably
from 20% to 80% water and most preferably from 25% to 65% water.
Non-aqueous compositions comprise less than 20% water, preferably
less than 15%, most preferably less than 10% water. Compositions
used in unitized dose products comprising a liquid composition
enveloped within a water-soluble film are often described to be
non-aqueous. Compositions according to the present invention for
this use preferably comprise from 2% to 15% water, more preferably
from 2% to 10% water and most preferably from 4% to 10% water.
[0013] The compositions of the present invention preferably have
viscosity from 1 to 10000 centipoises (1-10000 mPa*s), more
preferably from 100 to 7000 centipoises (100-7000 mPa*s), and most
preferably from 200 to 1500 centipoises (200-1500 mPa*s) at 20
s.sup.-1 and 21.degree. C. Viscosity can be determined by
conventional methods. Viscosity according to the present invention
however is measured using an AR 550 rheometer from TA instruments
using a plate steel spindle at 40 mm diameter and a gap size of 500
.mu.m.
Microcapsule
[0014] The microcapsule of the present invention comprises an
aldehyde-containing resin. More preferably the microcapsule has a
core-in-shell structure. More preferably the shell is an
aminoplast. Most preferably the microcapsule comprises a
formaldehyde-containing shell.
[0015] The microcapsule preferably comprises a core material and a
shell wall material that at least partially, preferably completely
surrounds the core material. Said microcapsule preferably has:
[0016] a.) a particle size coefficient of variation of from about
1.5 to about 6.0, from about 2.0 to about 3.5, or even from about
2.5 to about 3.2; [0017] b.) a fracture strength of from about 0.1
psia to about 110 psia, from about 1 to about 50 psia, or even from
about 4 to about 16 psia; [0018] c.) a benefit agent retention
ratio of from about 2 to about 110, from about 30 to about 90, or
even from about 40 to about 70; and [0019] d.) an average particle
size of from about 1 micron to about 100 microns, from about 5
microns to about 80 microns, or even from about 15 microns to about
50 microns.
(1) Benefit Agent Retention Ratio
[0019] [0020] a.) Add 1 gram of particle to 99 grams of composition
that the particle will be employed in. [0021] b.) Age the particle
containing composition of a.) above for 2 weeks at 40.degree. C. in
a sealed, glass jar. [0022] c.) Recover the particles from b.)
above by filtration. [0023] d.) Treat the particles of c.) above
with a solvent that will extract all the benefit agent from the
particles. [0024] e.) Inject the benefit agent containing solvent
from d.) above into a Gas Chromatograph and integrate the peak
areas to determine the total quantity of benefit agent extracted
from the particle sample. [0025] f.) This quantity is then divided
by the quantity that would be present if nothing had leaked out of
the microcapsule (e.g. the total quantity of core material that is
dosed into the composition via the microcapsules). This value is
then multiplied by the ratio of average particle diameter to
average particle thickness to obtain a Benefit Agent Retention
Ratio.
[0026] A detailed analytical procedure to measure the Benefit Agent
Retention Ratio is:
ISTD Solution
[0027] Weigh out 25 mg dodecane into a weigh boat. Rinse the
dodecane into a 1000 mL volumetric flask using ethanol. Add ethanol
to volume mark. Stir solution until mixed. This solution is stable
for 2 months.
Calibration Standard
[0028] Weigh out 75 mg of core material into a 100 mL volumetric
flask. Dilute to volume with ISTD solution to from above. This
standard solution is stable for 2 months. Mix well. Analyze via
GC/FID.
[0029] Basic Sample Prep (Prepare Samples in Triplicate)
[0030] Weigh 1.000 gram sample of aged composition containing
particles into a 100 mL tri-pour beaker. Record weight. Add 4 drops
(approximately 0.1 gram) 2-ethyl-1,3-Hexanediol into the tri-pour
beaker. Add 50 mL Deionized water to the beaker. Stir for 1 minute.
Using a 60 cc syringe, filter through a Millipore Nitrocellulose
Filter Membrane (1.2 micron, 25 mm diameter). Rinse through the
filter with 10 mL of Hexane. Carefully remove the filter membrane
and transfer to a 20 mL scintillation vial (using tweezers). Add 10
mL ISTD solution (as prepared above) to the scintillation vial
containing the filter. Cap tightly, mix, and heat vial at
60.degree. C. for 30 min. Cool to room temperature. Remove 1 mL and
filter through a 0.45-micron PTFE syringe filter into GC vial.
Several PTFE filters may be required to filter a 1 mL sample
aliquot. Analyze via GC/FID.
[0031] GG/FID Analysis Method:
[0032] Column--30 m.times.0.25 mm id, 1-um DB-1 phase. GC--6890 GC
equipped with EPC control and constant flow capability.
Method--50.degree. C., 1 min hold, temperature ramp of 4.degree.
C./min to 300.degree. C., and hold for 10 min.
Injector--1 uL splitless injection at 240.degree. C.
[0033] GC/FID Analysis Method--Microbore Column Method:
[0034] Column--20 m.times.0.1 mm id, 0.1 .mu.m DB-5. GC--6890 GC
equipped with EPC control and constant flow capability (constant
flow 0.4 mL/min). Method--50.degree. C., no hold, temperature ramp
of 16.degree. C./min to 275.degree. C., and hold for 3 min.
Injector--1 .mu.L split injection (80:1 split) at 250.degree.
C.
Calculations:
[0035] {{
% Total Perfume = A IS .times. W per - std .times. A per - sam A
per - std .times. A is - sam .times. W sam .times. 100 %
##EQU00001##
}} where A.sub.is=Area of internal standard in the core material
calibration standard; W.sub.per-std=weight of core material in the
calibration sample; A.sub.per-sam=Area of core material peaks in
the composition containing particle sample; A.sub.per-std=Area of
core material peaks in the calibration sample; A.sub.is-sam=Area of
internal standard in composition containing particle sample;
W.sub.sam=Weight of the composition containing particle sample
Retention_Ratio = ( Total_Perfume Perfume_Dosed _Into _Product _Via
_Microcapsules ) ( .mu. T ) ##EQU00002##
where .mu. is the average particle diameter, from Test Method 1 and
T is the average particle thickness as calculated from Test Method
3
(2) Fracture Strength
[0036] a.) Place 1 gram of particles in 1 liter of distilled
deionized (DI) water. [0037] b.) Permit the particles to remain in
the DI water for 10 minutes and then recover the particles by
filtration. [0038] c.) Determine the average rupture force of the
particles by averaging the rupture force of 50 individual
particles. The rupture force of a particle is determined using the
procedure given in Zhang, Z.; Sun, G; "Mechanical Properties of
Melamine-Formaldehyde microcapsules," J. Microencapsulation, vol
18, no. 5, pages 593-602, 2001. Then calculate the average fracture
pressure by dividing the average rupture force (in Newtons) by the
average cross-sectional area (as determined by Test Method 1 above)
of the spherical particle (.pi.r.sup.2, where r is the radius of
the particle before compression). [0039] d.) Calculate the average
fracture strength by using the following equation: {{
[0039] .sigma. fracture _ stress = P 4 ( d / T ) ##EQU00003##
}} where P is the average fracture pressure from a.) above, d is
the average diameter of the particle (as determined by Test Method
1 above), T is the average shell thickness of the particle shell as
determined by the following equation: {{
T = r capsule ( 1 - c ) .rho. perfume 3 [ c .rho. wall + ( 1 - c )
.rho. perfume ] ##EQU00004##
}} where c is the average perfume content in the particle; r is the
average particle radius; .rho..sub.wall is the average density of
the shell as determined by ASTM method B923-02, "Standard Test
Method for Metal Powder Skeletal Density by Helium or Nitrogen
Pycnometry", ASTM International. .rho..sub.perfume is the average
density of the perfume as determined by ASTM method D1480-93 (1997)
"Standard Test Method for Density and Relative Density (Specific
Gravity) of Viscous Materials by Bingham Pycnometer", ASTM
International.
[0040] In one aspect of the Applicants' invention, said
microcapsule may have and/or comprise any combination of the
parameters described in the present specification.
[0041] Suitable microcapsule wall materials include materials
selected from the group consisting of reaction products of one or
more amines with one or more formaldehydes, such as urea
cross-linked with formaldehyde or gluterformaldehyde, melamine
cross-linked with formaldehyde; gelatin-polyphosphate coacervates
cross-linked with gluterformaldehyde; and mixtures thereof. In one
aspect, the wall material comprises melamine cross-linked with
formaldehyde.
[0042] Useful core benefit agents include perfume raw materials,
silicone oils, waxes, hydrocarbons, higher fatty acids, essential
oils, lipids, skin coolants, vitamins, sunscreens, antioxidants,
glycerine, catalysts, bleach particles, silicon dioxide particles,
malodor reducing agents, dyes, brighteners, antibacterial actives,
antiperspirant actives, cationic polymers and mixtures thereof. In
one aspect, said perfume raw material is selected from the group
consisting of alcohols, ketones, formaldehydes, esters, ethers,
nitriles alkenes. In one aspect, said perfume may comprise a
perfume raw material selected from the group consisting of perfume
raw materials having a boiling point (B.P.) lower than about
250.degree. C. and a C log P lower than about 3, perfume raw
materials having a B.P. of greater than about 250.degree. C. and a
C log P of greater than about 3, perfume raw materials having a
B.P. of greater than about 250.degree. C. and a C log P lower than
about 3, perfume raw materials having a B.P. lower than about
250.degree. C. and a C log P greater than about 3 and mixtures
thereof. Perfume raw materials having a boiling point B.P. lower
than about 250.degree. C. and a C log P lower than about 3 are
known as Quadrant I perfume raw materials, perfume raw materials
having a B.P. of greater than about 250.degree. C. and a C log P of
greater than about 3 are known as Quadrant IV perfume raw
materials, perfume raw materials having a B.P. of greater than
about 250.degree. C. and a C log P lower than about 3 are known as
Quadrant II perfume raw materials, perfume raw materials having a
B.P. lower than about 250.degree. C. and a C log P greater than
about 3 are known as a Quadrant III perfume raw materials. In one
aspect, said perfume comprises a perfume raw material having B.P.
of lower than about 250.degree. C. In one aspect, said perfume
comprises a perfume raw material selected from the group consisting
of Quadrant I, II, III perfume raw materials and mixtures thereof.
In one aspect, said perfume comprises a Quadrant III perfume raw
material. Suitable Quadrant I, II, III and IV perfume raw materials
are disclosed in U.S. Pat. No. 6,869,923 B1.
Process of Making Microcapsules and Slurry Containing
Microcapsules
[0043] Microcapsules are commercially available. Processes of
making said microcapsules is described in the art. More particular
processes for making suitable microcapsules are disclosed in U.S.
Pat. No. 6,592,990 B2 and/or U.S. Pat. No. 6,544,926 B1 and the
examples disclosed herein.
[0044] The slurry of the present invention is the composition
resulting from this manufacturing process. Said slurry comprises
microcapsules, water and precursor materials for making the
microcapsules. The slurry may comprise other minor ingredients,
such as an activator for the polymerization process and/or a pH
buffer. To the slurry, a formaldehyde scavenger may be added.
Formaldehyde Scavenger
[0045] The Applicants have found that compositions comprising
formaldehyde-containing microcapsules discolour over time. This
phenomenon exists even in the absence of any benefit agent at the
core of the microcapsule. The Applicants have further found that
there is a preferred selection in the choice of formaldehyde
scavenger to achieve the most stable, especially colour stable
final composition. In one embodiment of the present invention, the
composition comprises one or more sulfur-based formaldehyde
scavenger. The liquid composition optionally additionally comprises
one or more non-sulfur-based formaldehyde scavenger.
[0046] The sulfur-based scavenger may be added to the slurry
containing the microcapsules prior to addition to the composition.
However, high levels of sulfur-based scavenger in the slurry could
result in high levels of sulfur dioxide emission, which would be
regarded as a plant safety issue. The sulfur-based formaldehyde
scavenger is therefore preferably added directly to the product.
The non-sulfur based scavenger, where present, is preferably added
to the slurry containing the microcapsules prior to addition to the
composition to ensure adequate formaldehyde control in the slurry.
The Applicants have found that if a non-sulfur based scavenger is
added directly to the detergent composition, even if also added via
the slurry, the composition continues to show discolouration,
despite the presence of scavenger.
[0047] The non-sulfur based formaldehyde scavenger is preferably
selected from the group consisting of urea, ethylene urea, lysine,
glycine, serine, carnosine, histidine, 3,4-diaminobenzoic acid,
allantoin, glycouril, anthranilic acid, methyl anthranilate, methyl
4-aminobenzoate, ethyl acetoacetate, acetoacetamide, malonamide,
ascorbic acid, 1,3-dihydroxyacetone dimer, biuret, oxamide,
benzoguanamine, pyroglutamic acid, pyrogallol, methyl gallate,
ethyl gallate, propyl gallate, triethanol amine, succinamide,
benzotriazol, triazole, indoline, oxamide, sorbitol, glucose,
cellulose, poly(vinyl alcohol), partially hydrolyzed
poly(vinylformamide), poly(vinyl amine), poly(ethylene imine),
poly(oxyalkyleneamine), poly(vinyl alcohol)-co-poly(vinyl amine),
poly(4-aminostyrene), poly(l-lysine), chitosan, hexane diol,
ethylenediamine-N,N'-bis acetoacetamide,
N-(2-ethylhexyl)acetoacetamide, 2-benzoyl acetoacetamide,
N-(3-phenylpropyl) acetoacetamide, lilial, helional, melonal,
triplal, 5,5-dimethyl-1,3-cyclohexanedione,
2,4-dimethyl-3-cyclohexenecarboxformaldehyde,
2,2-dimethyl-1,3-dioxan-4,6-dione, 2-pentanone, dibutyl amine,
triethylenetetramine, ammonium hydroxide, benzylamine,
hydroxycitronellol, cyclohexanone, 2-butanone, pentane dione,
dehydroacetic acid, ammonium hydroxide or a mixture thereof.
Preferably said non-sulfur-based scavenger is selected from the
group consisting of acetoacetamide, ammonium hydroxide and mixtures
thereof.
[0048] The sulfur-based formaldehyde scavenger is selected from
derivatives of sulphate. More particularly it is selected from the
group consisting of alkali or alkali earth metal dithionites,
pyrosulfites, sulfites, bisulfite, metasulfite, monoalkyl sulphite,
dialkyl sulphite, dialkylene sulphite, sulfides, thiosulfates and
thiocyanates (e.g. potassium thiocyanate), mercaptans, such as
thioglycolic acid, mercaptoethanol,
4-hydroxy-2-mercapto-6-methylpyrimidine, mercaptothiazoline,
thiodialkanoic acids, such as thiodipropionic acid,
dithiodialkanoic acids, such as 3,3'-dithiodipropionic acid,
sulfinates, such as sodium formaldehydesulfoxylate or
formamidinosulfinic acid, thiourea or mixtures thereof. Said
scavenger activity is preferably pH independent. Preferably said
sulfur based scavenger is selected from alkali or alkali earth
metal sulfite, bisulfite or mixtures thereof. Most preferably the
sulfur-based scavenger is potassium sulfite.
[0049] The sulfur-based scavenger according to the present
invention is present at a total level, based on total liquid
composition weight, of from about 0.001% to about 2.0%, more
preferably from about 0.01% to about 0.5%. Where non-sulfur based
formaldehyde scavenger is present, it is preferably present in the
composition at a total level of about 0.0001% to 1%, more
preferably 0.001% to 0.2% based on the liquid composition weight.
The ratio of the non-sulfur based scavenger to the sulfur based
scavenger, in the liquid composition, is preferably from 0.001:1 to
5:1, more preferably from 0.01:1 to 1:1. The ratio of the sulfur
based scavenger to microcapsule wall material is preferably from
0.05:1 to 10:1, more preferably from 0.1:1 to 6:1. The level of
microcapsule wall material is a measure of the level of wall
material ingredients used in the microcapsule wall material making
process, for example described in the Examples.
[0050] In one embodiment of the present invention there is provided
a liquid composition comprising a microcapsule, comprising an
aldehyde-containing resin, and one or more formaldehyde scavenger
which reacts with formaldehyde in such way as to achieve more then
60% reaction completeness in 15 minutes time at pH 8 at 21.degree.
C. Without being bound by theory, it is believed that the
sulfur-containing scavenger prevents product discoloration through
fast reaction with formaldehyde present in the product (see graph
below). Scavenging reaction kinetics are believed to be affected by
a number of factors including; low molecular weight scavengers are
more mobile to react with formaldehyde; simple scavenging reaction
is faster than complex, multiple stage reactions, water-solubility
of the scavenger, as the scavenger must be in the same phase as the
formaldehyde. Materials which react with formaldehyde at the same
or faster rate also prevent discoloration in the same manner.
Formaldehyde Scavenging Test Method:
[0051] The assessment of the scavenging kinetics of a formaldehyde
scavenger is performed through quantification of the formed
reaction product. The % reaction completion is defined as the
measured amount of reaction product divided by the maximum amount
of reaction product that can be formed theoretically (assuming that
all formaldehyde has been scavenged by the scavenger).
[0052] The kinetic experiments are conducted in a commercially
available buffer at pH8 (Merck no 1.09460, based on a boric
acid/sodium hydroxide/hydrogen chloride mix) at 21.degree. C. To
this buffer, 0.2 wt % of formaldehyde and 2.times. the theoretical
level of scavenger needed to scavenge all formaldehyde (assuming
that all formaldehyde has been scavenged), is added and mixed. For
example to define the reaction kinetics of formaldehyde and
potassium sulfite, 1 to 1 molar reaction, 2.1 wt % potassium
sulfite is added to 0.2 wt % formaldehyde. The yield of the
reaction between formaldehyde and scavenger in the liquid mixture
is measured directly by mass spectrometry. For the purposes of the
experiments herein, the Applicants used a triple-quadruple Mass
Spectrometer (API3000 from Sciex Applied Biosystems). The mass
spectrometer is tuned to monitor the sulfite/formaldehyde 1/1
reaction product (hydroxymethane sulfonic acid) and the
acetoacetamide/formaldehyde 2/1 reaction product
(2,4-diacetylglutaramide) over time. Measurements are taken
according to the suppliers manual.
[0053] FIG. 1 is a plot of the percentage of reaction completion
vs. formaldehyde scavenging kinetics of acetoacetamide and
potassium sulfite ant pH 8 and 21.degree. C.
[0054] As can be seen, from FIG. 1, at 15 minutes, Potassium
Sulphite scavenger has reached substantially 100% reaction (+/-5%
error) completion whereas Acetoacetamide has achieved only
approximately 35% reaction completion.
Optional Composition Ingredients
[0055] The liquid compositions of the present invention may
comprise other ingredients selected from the list of optional
ingredients set out below. Unless specified herein below, an
"effective amount" of a particular laundry adjunct is preferably
from 0.01%, more preferably from 0.1%, even more preferably from 1%
to 20%, more preferably to 15%, even more preferably to 10%, still
even more preferably to 7%, most preferably to 5% by weight of the
detergent compositions.
Pearlescent Agent
[0056] In one embodiment of the present invention the composition
may comprise a pearlescent agent.
[0057] The pearlescent agents may be organic or inorganic. Typical
examples of organic pearlescent agents include monoesters and/or
diesters of ethylene glycol, propylene glycol, diethylene glycol,
dipropylene glycol, triethylene glycol or tetraethylene glycol with
fatty acids containing from about 6 to about 22, preferably from
about 12 to about 18 carbon atoms, such as caproic acid, caprylic
acid, 2-ethyhexanoic acid, capric acid, lauric acid, isotridecanoic
acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid,
isostearic acid, oleic acid, elaidic acid, petroselic acid,
linoleic acid, linolenic acid, arachic acid, gadoleic acid, behenic
acid, erucic acid, and mixtures thereof.
[0058] Preferred inorganic pearlescent Agents include those
selected from the group consisting of mica, metal oxide coated
mica, silica coated mica, bismuth oxychloride coated mica, bismuth
oxychloride, myristyl myristate, glass, metal oxide coated glass,
guanine, glitter (polyester or metallic) and mixtures thereof.
Suitable micas includes muscovite or potassium aluminum hydroxide
fluoride. The platelets of mica are preferably coated with a thin
layer of metal oxide. Preferred metal oxides are selected from the
group consisting of rutile, titanium dioxide, ferric oxide, tin
oxide, alumina and mixtures thereof. The crystalline pearlescent
layer is formed by calcining mica coated with a metal oxide at
about 732.degree. C. The heat creates an inert pigment that is
insoluble in resins, has a stable color, and withstands the thermal
stress of subsequent processing
Surfactants or Detersive Surfactants
[0059] The compositions of the present invention may comprise from
about 1% to 80% by weight of a surfactant. Preferably such
compositions comprise from about 5% to 50% by weight of
surfactant.
[0060] Detersive surfactants utilized can be of the anionic,
nonionic, zwitterionic, ampholytic or cationic type or can comprise
compatible mixtures of these types. More preferably surfactants are
selected from the group consisting of anionic, nonionic, cationic
surfactants and mixtures thereof. Preferably the compositions are
substantially free of betaine surfactants. Detergent surfactants
useful herein are described in U.S. Pat. No. 3,664,961, Norris,
issued May 23, 1972, U.S. Pat. No. 3,919,678, Laughlin et al.,
issued Dec. 30, 1975, U.S. Pat. No. 4,222,905, Cockrell, issued
Sep. 16, 1980, and in U.S. Pat. No. 4,239,659, Murphy, issued Dec.
16, 1980. Anionic and nonionic surfactants are preferred.
[0061] Useful anionic surfactants can themselves be of several
different types. For example, water-soluble salts of the higher
fatty acids, i.e., "soaps", are useful anionic surfactants in the
compositions herein. This includes alkali metal soaps such as the
sodium, potassium, ammonium, and alkyl ammonium salts of higher
fatty acids containing from about 8 to about 24 carbon atoms, and
preferably from about 12 to about 18 carbon atoms. Soaps can be
made by direct saponification of fats and oils or by the
neutralization of free fatty acids. Particularly useful are the
sodium and potassium salts of the mixtures of fatty acids derived
from coconut oil and tallow, i.e., sodium or potassium tallow and
coconut soap. Soaps also have a useful building function.
[0062] Additional non-soap anionic surfactants which are suitable
for use herein include the water-soluble salts, preferably the
alkali metal, and ammonium salts, of organic sulfuric reaction
products having in their molecular structure an alkyl group
containing from about 10 to about 20 carbon atoms, a sulfonic acid
or sulfuric acid ester group and optional alkoxylation. (Included
in the term "alkyl" is the alkyl portion of acyl groups.) Examples
of this group of synthetic surfactants are a) the sodium, potassium
and ammonium alkyl sulfates, especially those obtained by sulfating
the higher alcohols (C.sub.8-C.sub.18 carbon atoms) such as those
produced by reducing the glycerides of tallow or coconut oil; b)
the sodium, potassium and ammonium alkyl polyethoxylate sulfates,
particularly those in which the alkyl group contains from 10 to 22,
preferably from 12 to 18 carbon atoms, and wherein the
polyethoxylate chain contains from 1 to 15, preferably 1 to 6
ethoxylate moieties; and c) the sodium and potassium alkylbenzene
sulfonates in which the alkyl group contains from about 9 to about
15 carbon atoms, in straight chain or branched chain configuration,
e.g., those of the type described in U.S. Pat. No. 2,220,099 and
2,477,383. Especially valuable are linear straight chain
alkylbenzene sulfonates in which the average number of carbon atoms
in the alkyl group is from about 11 to 13, abbreviated as
C.sub.11-C.sub.13 LAS.
[0063] Preferred nonionic surfactants are those of the formula
R.sup.1(OC.sub.2H.sub.4).sub.nOH, wherein R.sup.1 is a
C.sub.10-C.sub.16 alkyl group or a C.sub.8-C.sub.12 alkyl phenyl
group, and n is from 3 to about 80. Particularly preferred are
condensation products of C.sub.12-C.sub.15 alcohols with from about
5 to about 20 moles of ethylene oxide per mole of alcohol, e.g.,
C.sub.12-C.sub.13 alcohol condensed with about 6.5 moles of
ethylene oxide per mole of alcohol.
Fabric Care Benefit Agents
[0064] The compositions of the present invention may comprise a
fabric care benefit agent. As used herein, "fabric care benefit
agent" refers to any material that can provide fabric care benefits
such as fabric softening, color protection, pill/fuzz reduction,
anti-abrasion, anti-wrinkle, and the like to garments and fabrics,
particularly on cotton and cotton-rich garments and fabrics, when
an adequate amount of the material is present on the
garment/fabric. Non-limiting examples of fabric care benefit agents
include cationic surfactants, silicones, polyolefin waxes, latexes,
oily sugar derivatives, cationic polysaccharides, polyurethanes,
fatty acids and mixtures thereof. Fabric care benefit agents when
present in the composition, are suitably at levels of up to about
30% by weight of the composition, more typically from about 1% to
about 20%, preferably from about 2% to about 10% in certain
embodiments.
[0065] Preferred fabric care benefit agents include silicone fluids
such as poly(di)alkyl siloxanes, especially polydimethyl siloxanes
and cyclic silicones.
Detersive Enzymes
[0066] Suitable detersive enzymes for optional use herein include
protease, amylase, lipase, cellulase, carbohydrase including
mannanase and endoglucanase, and mixtures thereof. Enzymes can be
used at their art-taught levels, for example at levels recommended
by suppliers such as Novo and Genencor. Typical levels in the
compositions are from about 0.0001% to about 5%. When enzymes are
present, they can be used at very low levels, e.g., from about
0.001% or lower, in certain embodiments of the invention; or they
can be used in heavier-duty laundry detergent formulations in
accordance with the invention at higher levels, e.g., about 0.1%
and higher. In accordance with a preference of some consumers for
"non-biological" detergents, the present invention includes both
enzyme-containing and enzyme-free embodiments.
Deposition Aid
[0067] As used herein, "deposition aid" refers to any cationic or
amphoteric polymer or combination of cationic and amphoteric
polymers that significantly enhance the deposition of the fabric
care benefit agent onto the fabric during laundering. Preferably,
the deposition aid, where present, is a cationic or amphoteric
polymer. The amphoteric polymers of the present invention will also
have a net zero or cationic charge, i.e.; the total cationic
charges on these polymers will equal or exceed the total anionic
charge. The charge density of the polymer ranges from about 0.0
milliequivalents/g to about 6 milliequivalents/g. The charge
density is calculated by dividing the number of net charge per
repeating unit by the molecular weight of the repeating unit. In
one embodiment, the charge density varies from about 0.0
milliequivants/g to about 3 milliequivalents/g. The positive
charges could be on the backbone of the polymers or the side chains
of polymers.
Rheology Modifier
[0068] In a preferred embodiment of the present invention, the
composition comprises a rheology modifier. The rheology modifier is
selected from the group consisting of non-polymeric crystalline,
hydroxy-functional materials, polymeric rheology modifiers which
impart shear thinning characteristics to the aqueous liquid matrix
of the composition.
[0069] Generally the rheology modifier will comprise from 0.01% to
1% by weight, preferably from 0.05% to 0.75% by weight, more
preferably from 0.1% to 0.5% by weight, of the compositions
herein.
[0070] Structuring agent which are especially useful in the
compositions of the present invention comprises non-polymeric
(except for conventional alkoxylation), crystalline
hydroxy-functional materials which can form thread-like structuring
systems throughout the liquid matrix when they are crystallized
within the matrix in situ. Such materials can be generally
characterized as crystalline, hydroxyl-containing fatty acids,
fatty esters or fatty waxes. Preferred rheology modifiers include
crystalline, hydroxyl-containing rheology modifiers include castor
oil and its derivatives. Especially preferred are hydrogenated
castor oil derivatives such as hydrogenated castor oil and
hydrogenated castor wax. A preferred rheology modifier is castor
oil-based, crystalline, hydroxyl-containing rheology modifier
commercially available under the tradename THIXCIN.RTM. from Rheox,
Inc. (now Elementis).
[0071] Other types of rheology modifiers, besides the
non-polymeric, crystalline, hydroxyl-containing rheology modifiers
described hereinbefore, may be utilized in the liquid detergent
compositions herein. Polymeric materials which will provide
shear-thinning characteristics to the aqueous liquid matrix may
also be employed.
[0072] Suitable polymeric rheology modifiers include those of the
polyacrylate, polysaccharide or polysaccharide derivative type.
Polysaccharide derivatives typically used as rheology modifiers
comprise polymeric gum materials. Such gums include pectine,
alginate, arabinogalactan (gum Arabic), carrageenan, gellan gum,
xanthan gum and guar gum.
[0073] In the absence of rheology modifier and in order to impart
preferred shear thinning characteristics to the liquid composition,
the liquid composition can be internally structured through
surfactant phase chemistry or gel phases.
Builder
[0074] The compositions of the present invention may optionally
comprise a builder. Suitable builders are discussed below:
[0075] Suitable polycarboxylate builders include cyclic compounds,
particularly alicyclic compounds, such as those described in U.S.
Pat. Nos. 3,923,679; 3,835,163; 4,158,635; 4,120,874 and
4,102,903.
[0076] Other useful detergency builders include the ether
hydroxypolycarboxylates, copolymers of maleic anhydride with
ethylene or vinyl methyl ether, 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.
[0077] 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. Oxydisuccinates are also especially useful in
such compositions and combinations.
[0078] Specific examples of nitrogen-containing, phosphor-free
aminocarboxylates include ethylene diamine disuccinic acid and
salts thereof (ethylene diamine disuccinates, EDDS), ethylene
diamine tetraacetic acid and salts thereof (ethylene diamine
tetraacetates, EDTA), and diethylene triamine penta acetic acid and
salts thereof (diethylene triamine penta acetates, DTPA).
[0079] Other suitable polycarboxylates are disclosed in U.S. Pat.
No. 4,144,226, Crutchfield et al, issued Mar. 13, 1979 and in U.S.
Pat. No. 3,308,067, Diehl, issued Mar. 7, 1967. See also Diehl U.S.
Pat. No. 3,723,322. Such materials include the water-soluble salts
of homo- and copolymers of aliphatic carboxylic acids such as
maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic
acid, citraconic acid and methylenemalonic acid.
Bleach System
[0080] Bleach system suitable for use herein contains one or more
bleaching agents. Nonlimiting examples of suitable bleaching agents
are selected from the group consisting of catalytic metal
complexes, activated peroxygen sources, bleach activators, bleach
boosters, photobleaches, bleaching enzymes, free radical
initiators, and hyohalite bleaches.
[0081] Suitable activated peroxygen sources include, but are not
limited to, preformed peracids, a hydrogen peroxide source in
combination with a bleach activator, or a mixture thereof. Suitable
preformed peracids include, but are not limited to, compounds
selected from the group consisting of percarboxylic acids and
salts, percarbonic acids and salts, perimidic acids and salts,
peroxymonosulfuric acids and salts, and mixtures thereof. Suitable
sources of hydrogen peroxide include, but are not limited to,
compounds selected from the group consisting of perborate
compounds, percarbonate compounds, perphosphate compounds and
mixtures thereof. Suitable types and levels of activated peroxygen
sources are found in U.S. Pat. Nos. 5,576,282, 6,306,812 and
6,326,348.
Perfume
[0082] Perfumes are preferably incorporated into the detergent
compositions of the present invention. The perfume ingredients may
be premixed to form a perfume accord prior to adding to the
detergent compositions of the present invention. As used herein,
the term "perfume" encompasses individual perfume ingredients as
well as perfume accords. More preferably the compositions of the
present invention comprise perfume microcapsules.
[0083] The level of perfume accord in the detergent composition is
typically from about 0.0001% to about 5% or higher, e.g., to about
10%; preferably from about 0.0002% to about 4.0%, more preferably
from about 0.003% to about 3.0.%, most preferably from about 0.005%
to about 2.0% by weight of the detergent composition.
Solvent System
[0084] The solvent system in the present compositions can be a
solvent system containing water alone or mixtures of organic
solvents with water. Preferred organic solvents include
1,2-propanediol, ethanol, glycerol, dipropylene glycol, methyl
propane diol and mixtures thereof. Other lower alcohols,
C.sub.1-C.sub.4 alkanolamines such as monoethanolamine and
triethanolamine, can also be used. Solvent systems can be absent,
for example from anhydrous solid embodiments of the invention, but
more typically are present at levels in the range of from about
0.1% to about 98%, preferably at least about 10% to about 95%, more
usually from about 25% to about 75%.
Fabric Substantive and Hueing Dye
[0085] Dyes are conventionally defined as being acid, basic,
reactive, disperse, direct, vat, sulphur or solvent dyes, etc. For
the purposes of the present invention, direct dyes, acid dyes and
reactive dyes are preferred, direct dyes are most preferred. Direct
dye is a group of water-soluble dye taken up directly by fibers
from an aqueous solution containing an electrolyte, presumably due
to selective adsorption. In the Color Index system, directive dye
refers to various planar, highly conjugated molecular structures
that contain one or more anionic sulfonate group. Acid dye is a
group of water soluble anionic dyes that is applied from an acidic
solution. Reactive dye is a group of dyes containing reactive
groups capable of forming covalent linkages with certain portions
of the molecules of natural or synthetic fibers. From the chemical
structure point of view, suitable fabric substantive dyes useful
herein may be an azo compound, stilbenes, oxazines and
phthalocyanines.
[0086] Suitable fabric substantive dyes for use herein include
those listed in the Color Index as Direct Violet dyes, Direct Blue
dyes, Acid Violet dyes and Acid Blue dyes.
[0087] The hueing dye is included in the laundry detergent
composition in an amount sufficient to provide a tinting effect to
fabric washed in a solution containing the detergent. In one
embodiment, the composition comprises, by weight, from about
0.0001% to about 0.05%, more specifically from about 0.001% to
about 0.01%, of the hueing dye.
[0088] Exemplary hueing dyes include triarylmethane blue and violet
basic dyes as set forth in Table 2, methine blue and violet basic
dyes as set forth in Table 3, anthraquinone dyes as set forth in
Table 4, anthraquinone dyes basic blue 35 and basic blue 80, azo
dyes basic blue 16, basic blue 65, basic blue 66 basic blue 67,
basic blue 71, basic blue 159, basic violet 19, basic violet 35,
basic violet 38, basic violet 48, oxazine dyes basic blue 3, basic
blue 75, basic blue 95, basic blue 122, basic blue 124, basic blue
141, Nile blue A and xanthene dye basic violet 10, and mixtures
thereof.
Encapsulated Composition
[0089] The compositions of the present invention may be
encapsulated within a water-soluble film. The water-soluble film
may be made from polyvinyl alcohol or other suitable variations,
carboxy methyl cellulose, cellulose derivatives, starch, modified
starch, sugars, PEG, waxes, or combinations thereof.
[0090] In another embodiment the water-soluble film may include a
co-polymer of vinyl alcohol and a carboxylic acid. U.S. Pat. No.
7,022,656 B2 (Monosol) describes such film compositions and their
advantages. One benefit of these copolymers is the improvement of
the shelf-life of the pouched detergents thanks to the better
compatibility with the detergents. Another advantage of such films
is their better cold water (less than 10.degree. C.) solubility.
Where present the level of the co-polymer in the film material, is
at least 60% by weight of the film. The polymer can have any weight
average molecular weight, preferably from 1000 daltons to 1,000,000
daltons, more preferably from 10,000 daltons to 300,000 daltons,
even more preferably from 15,000 daltons to 200,000 daltons, most
preferably from 20,000 daltons to 150,000 daltons. Preferably, the
co-polymer present in the film is from 60% to 98% hydrolysed, more
preferably 80% to 95% hydrolysed, to improve the dissolution of the
material. In a highly preferred execution, the co-polymer comprises
from 0.1 mol % to 30 mol %, preferably from 1 mol % to 6 mol %, of
said carboxylic acid.
[0091] The water-soluble film of the present invention may further
comprise additional co-monomers. Suitable additional co-monomers
include sulphonates and ethoxylates. An example of preferred
sulphonic acid is 2-acrylamido-2-methyl-1-propane sulphonic acid
(AMPS). A suitable water-soluble film for use in the context of the
present invention is commercially available under tradename
M8630.TM. from Mono-Sol of Indiana, US. The water-soluble film
herein may also comprise ingredients other than the polymer or
polymer material. For example, it may be beneficial to add
plasticisers, for example glycerol, ethylene glycol,
diethyleneglycol, propane diol, 2-methyl-1,3-propane diol, sorbitol
and mixtures thereof, additional water, disintegrating aids,
fillers, anti-foaming agents, emulsifying/dispersing agents, and/or
antiblocking agents. It may be useful that the pouch or
water-soluble film itself comprises a detergent additive to be
delivered to the wash water, for example organic polymeric soil
release agents, dispersants, dye transfer inhibitors. Optionally
the surface of the film of the pouch may be dusted with fine powder
to reduce the coefficient of friction. Sodium aluminosilicate,
silica, talc and amylose are examples of suitable fine powders.
[0092] The encapsulated pouches of the present invention can be
made using any convention known techniques. More preferably the
pouches are made using horizontal form filling thermoforming
techniques.
Other Adjuncts
[0093] Examples of other suitable cleaning adjunct materials
include, but are not limited to, alkoxylated benzoic acids or salts
thereof such as trimethoxy benzoic acid or a salt thereof (TMBA);
enzyme stabilizing systems; chelants including aminocarboxylates,
aminophosphonates, nitrogen-free phosphonates, and phosphorous- and
carboxylate-free chelants; inorganic builders including inorganic
builders such as zeolites and water-soluble organic builders such
as polyacrylates, acrylate/maleate copolymers and the like
scavenging agents including fixing agents for anionic dyes,
complexing agents for anionic surfactants, and mixtures thereof;
effervescent systems comprising hydrogen peroxide and catalase;
optical brighteners or fluorescers; soil release polymers;
dispersants; suds suppressors; dyes; colorants; filler salts such
as sodium sulfate; hydrotropes such as toluenesulfonates,
cumenesulfonates and naphthalenesulfonates; photoactivators;
hydrolysable surfactants; preservatives; anti-oxidants;
anti-shrinkage agents; anti-wrinkle agents; germicides; fungicides;
color speckles; colored beads, spheres or extrudates; sunscreens;
fluorinated compounds; clays; luminescent agents or
chemiluminescent agents; anti-corrosion and/or appliance protectant
agents; alkalinity sources or other pH adjusting agents;
solubilizing agents; processing aids; pigments; free radical
scavengers, and mixtures thereof. Suitable materials include those
described in U.S. Pat. Nos. 5,705,464, 5,710,115, 5,698,504,
5,695,679, 5,686,014 and 5,646,101. Mixtures of adjuncts--Mixtures
of the above components can be made in any proportion.
Composition Preparation
[0094] The compositions herein can generally be prepared by first
preparing a slurry of microcapsules and optionally a formaldehyde
scavenger, preferably a non-sulfur containing formaldehyde
scavenger, and then combining said slurry with the remaining
ingredients including the sulfur-containing formaldehyde
scavenger.
[0095] If a rheology modifier is used, it is preferred to first
form a pre-mix within which the rheology modifier is dispersed in a
portion of the water eventually used to comprise the compositions
and then combine the premix with the composition.
EXAMPLES
[0096] While particular embodiments of the present invention have
been illustrated and described, it would be obvious to those
skilled in the art that various other changes and modifications can
be made without departing from the spirit and scope of the
invention. It is therefore intended to cover in the appended claims
all such changes and modifications that are within the scope of
this invention.
[0097] Examples 1 and 2 are examples of preferred microcapsules and
methods for making same.
Example 1: 84 wt % Core/16 wt % Wall Melamine Formaldehyde (MF)
Capsule
[0098] 25 grams of butyl acrylate-acrylic acid copolymer emulsifier
(Colloid C351, 25% solids, pka 4.5-4.7, (Kemira Chemicals, Inc.
Kennesaw, Ga. U.S.A.) is dissolved and mixed in 200 grams deionized
water. The pH of the solution is adjusted to pH of 4.0 with sodium
hydroxide solution. 8 grams of partially methylated methylol
melamine resin (Cymel 385, 80% solids, (Cytec Industries West
Paterson, N.J., U.S.A.)) is added to the emulsifier solution. 200
grams of perfume oil is added to the previous mixture under
mechanical agitation and the temperature is raised to 50.degree. C.
After mixing at higher speed until a stable emulsion is obtained,
the second solution and 4 grams of sodium sulfate salt are added to
the emulsion. This second solution contains 10 grams of butyl
acrylate-acrylic acid copolymer emulsifier (Colloid C351, 25%
solids, pka 4.5-4.7, Kemira), 120 grams of distilled water, sodium
hydroxide solution to adjust pH to 4.8, 25 grams of partially
methylated methylol melamine resin (Cymel 385, 80% solids, Cytec).
This mixture is heated to 70.degree. C. and maintained overnight
with continuous stirring to complete the encapsulation process. 23
grams of acetoacetamide (Sigma-Aldrich, Saint Louis, Mo., U.S.A.)
is added to the suspension. An average capsule size of 30 um was
obtained as analyzed by a Model 780 Accusizer.
Example 2: 80 wt % Core/20 wt % Wall Melamine Formaldehyde
Capsule
[0099] 18 grams of a blend of 50% butyl acrylate-acrylic acid
copolymer emulsifier (Colloid C351, 25% solids, pka 4.5-4.7,
Kemira) and 50% polyacrylic acid (35% solids, pKa 1.5-2.5, Aldrich)
is dissolved and mixed in 200 grams deionized water. The pH of the
solution is adjusted to pH of 3.5 with sodium hydroxide solution.
6.5 grams of partially methylated methylol melamine resin (Cymel
385, 80% solids Cytec) is added to the emulsifier solution. 200
grams of perfume oil is added to the previous mixture under
mechanical agitation and the temperature is raised to 60.degree. C.
After mixing at higher speed until a stable emulsion is obtained,
the second solution and 3.5 grams of sodium sulfate salt are poured
into the emulsion. This second solution contains 10 grams of butyl
acrylate-acrylic acid copolymer emulsifier (Colloid C351, 25%
solids, pka 4.5-4.7, Kemira), 120 grams of distilled water, sodium
hydroxide solution to adjust pH to 4.6, 30 grams of partially
methylated methylol melamine resin (Cymel 385, 80% Cytec). This
mixture is heated to 75.degree. C. and maintained 6 hours with
continuous stifling to complete the encapsulation process. 23 grams
of acetoacetamide (Sigma-Aldrich, Saint Louis, Mo., U.S.A.) is
added to the suspension.
[0100] To demonstrate the benefit of the present invention, the
Applicants prepared liquid detergent matrix A, in table 1
below.
TABLE-US-00001 TABLE 1 Active Material in weight % A C14-C15 alkyl
poly ethoxylate 7 3.39 C12-C14 alkyl poly ethoxylate 7 1.13 C12-C14
alkyl poly ethoxylate 3 sulfate Na salt 7.66 Alkylbenzene sulfonic
acid 1.17 Citric Acid 2.73 C12-18 fatty acid 5.06 Enzymes 0.2 Boric
Acid 1.40 Trans-sulphated ethoxylated hexamethylene diamine quat
0.81 Diethylene triamine penta methylene phosphonic acid 0.12
Hydrogenated Castor Oil structurant 0.300 Ethanol 1.59 1,2
propanediol 0.07 Sodium hydroxide 3.48 Silicone PDMS emulsion
0.0025 Blue Dye 0.0006 Preservative Acticide MBS 2550 (ex Thor)
0.0135 Perfume Nil Merquat 5300 polymer (1) 0.19 Water Up to
95%
[0101] From this liquid detergent A, a number of samples (A1-A9)
were made through addition of different levels of scavengers, micro
capsules, perfume and water (up to 100). The blue detergent samples
were placed in storage for 4 months at 35.degree. C. in glass
bottles, and protected with aluminum foil from the day light. After
storage, the product discoloration of the detergent samples is
graded by two different trained color graders, utilizing a PSU
scale. The PSU scale as referenced herein is a paired comparison
between the color of reference liquid laundry detergent A1 and the
color of test liquid laundry detergent A2 to A9. The glass bottles
with detergent are compared next to each other in standard day
light conditions. The distance between the grader and the samples
is 2 meters, and the samples are at eye height. The grading scale
is from 0 to 4 (see below in Table 2). The grading for each laundry
detergent is the average of the grades given by the 2 trained color
graders. Results are provided in Table 3.
TABLE-US-00002 TABLE 2 PSU Grading Scale SCORE MEANING 0 There is
no difference 1 I think this one is more greenish (unsure) 2 I know
this one is more greenish (sure) 3 This one is a lot more greenish
4 This one is clearly green
TABLE-US-00003 TABLE 3 A1 A2 A3 A4 A5 A6 A7 A8 A9 Scavenger 1 -- --
0.035% 0.035% 0.035% 0.035% 0.035% 0.035% 0.035% Acetoacetamide
Scavenger 2 -- -- -- -- -- -- 0.1 0.2 0.2 K-sulphite PMC (2) -- 0.3
0.3 0.3 -- -- 0.3 0.3 -- PaMC (3) -- -- -- -- 0.3 0.3 -- -- 0.3
Perfume -- -- -- 0.6 -- 0.6 0.6 0.6 -- Water Up Up Up to Up to Up
to Up to Up to Up to Up to to to 100 100 100 100 100 100 100
Detergent Ref 4 4 4 4 4 1.5 0.5 0.5 discoloration after 4 months
storage at 35.degree. C. (PSU) PASS if Ref FAIL FAIL FAIL FAIL FAIL
PASS PASS PASS Delta PSU < 2 (1) Merquat 5300: terpolymer with
mole ratio: 90% PAM/5% AA/5% MAPTAC produced by Nalco. (2) PMC:
Perfume Micro Capsule: Perfume oil encapsulated in a
melamine-formaldehyde shell (3) PaMC: Paraffin Micro Capsule:
Paraffin oil (Marcol 152 ex Exxon) encapsulated in
melamine-formaldehyde shell Levels for (2) and (3) are expressed as
perfume oil or paraffin oil delivered via capsules.
[0102] The following are examples of liquid compositions according
to the present invention that pass the above success criteria,
table 4.
TABLE-US-00004 TABLE 4 Active Material in weight % Composition pH:
7.5-8.5 1 2 3 4 5 6 C14-C15 alkyl poly ethoxylate 7 6.0 6.0 6.0 6.0
3.39 6.0 C12-C14 alkyl poly ethoxylate 7 2.0 2.0 2.0 2.0 1.13 2.0
C12-C14 alkyl poly ethoxylate 3 13.55 13.55 13.55 13.55 7.66 13.55
sulfate Na salt Alkylbenzene sulfonic acid 1.17 1.17 1.17 1.17 1.17
1.17 Citric Acid 4.83 4.83 4.83 4.83 2.73 4.83 C12-18 fatty acid
8.95 8.95 8.95 8.95 5.06 8.95 Enzymes 0.8 0.8 0.8 0.8 0.2 0.4 Boric
Acid 1.92 1.92 1.92 1.92 1.40 1.92 Trans-sulphated ethoxylated 1.43
1.43 1.43 1.43 0.81 1.43 hexamethylene diamine quat Diethylene
triamine penta 0.21 0.21 0.21 0.21 0.12 0.21 methylene phosphonic
acid Hydrogenated Castor Oil 0.3 0.3 0.3 0.3 0.3 0.3 structurant
Ethanol 2.2 2.2 2.2 2.2 1.59 2.2 1, 2 propanediol 0.27 0.27 0.27
0.27 0.07 0.27 Glycerol -- -- -- -- 0.05 0.05 Sodium hydroxide 6.2
6.2 6.2 6.2 3.48 6.2 Silicone PDMS emulsion 0.0025 0.0025 0.0025
0.0025 0.0025 0.0025 Dye 0.0006 0.0006 0.0006 0.0006 0.0008 0.0006
Preservative Acticide MB52550 -- -- -- -- 0.0135 -- Mearlin
Superfine 9120V+ pearl -- -- -- -- 0.05 0.05 agent (ex BASF)
Perfume -- -- 0.6 0.6 0.65 1.3 Merquat 5300 .sup.(1) 0.3 0.3 0.3
0.3 0.19 0.3 Acetoacetamide 0.07 0.075 -- -- 0.035 0.07 NH.sub.4OH
-- -- 0.05 -- -- -- PMC: Perfume microcapsules .sup.(2) 0.6 -- 0.6
0.6 0.3 0.6 PaMC: Paraffin microcapsule .sup.(3) -- 0.65 -- -- --
-- Potassium Sulphite 0.2 0.3 0.4 0.4 0.1 0.2 Water Up to Up to Up
to Up to Up to Up to 100 100 100 100 100 100 .sup.(1) Merquat 5300:
terpolymer with mole ratio: 90% PAM/5% AA/5% MAPTAC produced by
Nalco. .sup.(2) PMC: Perfume Micro Capsule: Perfume oil
encapsulated in a melamine-formaldehyde shell .sup.(3) PaMC:
Paraffin Micro Capsule: Paraffin oil (Marcol 152 ex Exxon)
encapsulated in melamine-formaldehyde shell Levels for (2) and (3)
are expressed as perfume oil or paraffin oil delivered via
capsules.
[0103] The following are examples of unit dose executions wherein
the liquid composition is enclosed within a PVA film (Table 5). The
preferred film used in the present examples is Monosol M8630 76
.mu.m thickness.
TABLE-US-00005 TABLE 5 Active Material in weight % Composition pH
7.5 for a pouch (39 mL) 16 17 18 19 20 Alkylbenzene 22.60 22.60
22.60 22.60 22.60 sulfonic acid C12-14 Alcohol 16.49 16.49 16.49
16.49 16.49 ethoxylate EO7 C12-18 fatty acid 17.70 17.70 17.70
17.70 17.70 Protease 0.3 0.3 0.3 0.3 0.3 Silicone oil 1.23 1.23
1.23 1.23 1.23 (PDMS) Optical brightener 0.27 0.27 0.27 0.27 0.27
Propylene glycol 13.14 13.14 13.14 13.14 13.14 Glycerol 6.89 6.89
6.89 6.89 6.89 Monoethanolamine 6.74 6.74 6.74 6.74 6.74 Caustic
soda 1.09 1.09 1.09 1.09 1.09 Potassium sulfite 0.17 0.30 0.30 0.30
0.30 Added water 1.97 1.97 1.97 1.97 1.97 Hydrogenated 0.23 0.23
0.23 0.23 0.23 castor oil PMC: Perfume 0.45 1.00 1.0 1.0 1.0
microcapsule (2) Acetoacetamide 0.05 0.11 0.11 -- -- NH4OH -- -- --
0.1 0.1 Perfume 1.89 1.89 1.89 1.89 1.89 Dyes 0.0058 0.0058 0.0058
0.0058 0.0058 Mearlin MP3001 0.10 pearl agent (ex BASF) Water To
100 To 100 To 100 To 100 To 100
[0104] The dimensions and values disclosed herein are not to be
understood as being strictly limited to the exact numerical values
recited. Instead, unless otherwise specified, each such dimension
is intended to mean both the recited value and a functionally
equivalent range surrounding that value. For example, a dimension
disclosed as "40 mm" is intended to mean "about 40 mm".
[0105] Every document cited herein, including any cross referenced
or related patent or application, is hereby incorporated herein by
reference in its entirety unless expressly excluded or otherwise
limited. The citation of any document is not an admission that it
is prior art with respect to any invention disclosed or claimed
herein or that it alone, or in any combination with any other
reference or references, teaches, suggests or discloses any such
invention. Further, to the extent that any meaning or definition of
a term in this document conflicts with any meaning or definition of
the same term in a document incorporated by reference, the meaning
or definition assigned to that term in this document shall
govern.
[0106] While particular embodiments of the present invention have
been illustrated and described, it would be obvious to those
skilled in the art that various other changes and modifications can
be made without departing from the spirit and scope of the
invention. It is therefore intended to cover in the appended claims
all such changes and modifications that are within the scope of
this invention.
* * * * *