U.S. patent application number 14/862182 was filed with the patent office on 2016-03-31 for cleaning compositions comprising alkoxylated polyalkyleneimines and sulfonate group-containing copolymers.
The applicant listed for this patent is The Procter & Gamble Company. Invention is credited to Praveen Kumar DEPA, Akiko HEMMI, Rachel Marie HILER, Xiaoyan LIU, Bonny Kay LUI, Rika MATSUMOTO, Hirotaka MIZOGUCHI, Peng QIN, William Coffin SHEAROUSE, Mark Allen SMERZNAK, Patrick Christopher STENGER, Stacey Lee VOSTERS, Xiaoli WANG, Xianling ZHAI.
Application Number | 20160090554 14/862182 |
Document ID | / |
Family ID | 55583768 |
Filed Date | 2016-03-31 |
United States Patent
Application |
20160090554 |
Kind Code |
A1 |
WANG; Xiaoli ; et
al. |
March 31, 2016 |
CLEANING COMPOSITIONS COMPRISING ALKOXYLATED POLYALKYLENEIMINES AND
SULFONATE GROUP-CONTAINING COPOLYMERS
Abstract
A cleaning composition containing an alkoxylated
polyalkyleneimine and a sulfonate group-containing copolymer is
provided, which exhibits significant improved whiteness maintenance
benefit when used to treat fabrics.
Inventors: |
WANG; Xiaoli; (Beijing,
CN) ; ZHAI; Xianling; (Beijing, CN) ; QIN;
Peng; (Beijing, CN) ; LIU; Xiaoyan; (Beijing,
CN) ; SMERZNAK; Mark Allen; (Beijing, CN) ;
STENGER; Patrick Christopher; (Fairfield, OH) ; LUI;
Bonny Kay; (Cincinnati, OH) ; DEPA; Praveen
Kumar; (Hyde Park, OH) ; SHEAROUSE; William
Coffin; (Cincinnati, OH) ; VOSTERS; Stacey Lee;
(Cincinnati, OH) ; HILER; Rachel Marie;
(Cincinnati, OH) ; HEMMI; Akiko; (Osaka, JP)
; MIZOGUCHI; Hirotaka; (Osaka, JP) ; MATSUMOTO;
Rika; (Osaka, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
The Procter & Gamble Company |
Cincinnati |
OH |
US |
|
|
Family ID: |
55583768 |
Appl. No.: |
14/862182 |
Filed: |
September 23, 2015 |
Current U.S.
Class: |
510/230 ;
510/235; 510/299; 510/406; 510/476 |
Current CPC
Class: |
C11D 3/378 20130101;
C11D 3/3723 20130101; C11D 3/0036 20130101 |
International
Class: |
C11D 3/00 20060101
C11D003/00; C11D 17/04 20060101 C11D017/04; C11D 3/37 20060101
C11D003/37 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 25, 2014 |
WO |
CN2014/087376 |
Sep 15, 2015 |
WO |
CN2015/089571 |
Claims
1. A cleaning composition comprising: (1) from 0.01% to 20% by
weight of at least one alkoxylated polyalkyleneimine that
comprises: a polyalkyleneimine core having an average
number-average molecular weight (MW.sub.PEI) ranging from 100 to
100,000 Daltons; and at least one side chain bonded to a nitrogen
atom in the polyalkyleneimine core, wherein said at least one side
chain has an empirical formula (I) of: -(EO).sub.b(PO).sub.c--R (I)
wherein: EO is ethylene oxide; b has a weight average value ranging
from 3 to 60; PO is propylene oxide; c has a weight average value
ranging from 0 to 60; R is selected from the group consisting of
hydrogen, C.sub.1-C.sub.4 alkyls, and combinations thereof; (2)
from 0.01% to 20% by weight of a sulfonate group-containing
copolymer that comprises: a structural unit (a) derived from a
sulfonate group-containing monomer (A); and a structural unit (b)
derived from a polyoxyalkylene monomer (B) represented by formula
(II): ##STR00008## wherein R.sup.1 represents a hydrogen atom or a
methyl group; R.sup.2 represents a direct bond, CH.sub.2, or
CH.sub.2CH.sub.2; Z may be the same or different and each Z
represents a structural unit derived from a C.sub.2-C.sub.20
alkylene oxide; n is from 1 to 200; and R.sup.0 represents hydrogen
atom or a C.sub.1-C.sub.30 organic group; and a structural unit (c)
derived from a carboxyl group-containing monomer (C).
2. The cleaning composition of claim 1, wherein MW.sub.PEI of the
polyalkyleneimine core of said at least one alkoxylated
polyalkyleneimine ranges from 100 to 5000 Daltons, and preferably
from 200 to 1000 Daltons; and wherein b ranges from 5 to 40,
preferably from 10 to 30, more preferably from 15 to 25; and
wherein c is 0.
3. The cleaning composition of claim 1, wherein MW.sub.PEI of the
polyalkyleneimine core of said at least one alkoxylated
polyalkyleneimine ranges from 100 to 5000 Daltons, and preferably
from 200 to 1000 Daltons; and wherein b ranges from 10 to 50,
preferably from 15 to 40, more preferably from 20 to 30; and
wherein c ranges from 1 to 50, preferably from 5 to 40, and more
preferably from 10 to 30.
4. The cleaning composition of claim 1, wherein said at least one
alkoxylated polyalkyleneimine comprises: (1) a first alkoxylated
polyalkyleneimine having a polyalkyleneimine core with MW.sub.PEI
ranging from 100 to 5000 Daltons, and preferably from 200 to 1000
Daltons, with b ranging from 5 to 40, preferably from 10 to 30,
more preferably from 15 to 25, and with c being 0; and (2) a second
alkoxylated polyalkyleneimine having a polyalkyleneimine core with
MW.sub.PEI ranging from 100 to 5000 Daltons, and preferably from
200 to 1000 Daltons, with b ranging from 10 to 50, preferably from
15 to 40, more preferably from 20 to 30, and with c ranging from 1
to 50, preferably from 5 to 40, and more preferably from 10 to
30.
5. The cleaning composition of claim 4, wherein the weight ratio
between said first and second alkoxylated polyalkyleneimines ranges
from 1:10 to 10:1, preferably from 1:5 to 5:1, and more preferably
from 1:2 to 2:1.
6. The cleaning composition according to claim 1, wherein said at
least one alkoxylated polyalkyleneimine is present in an amount
ranging from 0.05% to 15%, preferably from 0.1% to 10%, and more
preferably from 0.5% to 5%, by total weight of the cleaning
composition.
7. The cleaning composition according to claim 1, wherein the
sulfonate group-containing copolymer comprises: (1) from 1% to 38%,
preferably from 4% to 20% and more preferably from 5% to 16%, by
mass in an acid form equivalent of the structural unit (a) in 100%
by mass of all monomer structural units constituting the sulfonate
group-containing copolymer; and (2) from 9% to 76%, preferably from
20% to 49% and more preferably from 30% to 45%, by mass of the
structural unit (b) in 100% by mass of all monomer structural units
constituting the sulfonate group-containing copolymer; and (3) from
20% to 90%, preferably from 25% to 75% and more preferably from 35%
to 55%, by mass in acid form equivalent of the structural unit (c)
in 100% by mass of all monomer structural units constituting the
sulfonate group-containing copolymer.
8. The cleaning composition of claim 7, wherein said sulfonate
group-containing copolymer is characterized by a parameter of
P.times.MW.sub.S.times.n that ranges from 950,000 to 8,000,000, and
preferably from 1,000,000 to 50,000,000, wherein: P is defined as
the ratio by mass of the structural unit (b) to the structural unit
(a) in the sulfonate group-containing copolymer; and MW.sub.S is
the weight average molecular weight of the sulfonate
group-containing copolymer; and n is as defined in formula
(II).
9. The cleaning composition according to claim 8, wherein MW.sub.S
ranges from 20,000 to 200,000, preferably from 25,000 to 100,000,
and more preferably from 30,000 to 75,000; and wherein P ranges
from 1.2 to 20, preferably from 1.5 to 15, more preferably from 2
to 10, and most preferably from 2.5 to 5; and wherein n ranges from
5 to 100, preferably form 10 to 80, and more preferably from 40 to
60.
10. The cleaning composition according to claim 1, wherein the
sulfonate group-containing monomer (A) is a compound represented by
the following formula (III): ##STR00009## wherein R.sup.3
represents a hydrogen atom or a methyl group; R.sup.4 represents a
direct bond, CH.sub.2, or CH.sub.2CH.sub.2; X and Y each represent
a hydroxy group or SO.sub.3M where M represents a hydrogen atom,
Li, Na, or K, and at least one of X and Y is SO.sub.3M.
11. The cleaning composition according to claim 1, wherein the
sulfonate group-containing copolymer comprises: from 5% to 16% by
mass of the structure unit (a) in acid form equivalent in 100% by
mass of all monomer structural units constituting the sulfonate
group-containing copolymer, wherein the sulfonate group-containing
monomer (A) is 3-allyloxy-2-hydroxypropanesulfonate; and from 30%
to 45% by mass of the structure unit (b) in 100% by mass of all
monomer structural units constituting the sulfonate
group-containing copolymer, wherein the polyoxyalkylene monomer (B)
comprises an ethylene oxide-derived group having from 40 to 60
repeating oxyethylene units; and from 35% to 55% by mass of the
structure unit (c) in acid form equivalent in 100% by mass of all
monomer structural units constituting the sulfonate
group-containing copolymer, wherein the carboxyl group-containing
monomer (C) is acrylic acid or a salt thereof.
12. The cleaning composition according to claim 1, wherein said
sulfonate group-containing copolymer is present in an amount
ranging from 0.05% to 15%, preferably from 0.1% to 10%, and more
preferably from 0.5% to 5%, by total weight of the cleaning
composition.
13. The cleaning composition according to claim 1, which is
selected from the group consisting of a laundry detergent
composition, a hard surface cleaning composition, a hand
dishwashing composition, and an automatic dishwashing composition;
and wherein the cleaning composition further comprises a surfactant
selected from the group consisting of anionic surfactants, cationic
surfactants, nonionic surfactants, amphoteric surfactants,
zwitterionic surfactants, and mixtures thereof, and wherein said
surfactant is preferably an anionic surfactant selected from the
group consisting of alkyl benzene sulfonate, alkoxylated alkyl
sulfates, alkyl sulfates, and mixtures thereof.
14. The cleaning composition according to claim 1, wherein the
cleaning composition is a liquid composition, and preferably in a
single phase or multiphase unit dose form as encapsulated by a
single compartment or multi-compartment water-soluble pouch.
15. Use of the cleaning composition according to claim 1 for
treating fabrics to achieve improved whiteness maintenance
benefit.
16. A method of treating a soiled material, comprising the steps
of: a) providing a cleaning composition according to claim 1; b)
contacting the cleaning composition with at least a portion of the
soiled material; and c) optionally, rinsing the soiled material.
Description
FIELD OF THE INVENTION
[0001] The present invention is in the field of cleaning
compositions.
BACKGROUND OF THE INVENTION
[0002] An important purpose of detergents and/or cleaning
compositions is to remove soils and stains from fabrics to achieve
consumer perceivable cleaning benefit. The ability of a particular
detergent or cleaning composition to remove soils and stains is
determined not only by the surfactant activity level in the
composition, but also by many others factors.
[0003] For example, the wash water used with detergents or cleaning
compositions may contain various metal ions (e.g., calcium or
magnsium ions) that can chemically combine with surfactants in the
wash to form insoluble precipitates, which not only render the
surfactant ineffective for soil/stain remval, but also form scums
that further soil the fabric surface. Therefore, water with a
higher concentration of metal ions (i.e., hard water) presents a
particularly challenging wash condition. This challenge is further
exacerbated by the recent change in consumers' laundering habits
that are aiming at reducing energy consumption (e.g., by re-using
wash water, such as re-using bath water for laundering) and
improving environmental sustainability (e.g., by eliminating
phosphate and/or zeolite builders and reducing total surfactant
content in detergents) of the laundering processes. This brings
additional challenges because re-used wash water tends to have
harder (i.e., high concentrations of metal ions) and increased
levels of soil contaminants, and elimination of phosphate and/or
zeolite builder and reduction of total surfactant content in the
detergent or cleaning compositions may lead to significant
reduction in the cleaning performance.
[0004] Various polymers have been used in detergents or cleaning
compositions in recent years as detergent builders in augmenting
the cleaning power of surfactants. For example, some polymers can
bind calcium ions and/or other alkali earth metal ions in water,
thereby improving the water hardness tolerance of the detergents or
cleaning compositions and allowing either elimination or
significant reduction of conventional phosphate and/or zeolite
builders in such compositions. Other polymers can effectively
suspend soil particles (either inorganic or organic) that have
already been removed from the fabric surface by surfactants, in the
wash liquor and prevent their redeposition back onto the fabric
surface during subsequent wash and rinse steps.
[0005] Water-soluble copolymers formed by polymerization of one or
more monomers derived from unsaturated monocarboxylic acid,
unsaturated polyalkylene glycol, and sulfonate group-containing
hydrocarbons (such as those disclosed in Japanese Patent
Application Publication Nos. JP2004-75977 and JP2010-111792A; U.S.
Pat. No. 6,451,952 and U.S. Pat. No. 7,390,776) have demonstrated
effectiveness as polymeric detergent builders. Specifically,
JP2010-111792A discloses a group of copolymers containing
structural units derived from sulfonate group-containing monomers,
polyoxyalkylene monomers, and carboxylic acid monomers, which
exhibited improved effectiveness in anti-soil redeposition and can
be used in detergent or cleaning compositions to improve the
overall cleaning performance thereof.
[0006] However, there is still room for further improvement in the
cleaning performance of the afore-mentioned copolymers. In
particular, there is a need for laundry detergent compositions with
further improved fabric whiteness maintenance benefit (i.e., less
reduction in fabric whiteness after repeated wearing and wash
cycles over extended periods of time), in comparison with that
currently enabled by the afore-mentioned copolymers.
SUMMARY OF THE INVENTION
[0007] The present invention relates to a cleaning composition,
preferably a laundry detergent composition and more preferably a
liquid laundry detergent composition, which contains one or more
alkoxylated polyalkyleneimines in combination with a sulfonate
group-containing copolymer. It is a surprising and unexpected
discovery of the present invention that when a sulfonate
group-containing copolymer is combined with one or more alkoxylated
polyalkyleneimines in a cleaning composition, the resulting
cleaning composition exhibits significant improvement in its
cleaning performance, more specifically its whiteness maintenance
benefit, in comparison with compositions containing either the
sulfonate group-containing copolymer alone or the one or more
alkoxylated polyalkyleneimines alone.
[0008] The alkoxylated polyalkyleneimine used for practicing the
present invention contains a polyalkyleneimine core having an
average number-average molecular weight (MW.sub.PEI) ranging from
100 to 100,000 Daltons, and at least one side chain bonded to a
nitrogen atom in the polyalkyleneimine core. The at least one side
chain has an empirical formula (I) of:
-(EO).sub.b(PO).sub.c--R (I)
While: EO is ethylene oxide; b has a weight average value ranging
from 3 to 60; PO is propylene oxide; c has a weight average value
ranging from 0 to 60; and R is selected from the group consisting
of hydrogen, C.sub.1-C.sub.4 alkyls, and combinations thereof. The
alkoxylated polyalkyleneimine or polyalkyleneimines (there can be
two or more alkoxylated polyalkyleneimines in the same composition)
may be present in the cleaning composition of the present invention
in an amount ranging from about 0.01% to about 20% by total weight
of the cleaning composition.
[0009] The sulfonate group-containing copolymer used for practicing
the present invention contains at least three structural units,
(a), (b), and (c).
[0010] The first structural unit (a) is derived from a sulfonate
group-containing monomer (A).
[0011] The second structural unit (b) is derived from a
polyoxyalkxylene monomer (B), which can be presented by formula
(II) as follows:
##STR00001##
while R.sup.1 represents a hydrogen atom or a methyl group; R.sup.2
represents a direct bond, CH.sub.2, or CH.sub.2CH.sub.2; Z may be
the same or different and each Z represents a structural unit
derived from a C.sub.2-C.sub.20 alkylene oxide; n is from 1 to 200;
and R.sup.0 represents hydrogen atom or a C.sub.1-C.sub.30 organic
group.
[0012] The third structural unit (c) is derived from a carboxyl
group-containing monomer (C). The sulfonate group-containing
copolymer may be present in the cleaning composition of the present
invention in an amount ranging from about 0.01% to about 20% by
total weight of the cleaning composition.
[0013] The cleaning composition of the present invention can be in
any solid or liquid product form. It can be a laundry detergent
composition, a hard surface cleaning composition, a hand
dishwashing composition, or an automatic dishwashing composition.
Preferably, the cleaning composition is in a liquid form and is
more preferably in a single phase or multiphase unit dose form as
encapsulated by a single compartment or multi-compartment
water-solution pouch. It may further comprise, in addition to the
one or more alkoxylated polyalkyleneimines and the sulfonate
group-containing copolymer as described hereinabove, one or more
surfactants selected from the group consisting of anionic
surfactants, cationic surfactants, nonionic surfactants, amphoteric
surfactants, zwitterionic surfactants, and mixtures thereof.
Preferably, the surfactants comprise an anionic surfactant selected
from the group consisting of alkyl benzene sulfonate, alkoxylated
alkyl sulfates, alkyl sulfates, and mixtures thereof.
[0014] The present invention also relates to use of the
above-described cleaning composition for treating fabrics to
achieve improved whiteness maintenance benefit.
[0015] These and other features of the present invention will
become apparent to one skilled in the art upon review of the
following detailed description when taken in conjunction with the
appended claims. Note that preferred embodiments of the present
invention include any combination of two or more of those preferred
embodiments of the present invention as described hereinbelow.
DETAILED DESCRIPTION OF THE INVENTION
Definitions
[0016] As used herein, the articles "a" and "an" when used in a
claim, are understood to mean one or more of what is claimed or
described.
[0017] As used herein, the term "substantially free of" or
"substantially free from" means that the indicated material is
present in an amount of no more than about 5 wt %, preferably no
more than about 2%, and more preferably no more than about 1 wt %
by weight of the composition.
[0018] As used therein, the term "essentially free of" or
"essentially free from" means that the indicated material is
present in an amount of no more than about 0.1 wt % by weight of
the composition, or preferably not present at an analytically
detectible level in such composition. It may include compositions
in which the indicated material is present only as an impurity of
one or more of the materials deliberately added to such
compositions.
[0019] As used herein the phrase "cleaning composition," "detergent
composition," or "detergent or cleaning composition" are used
interchangeably herein to refer to compositions and formulations
designed for cleaning soiled material. Such compositions include
but are not limited to, laundry detergent compositions, fabric
softening compositions, fabric enhancing compositions, fabric
freshening compositions, laundry prewash, laundry pretreat, laundry
additives, spray products, dry cleaning agent or composition,
laundry rinse additive, wash additive, post-rinse fabric treatment,
ironing aid, dish washing compositions, hard surface cleaning
compositions, unit dose formulation, delayed delivery formulation,
detergent contained on or in a porous substrate or nonwoven sheet,
and other suitable forms that may be apparent to one skilled in the
art in view of the teachings herein. Such compositions may be used
as a pre-cleaning treatment, a post-cleaning treatment, or may be
added during the rinse or wash cycle of the cleaning process. The
cleaning compositions may have a form selected from liquid, powder,
single-phase or multi-phase unit dose or pouch form, tablet, gel,
paste, bar, or flake. In a preferred embodiment of the present
invention, the cleaning composition of the present invention is a
liquid laundry or dish detergent composition, which is in a single
phase or multiphase unit dose form as encapsulated by a single
compartment or multi-compartment water-soluble pouch, e.g., formed
by a water-soluble polymer such as polyvinyl alcohol (PVA) or
copolymers thereof. More preferably, the cleaning composition of
the present invention is a liquid laundry detergent composition
designated for treating fabrics to achieve improved whiteness
maintenance benefit.
[0020] As used herein, the term "laundry detergent" means a liquid
or solid composition, and includes, unless otherwise indicated,
granular or powder-form all-purpose or "heavy-duty" washing agents,
especially cleaning detergents as well as cleaning auxiliaries such
as bleach additives or pretreat types. In a preferred embodiment of
the present invention, the laundry detergent is a liquid laundry
detergent composition.
[0021] As used herein, the term "soiled material" refers
non-specifically to any type of flexible material consisting of a
network of natural or artificial fibers, including natural,
artificial, and synthetic fibers, such as, but not limited to,
cotton, linen, wool, polyester, nylon, silk, acrylic, and the like,
as well as various blends and combinations. Soiled material may
further refer to any type of hard surface, including natural,
artificial, or synthetic surfaces, such as, but not limited to,
tile, granite, grout, glass, composite, vinyl, hardwood, metal,
cooking surfaces, plastic, and the like, as well as blends and
combinations.
[0022] As used herein, the term "water hardness" or "hardness"
means uncomplexed cations ion (i.e., Ca.sup.2+ or Mg.sup.2+)
present in water that have the potential to precipitate under
alkaline conditions, and thereby diminishing the surfactancy and
cleaning capacity of surfactants. Further, the terms "high water
hardness" and "elevated water hardness" can be used interchangeably
and are relative terms for the purposes of the present invention,
and are intended to include, but not limited to, a hardness level
containing at least 12 grams of calcium ion per gallon water (gpg,
"American grain hardness" units).
[0023] As used herein, the term "average molecular weight"
typically refers to the weight average molecular weight of the
polymer chains in a polymer composition, unless otherwise
specified. Further, the "weight average molecular weight" or
"average weight-average molecular weight" (M.sub.w) of a polymer
may be calculated using the equation:
M.sub.w=(.SIGMA..sub.iN.sub.iM.sub.i.sup.2)/(.SIGMA..sub.iN.sub.iM.sub.i-
)
wherein N.sub.i is the number of molecules having a molecular
weight M.sub.i. The weight average molecular weight must be
measured by the method described in the Test Methods section.
[0024] As used herein, the "number average molecular weight" or
"average number-average molecular weight" (M.sub.n) of a polymer
may be calculated using the equation:
M.sub.n=(.SIGMA..sub.iN.sub.iM.sub.i)(.SIGMA..sub.iN.sub.i)
wherein N.sub.i is the number of molecules having a molecular
weight M.sub.i. The number average molecular weight can be
determined in accordance with ASTM Method D6474-12 (2012).
[0025] As used herein, the term "acid form equivalent" means that
the proportion (compositional ratio) of the mass of each of the
sulfonate group-containing monomer, the carboxyl group-containing
monomer, and other acid group-containing monomers of the sulfonate
group-containing copolymer of the present invention, which is
calculated as the proportion of the acid form of the each monomer.
The same shall apply to calculation of the proportion of the mass
of the structural unit derived from the monomer relative to the
mass of the structural units derived from all monomers contained in
the copolymer. For example, calculation of the proportion of the
mass of sodium acrylate or a structural unit derived therefrom
relative to the mass of all monomer components means calculation of
the mass of acrylic acid, or the structural unit derived from
acrylic acid, as an acid of sodium acrylate; calculation of the
proportion of the mass of sodium
3-allyloxy-2-hydroxypropanesulfonate or a structural unit derived
therefrom relative to the mass of all monomer components means
calculation of the mass of 3-allyloxy-2-hydroxypropanesulfonic
acid, or the structural unit derived from
3-allyloxy-2-hydroxypropanesulfonic acid, as an acid of sodium
3-allyloxy-2-hydroxypropanesulfonate. Further, the proportions of
the masses of an amine salt group-containing monomer and an amine
salt structure-containing structural unit may also be calculated as
the proportions of the masses of an amine (amino group)-containing
monomer and an amine structure (amino group structure)-containing
structural unit, respectively.
Alkoxylated Polyalkyleneimines
[0026] The cleaning composition of the present invention contains
at least one, and preferably two or more, alkoxylated
polyalkyleneimines.
[0027] The alkoxylated polyalkylenimines of the present invention
may be represented as containing repeating units of formulae (1),
(2), (3) and (4)
##STR00002##
wherein: [0028] # in each case denotes one-half of a bond between a
nitrogen atom and the free binding position of a group A.sup.1 of
two adjacent repeating units of formulas (1), (2), (3) or (4);
[0029] A.sup.1 is independently selected from linear or branched
C.sub.2-C.sub.6 alkylene; and [0030] E is independently selected
from alkylenoxy units of the formula (5):
##STR00003##
[0030] wherein: [0031] * in each case denotes the bond to the
nitrogen atom of the repeating unit of formula (1), (2) or (4);
[0032] A.sup.2 is in each case independently selected from
1,2-propylene, 1,2-butylene and 1,2-isobutylene; [0033] R is in
each case independently selected from hydrogen and
C.sub.1-C.sub.4-alkyl; [0034] m has an average value in the range
of from 0 to about 2; [0035] n has an average value in the range of
from about 20 to about 50; and [0036] p is a rational number from
about 10 to about 50. Each individual alkoxylated polyalkyleneimine
may consist of 1 repeating unit of formula (1), x repeating units
of formula (2), y repeating units of formula (3) and y+1 repeating
units of formula (4), wherein x and y in each case have a value in
the range of from 0 to about 150; and the polymer has a degree of
quaternization of from 0 to about 50%. For more information
regarding the alkoxylated polyalkyleneimines, please see U.S. Pat.
No. 8,097,579B and WO2006/108856A1.
[0037] In a simplified representation, the alkoxylated
polyalkyleneimines of the present invention can be considered as
having a polyalkyleneimine core and at least one side chain bonded
to a nitrogen atom in the polyalkyleneimine core.
[0038] The polyalkyleneimine core is formed by the repeating units
of formulae (1), (2), (3) and (4) as described hereinabove, but
minus the alkylenoxy units E. The polyalkyleneimine core of the
alkoxylated polyalkyleneimine of the present invention has an
average number-average molecular weight (MW.sub.PEI) ranging from
about 100 to about 100,000 Daltons, preferably from about 100 to
about 5000 Daltons, and more preferably from about 200 to about
1000 Daltons.
[0039] The at least one side chain of the alkoxylated
polyalkyleneimine, which is formed by the alkylenoxy units E as
described hereinabove, preferably has an inner polyethylene oxide
block and an outer polypropylene oxide block, which can be
represented by an empirical formula (I) of:
-(EO).sub.b(PO).sub.c--R (I)
while EO is ethylene oxide; b has a weight average value ranging
from about 3 to about 60; PO is propylene oxide; c has a weight
average value ranging from 0 to about 60; R is selected from the
group consisting of hydrogen, C.sub.1-C.sub.4 alkyls, and
combinations thereof.
[0040] In one embodiment of the present invention, the cleaning
composition may contain a first alkoxylated polyalkyleneimine,
which has a polyalkyleneimine core with MW.sub.PEI ranging from
about 100 to about 5000 Daltons, and preferably from about 200 to
about 1000 Daltons; b ranges from about 5 to about 40, preferably
from about 10 to about 30, more preferably from about 15 to 25; and
wherein c is 0. Said alkoxylated polyalkyleneimine can be
represented by an empirical formula of
(PEI).sub.200-1000(EO).sub.15-25. Preferably, not not necessarily,
the cleaning composition contains only such first alkoxylated
polyalkyleneimine, i.e., without any other alkoxylated
polyalkyleneimine.
[0041] In another embodiment of the present invention, the cleaning
composition may contain a second alkoxylated polyalkyleneimine,
which has a polyalkyleneimine core with MW.sub.PEI ranging from
about 100 to about 5000 Daltons, and preferably from about 200 to
about 1000 Daltons; b ranges from about 10 to about 50, preferably
from about 15 to about 40, more preferably from about 20 to about
30; and wherein c ranges from about 1 to about 50, preferably from
about 5 to about 40, and more preferably from about 10 to about 30.
Said first alkoxylated polyalkyleneimine can be represented by an
empirical formula of
(PEI).sub.200-1000(EO).sub.20-30(PO).sub.10-30. Preferably, not not
necessarily, the cleaning composition contains only such second
alkoxylated polyalkyleneimine, i.e., without the first alkoxylated
polyalkyleneimine or any other alkoxylated polyalkyleneimine.
[0042] In yet another embodiment of the present invention, the
cleaning composition contains both the first and second alkoxylated
polyalkyleneimines Preferably, the weight ratio between such first
and second alkoxylated polyalkyleneimines ranges from about 1:10 to
about 10:1, preferably from about 1:5 to about 5:1, and more
preferably from about 1:2 to about 2:1. In addition to the first
and second alkoxylated polyalkyleneimines, the cleaning composition
of the present invention may comprise other alkoxylated
polyalkyleneimines falling within the description provided
hereinabove.
[0043] The alkoxylated polyalkyleneimine(s) may be present in the
cleaning composition of the present invention in an amount ranging
from about 0.01% to about 20%, preferably from about 0.05% to about
15%, more preferably from about 0.1% to about 10%, and most
preferably from about 0.5% to about 5%, by total weight of such
cleaning composition. In a particularly preferred embodiment of the
present invention, the cleaning composition contains from about
0.1% to about 5% by weight of the first alkoxylated
polyalkyleneimine, and from 0% to about 2% by weight of the second
alkoxylated polyalkyleneimine.
Sulfonate Group-Containing Copolymer
[0044] As mentioned hereinabove, the cleaning composition of the
present invention further contains a sulfonate group-containing
copolymer comprising: (i) a structural unit (a) derived from a
sulfonate group-containing monomer (A); (ii) a structural unit (b)
derived from a polyoxyalkylene monomer (B); and (iii) a structural
unit (c) derived from a carboxyl group-containing monomer (C).
[0045] Sulfonate Group-Containing Monomer (A)
[0046] The sulfonate group-containing monomer (A) of the present
invention, which is also referred to as a sulfonate
group-containing unsaturated monomer, is a monomer having a
sulfonate group and a carbon-carbon double bond. The sulfonate
group is intended to include sulfonic acids and their salts.
Examples of salts of sulfonic acids include, but are not
particularly limited to: metal salts, ammonium salts, and organic
amine salts of sulfonic acids. Suitable metal salts preferably
include, for example, alkali metal ions such as sodium ions or
potassium ions; alkaline earth metal ions such as magnesium ions,
calcium ions, strontium ions, or barium ions; aluminum ions; or
ferric or ferrous ions. Suitable organic amine salts preferably
include organic amine groups such as, for example, an alkanolamine
such as monoethanolamine, diethanolamine, or triethanolamine; an
alkylamine such as monoethylamine, diethylamine, or triethylamine;
or a polyamine such as ethylenediamine or triethylenediamine. The
salts of sulfonic acids are preferably potassium sulfonate, sodium
sulfonate, ammonium sulfonate, or quaternary amines of sulfonic
acids.
[0047] The sulfonate group-containing monomer (A) may contain one
or more sulfonate groups. In one preferred but not necessary
embodiment of the present invention, the monomer (A) is represented
by the following formula (III):
##STR00004##
wherein R.sup.3 represents a hydrogen atom or a methyl group;
R.sup.4 represents a direct bond, CH.sub.2, or CH.sub.2CH.sub.2; X
and Y each represent hydroxy or SO.sub.3M where M represents a
hydrogen atom, Li, Na, or K, and at least one of X and Y is
SO.sub.3M.
[0048] It is preferred that one of X and Y in the above formula
(III) is a SO.sub.3M and the other is a hydroxy group. It is more
preferred that X is a hydroxy group and Y is a SO.sub.3M. Further,
M may represent an ammonium group or an organic amine group as
mentioned hereinabove regarding the salts of sulfonic acid. The
term "direct bond" as used herein refers to a covalent bond
directly connecting two adjacent atoms. Therefore, when R.sup.4 is
a direct bond, the carbon atom and the oxygen atom adjacent to
R.sup.4 are directly connected to each other by a covalent bond
without any other atom in between.
[0049] Suitable examples of the sulfonate group-containing monomer
(A) include, but are not limited to: compounds represented by the
formula (III) as described hereinabove,
2-acrylamide-2-methylpropanesulfonic acid, styrene sulfonic acid,
(meth)allylsulfonic acid, vinyl sulfonic acid,
2-(meth)allyloxyethylenesulfonic acid, and salts thereof.
Specifically, compounds falling within the formula (III) as
described hereinabove, such as
3-(meth)allyloxy-2-hydroxypropanesulfonic acid and
3-(meth)allyloxy-1-hydroxypropanesulfonic acid as well as salts
thereof are, are preferred examples of the sulfonate
group-containing monomer (A) of the present invention because it
has been observed that copolymers of the present invention having a
structural unit derived from a compound represented by the formula
(III) has improved anti-soil redeposition properties and increased
preservation stability. In order to more successfully ensure the
effect of the present invention enough,
3-allyloxy-2-hydroxypropanesulfonic acid and the sodium salt
thereof are more preferred. Alternatively,
2-acrylamide-2-methylpropanesulfonic acid and the sodium salt there
of are also preferred examples of the sulfonate group-container
monomer (A) for the practice of the present invention.
[0050] The sulfonate group-containing copolymer contains preferably
from about 1% to about 38% by mass in acid form equivalent of the
structural unit (a) in 100% by mass of all structural units
constituting the sulfonate group-containing copolymer, more
preferably from about 2% to about 30% by mass, still more
preferably from about 3% to about 25% by mass, further more
preferably from about 4% to about 20% by mass, particularly
preferably from about 5% to about 18% by mass, and most preferably
from about 5% to about 16% by mass.
[0051] Further, the sulfonate group-containing copolymer preferably
contains no more than about 1% by mass of the structural unit (a)
derived from the sulfonate group-containing monomer (A) that has
two or more sulfonate groups, in 100% by mass of all structural
units constituting the sulfonate group-containing copolymer.
[0052] The structural unit (a) hereinabove is a copolymerized
structural unit formed by radical polymerization of the sulfonate
group-containing monomer represented by the formula (III), and the
structural unit (a) itself can be represented by the following
formula (IV):
##STR00005##
wherein R.sup.3, R.sup.4, X, and Y are all the same as defined
hereinabove in formula (III).
[0053] The method for preparing the sulfonate group-containing
monomer (A) is not particularly limited, and any suitable method
can be used for the preparation. For example, a method for adding a
hydrogen sulfite to the glycidyl group of (meth)allylglycidyl ether
is mentioned as an example of a simple method for the
preparation.
[0054] Polyoxyalkylene Monomer (B)
[0055] The polyoxyalkylene monomer (B) of the present invention is
characterized by having a structure represented by the following
formula (II):
##STR00006##
wherein R.sup.1 can be either a hydrogen atom or a methyl group,
and R.sup.2 can be a direct bond, CH.sub.2, or CH.sub.2CH.sub.2.
Preferably, R.sup.1 and R.sup.2 are respectively: (i) a hydrogen
atom and CH.sub.2; (ii) a methyl group and CH.sub.2; or (iii) a
methyl group and CH.sub.2CH.sub.2. More preferably, R.sup.1 and
R.sup.2 are respectively a methyl group and CH.sub.2, or a methyl
group and CH.sub.2CH.sub.2. Most preferably, R.sup.1 and R.sup.2
are respectively a methyl group and CH.sub.2CH.sub.2.
[0056] Z represents one or more structural units, either the same
or different from each other, and each of which is derived from a
C.sub.2-C.sub.20 alkylene oxide. The number "n" represents the
average number of alkylene oxide-derived structural repeating units
Z, and it is from about 1 to about 200.
[0057] R.sup.0 represents a hydrogen atom or a C.sub.1-C.sub.30
organic group. Examples of the organic group in R.sup.0 include
C.sub.1-C.sub.30 alkyl, C.sub.2-C.sub.30 alkenyl, and
C.sub.6-C.sub.30 aryl. These may further have a substituent group.
Examples of the substituent group include heterocyclic rings,
alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups,
alkoxycarbonyl groups, aryloxycarbonyl groups, sulfamoyl groups,
acyl groups, acyloxy groups, amide groups, carbamoyl groups, ureido
groups, alkylsulfonyl groups, arylsulfonyl groups, amino groups,
halogens, fluorohydrocarbon groups, cyano groups, nitro groups,
hydroxy, mercapto, and silyl groups. Specific examples of the
C.sub.1-C.sub.30 organic group include methyl, ethyl, butyl, octyl,
lauryl, cyclohexyl, phenyl, naphthyl, pyridyl, pyrimidyl,
imidazolidyl, morpholyl, butenyl, pentenyl, hexenyl, heptenyl,
methylcarbonyl, and ethylcarbonyl. R.sup.0 is preferably a hydrogen
atom or a methyl group, and more preferably a hydrogen atom.
[0058] In the formula (II), the structural unit Z derived from an
alkylene oxide represents an oxyalkylene structural unit containing
a ring-opening alkylene oxide. For example, in cases where the
alkylene oxide is ethylene oxide (EO), the structural unit Z is a
--OCH.sub.2CH.sub.2-- (oxyethylene) structural unit containing a
ring-opening ethylene oxide. The oxyalkylene structural unit Z is
derived from an alkylene oxide having from about 2 to about 20
carbon atoms, preferably from about 2 to about 15 carbon atoms,
more preferably from about 2 to about 10 carbon atoms, still more
preferably from about 2 to about 5 carbon atoms, particularly
preferably from about 2 to about 3 carbon atoms, and most
preferably about 2 carbon atoms.
[0059] Examples of the structural unit Z derived from an alkylene
oxide include structural units derived from compounds such as
ethylene oxide (EO), propylene oxide (PO), isobutylene oxide,
1-butene oxide, 2-butene oxide, trimethylethylene oxide,
tetramethylene oxide, tetramethylethylene oxide, butadiene
monoxide, octylene oxide, styrene oxide, and 1,1-diphenyl ethylene
oxide. In particular, the structural unit Z is preferably derived
from EO or PO (that is, oxyethylene or oxypropylene), and is more
preferably oxyethylene. Such a structural unit can contain a single
species of oxyalkylene, or it may contain two or more species of
oxyalkylenes.
[0060] A preferred polyoxyalkylene monomer (B) of the present
invention mainly includes multiple repating structural units of
oxyethylene (--O--CH.sub.2CH.sub.2--). In this case, the phrase
"mainly includes . . . oxyethylene" means that if two or more
species of oxyalkylenes are present in the monomer, oxyethylene
accounts for most of all oxyalkylenes (e.g., no less than about 50
mol %, or preferably no less than about 70 mol %, or more
preferably no less than about 80 mol % or about 90 mol %, or most
preferably about 100%, relative to 100 mol % of all oxyalkylaenes).
This allows smooth progress of polymerization in a production
process, and provides excellent effects such as improvement in
water solubility or anti-redeposition properties. If the proportion
of the oxyethylene is not less than about 50 mol %, the
hydrophilicity of the group formed by the oxyalkylene can be
further improved.
[0061] In the formula (II), n represents the average number of the
alkylene oxide-derived structural repeating units Z, and it can
range from about 1 to about 200, preferably from about 5 to about
100, more preferably from about 10 to about 80, and still more
preferably from about 20 to about 80 or from about 25 to about 70,
and most preferably from about 40 to about 60. When n is in the
above preferred ranges, the compatibility with liquid detergents
and the anti-redeposition properties of the resulting sulfonate
group-containing copolymer tend to be improved.
[0062] The sulfonate group-containing copolymer of the present
invention preferably contains from about 9% to about 76% by mass of
the structural unit (b) in 100% by mass of all structural units
constituting the sulfonate group-containing copolymer, more
preferably from about 10% to about 70% by mass, still more
preferably from about 12% to about 65% by mass, further more
preferably from about 15% to about 60% by mass, particularly
preferably from about 18% to about 50% by mass or from about 20% to
about 49% by mass, and most preferably from about 30% to about 45%
by mass. In the calculation of the total weight of all structural
units derived from all monomers in the present invention, the
weights of the sulfonate group-containing monomer, the carboxyl
group-containing monomer, and other acid group-containing monomers
contained in all monomer components are calculated as the weights
of their acids monomers.
[0063] The copolymer of the present invention is characterized by
having the structural unit (b) derived from the polyoxyalkylene
monomer (B) represented by the formula (II) hereinabove. The
structural unit (b) derived from the polyoxyalkylene monomer herein
is a copolymerized structural unit formed by radical polymerization
of the polyoxyalkylene monomer (B), and is represented by the
following formula (V):
##STR00007##
wherein R.sup.1, R.sup.2, Z, n, and R.sup.0 are all the same as
defined hereinabove in formula (II).
[0064] The polyoxyalkylene monomer (B) of the present invention as
described hereinabove may be produced by any suitable method.
Preferably, it is produced by method (1) in which an alkylene oxide
is added to an alcohol having a carbon-carbon double bond, such as
allyl alcohol, methallyl alcohol, or isoprenol; alternatively, it
is produced by method (2) in which a polyalkylene glycol is added
to a halide having a carbon-carbon double bond, such as allyl
chloride, methallyl chloride, isoprenyl chloride, or vinyl
chloride.
[0065] In the above-described method (1), an alkylene oxide is
added to an alcohol having a carbon-carbon double bond by, for
example, a) anionic polymerization in which a hydroxide of an
alkali metal, a strong alkali such as an alkoxide, or alkylamine is
used as a base catalyst, b) cationic polymerization in which a
halide of a metal or metalloid, mineral acid, or acetic acid is
used as a catalyst, or c) coordination polymerization in which a
combination of an alkoxide of a metal such as aluminum, iron, or
zinc, an alkaline-earth compound, and/or Lewis acid is used. Thus,
the alkylene oxide is added to the hydroxy group of the alcohol,
and the length of the polyoxyalkylene chain so formed is determined
by the charge ratio of the alkylene oxide and the alcohol added
during the polymerization.
[0066] The polyoxyalkylene monomer (B) of the present invention as
described hereinabove has good stability during polymerization.
Accordingly, the anti-redeposition properties of the resulting
copolymer are improved. Further, the polyoxyalkylene monomer (B) of
the present invention as described hereinabove provides a copolymer
with favorable temporal stability. Further, when processed into
various products (compositions) for various applications, the
copolymer of the present invention, i.e., containing the structural
unit (b) derived from the polyoxyalkylene monomer (B) as described
hereinabove, shows excellent stability, and whereby the resulting
products preferably exhibit stable performance.
[0067] Carboxyl Group-Containing Monomer (C)
[0068] The carboxyl group-containing monomer (C) of the present
invention, which is also referred to as a carboxyl group-containing
unsaturated monomer, is a monomer having a carboxyl group and a
carbon-carbon double bond. The carboxyl group is intended to
include carboxylic acids and their salts. Examples of the salts of
the carboxylic acids include, but are not particularly limited to,
metal salts, ammonium salts, and organic amine salts of carboxylic
acids. Preferred examples of metal ions in the metal salts include
alkali metal ions such as sodium and potassium ions; alkaline earth
metal ions such as magnesium, calcium, strontium, and barium ions;
aluminum ions; and ferric or ferrous ions. Further, preferred
examples of organic amine groups of the organic amine salts include
alkanolamines such as monoethanolamine, diethanolamine, and
triethanolamine; alkylamines such as monoethylamine, diethylamine,
and triethylamine; polyamines such as ethylenediamine and
triethylenediamine. Examples of the salts of the carboxylic acids
include lithium salts, potassium salts, sodium salts, ammonium
salts, and quaternary amine salts.
[0069] Examples of the carboxyl group-containing monomer (C)
include (meth)acrylic acid, maleic acid and anhydride thereof,
fumaric acid, itaconic acid, crotonic acid, 2-methylene glutaric
acid, and salts thereof. Particularly preferred carboxyl
group-containing monomer (C) is (meth)acrylic acid, maleic acid or
anhydride thereof, or a salt thereof, due to their high
polymerizability and their ability to form a copolymer with high
anti-redeposition properties. Still more preferred carboxyl
group-containing monomer (C) is acrylic acid, maleic acid or
anhydride thereof, or a salt thereof. Most preferred carboxyl
group-containing monomer (C) is acrylic acid or its salt. In the
event where the carboxyl group-containing monomer (C) is a compound
that can form an acid anhydride, such as maleic acid, the monomer
then may be in the acid anhydride form, such as maleic anhydride.
The carboxyl group-containing monomers described hereinabove may be
used either alone or in combinations of two, three, four or
more.
[0070] The sulfonate group-containing copolymer of the present
invention contains from about 20% to about 90% by mass in acid form
equivalent of the structural unit (c) in 100% by mass of all
structural units constituting the sulfonate group-containing
copolymer. The amount of the structural unit (c) is preferably from
about 25% to about 85% by mass, more preferably from about 25% to
about 80% by mass, still more preferably from about 25% to about
75% by mass, still more preferably from about 35% to about 73% by
mass or from about 35% to about 70%, yet more preferably from about
35% to about 55%, and most preferably from about 40% to about 55%
by mass. The sulfonate group-containing polymer of the present
invention having a proportion of the structural unit (c) of from
about 20% to about 90% by mass has improved anti-redeposition
properties, particularly anti-redeposition properties against
hydrophilic soil under high hardness condition. In order to improve
the compatibility with liquid detergents as well as the
anti-redeposition properties, the proportion of the structural unit
(c) is most preferably from about 40% to about 55% by mass. In
light of the structure, the proportion of the mass of the carboxyl
group-containing monomer that corresponds to a salt of an acid is
calculated as the mass of the acid. In cases where the carboxyl
group-containing monomer is an acid anhydride, the mass of the
monomer is calculated as the mass of the dicarboxylic acid, which
is an acid of the monomer, prepared from the acid anhydride by
hydrolysis.
[0071] The sulfonate group-containing copolymer of the present
invention contains preferably from about 1% to about 100% by mass,
more preferably from about 20% to about 100% by mass, still more
preferably from about 50% to about 100% by mass, particularly
preferably from about 80% to about 100% by mass, and most
preferably 100% by mass, in acid form equivalent of a structural
unit derived from a monocarboxylic acid such as (meth)acrylic acid
in 100% by mass of the total of the structural unit (c) derived
from the carboxyl group-containing monomer (C).
[0072] The copolymer of the present invention contains the
structural unit (c) derived from the carboxyl group-containing
monomer (C). The structural unit (c) is a copolymerized structural
unit formed by radical polymerization of the carboxyl
group-containing monomer (C). For example, in cases where the
carboxyl group-containing monomer (C) is acrylic acid or a sodium
salt thereof, the corresponding structural unit (c) is represented
by --CH.sub.2--CH(COOH)-- or --CH.sub.2--CH(COONa)--.
[0073] Other Monomers
[0074] The sulfonate group-containing copolymer of the present
invention may contain an additional structural unit (e) derived
from a monomer (E) other than the sulfonate group-containing
monomer (A), the polyoxyalkylene monomer (B), and the carboxyl
group-containing monomer (C).
[0075] The monomer (E) is not particularly limited, provided that
it is copolymerizable with the monomers (A), (B), and (C). Examples
of suitable monomers (E) include, but are not limited to: hydroxy
group-containing alkyl (meth)acrylates such as 2-hydroxyethyl
(meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl
(meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl
(meth)acrylate, and .alpha.-(hydroxymethyl)ethyl (meth)acrylate;
alkyl (meth)acrylates prepared by esterification of (meth)acrylic
acid with a C.sub.1-C.sub.18 alcohol, such as methyl
(meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate,
cyclohexyl (meth)acrylate, and lauryl (meth)acrylate; amino
group-containing acrylates such as dimethylaminoethyl
(meth)acrylate and quaternized dimethylaminoethyl (meth)acrylate;
amide group-containing monomers such as (meth)acrylamide, dimethyl
acrylamide, and isopropyl acrylamide; vinyl esters such as vinyl
acetate; alkenes such as ethylene and propylene; aromatic vinyl
monomers such as styrene; maleimide derivatives such as maleimide,
phenyl maleimide, and cyclohexyl maleimide; nitrile
group-containing vinyl monomers such as (meth)acrylonitrile;
phosphonic acid (salt) group-containing monomers such as
vinylphosphonic acid, (meth)allylphosphonic acid, and their salts;
aldehyde group-containing vinyl monomers such as (meth)acrolein;
alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether,
and butyl vinyl ether; other functional group-containing monomers
such as vinyl chloride, vinylidene chloride, allyl alcohol, and
vinyl pyrrolidone. These other monomers may be used either alone or
in combinations of two, three, four or more.
[0076] The structural unit (e) derived from the monomer (E) herein
is a copolymerized structural unit formed by radical polymerization
of the monomer (E). For example, in cases where the monomer (E) is
methyl acrylate, the structural unit (e) is a structural unit
represented by --CH.sub.2--CH(COOCH.sub.3)--.
[0077] The sulfonate group-containing copolymer may contain only
one structure unit (e) or two or more structure units (e) as
described hereinabove.
[0078] Preferably, the copolymer of the present invention contains
from 0% to about 30% by mass, more preferably from 0% to about 20%
by mass, still more preferably from 0% to about 10% by mass, and
most preferably 0% by mass of the structural unit (e) derived from
the monomer (E) in 100% by mass of all structural units
constituting the sulfonate group-containing copolymer.
[0079] Preferably, two or more of the structural units (a), (b),
(c), and optionally (e) satisfy the above-described proportions (by
mass) in the copolymer of the present invention. That is, the
copolymer of the present invention containing a combination of the
structural units (a), (b), (c) and optionally (e) with the
above-described preferred proportions (by mass) is also a preferred
embodiment of the copolymer of the present invention. The total of
the proportions of the combination is 100% by mass.
[0080] The sulfonate group-containing copolymer as described
hereinabove preferably contains from about 1% to about 38%, more
preferably from about 4% to about 20% and most preferably from
about 5% to about 16%, by mass in an acid form equivalent of the
structural unit (a) in 100% by mass of all monomer structural units
constituting the sulfonate group-containing copolymer. It may also
contain from about 9% to about 76%, preferably from about 20% to
about 49% and more preferably from about 30% to about 45%, by mass
of the structural unit (b) in 100% by mass of all monomer
structural units constituting the sulfonate group-containing
copolymer. The number "n" in formula (II), which represents the
average number of repeating oxyalkylene unit Z, is preferably from
about 5 to about 100, more preferably form about 10 to about 80,
still more preferably from about 25 to 70, and most preferably from
about 40 to about 60. The sulfonate group-containing copolymer may
also contain from about 20% to about 90%, preferably from about 25%
to about 75% and more preferably from about 35% to about 55%, by
mass in acid form equivalent of the structural unit (c) in 100% by
mass of all monomer structural units constituting the sulfonate
group-containing copolymer.
[0081] In a particularly preferred embodiment of the present
invention, the sulfonate group-containing copolymer contains:
[0082] (i) from about 5% to about 16% by mass of the structure unit
(a) in acid form equivalent in 100% by mass of all monomer
structural units constituting the sulfonate group-containing
copolymer, wherein the sulfonate group-containing monomer (A) is
3-allyloxy-2-hydroxypropanesulfonate; [0083] (ii) from about 30% to
about 45% by mass of the structure unit (b) in 100% by mass of all
monomer structural units constituting the sulfonate
group-containing copolymer, wherein the polyoxyalkylene monomer (B)
comprises an ethylene oxide-derived group having from about 40 to
about 60 repeating oxyethylene units; and [0084] (iii) from about
35% to about 55% by mass of the structure unit (c) in acid form
equivalent in 100% by mass of all monomer structural units
constituting the sulfonate group-containng copolymer, wherein the
carboxyl group-containing monomer (C) is acrylic acid or a salt
thereof,
[0085] Further, it is preferred that the sulfonate group-containing
copolymer is characterized by a parameter of
P.times.MW.sub.S.times.n that ranges from about 950,000 to about
800,000,000, in which: [0086] P is defined as the ratio by mass of
the structural unit (b) to the structural unit (a) in the sulfonate
group-containing copolymer is P; [0087] MW.sub.S is the weight
average molecular weight of the sulfonate group-containing
copolymer; and [0088] n is defines as the same hereinabove in
formula (II).
[0089] The product of P.times.Mw.times.n is preferably not less
than about 1,000,000, more preferably not less than about
1,500,000, and most preferably not less than about 2,000,000. The
product of P.times.Mw.times.n is preferably not more than about
500,000,000, more preferably not more than about 100,000,000. For
example, it may preferably range from 1,000,000 to 50,000,000.
[0090] Without being bound by any theory, it is believe that
sulfonate group-containing copolymers characterized by such a
parameter have improved adsorption for hydrophilic soil, which in
turn leads to further improved anti-soil redeposition efficacy,
especially against hydrophilic soil under wash conditions marked by
higher water hardness (i.e., higher water hardness tolerance).
Cleaning compositions formulated with such sulfonate
group-containing copolymers produce a low amount of salt
precipitates and have a high washing effect even when used in an
area where there is hard water with high concentrations of calcium
ions and magnesium ions (for example, not less than 100 mg/L). The
effect is particularly remarkable when the cleaning compositions
contain an anionic surfactant such as LAS. Further, such cleaning
compositions exhibit improved fabric whiteness maintenance benefit
and/or satisfactory phase stability when in a liquid form.
[0091] Preferably, but not necessarily, the weight average
molecular weight (MW.sub.S) of the sulfonate group-containing
copolymer is from about 20,000 to about 200,000, more preferably
from about 22,000 to about 150,000, yet more preferably from about
25,000 to about 100,000, still more preferably from about 30,000 to
about 80,000, and most preferably from about 30,000 to about
75,000. Without being bound by any theory, it is believed that the
sulfonate group-containing polymer of the present invention with
the specified weight average molecular weight MW.sub.S, i.e., from
about 20,000 to about 200,000 has improved anti-redeposition
properties, particularly anti-redeposition properties against
hydrophilic soil under high water hardness conditions. On one hand,
if the weight average molecular weight MW.sub.S of the copolymer is
larger than about 200,000, the copolymer may become highly viscous
and difficult to handle. On the other hand, if MW.sub.S is smaller
than about 20,000, the anti-redeposition properties of the
copolymer significantly deteriorate, resulting in poorer
performance as a detergent builder. The weight average molecular
weight MW.sub.S of the sulfonate group-containing copolymer of the
present invention is determined by the specific method used in the
examples as described hereinafter.
[0092] The ratio by mass (P) of the structural unit (b) to the
structural unit (a) in the sulfonate group-containing copolymer is
preferably from about 1.2 to about 20, more preferably from about
1.3 to about 20, yet more preferably from about 1.5 to about 15,
still more preferably from about 2 to about 10, and most preferably
from about 2.5 to about 5. When the ratio by mass (P) is
calculated, the masses of the structural unit (a) and the
structural unit (b) are calculated as the masses of the acid form
equivalents of them, i.e., P is determined as a mass ratio of the
acid form equivalent of the structural unit (b) to the acid form
equivalent of the structural unit (a). The ratio by mass of the
structural unit (a) to the structural unit (b) to the structural
unit (c) can also be expressed in the form of the proporationso of
the structural units (a), (b), and (c), for example, preferably (1
to 38)/(9 to 76)/(20 to 90), more preferably (2 to 30)/(10 to
70)/(25 to 85), still more preferably (3 to 25)/(12 to 65)/(30 to
80), further more preferably (4 to 20)/(15 to 60)/(35 to 75),
particularly preferably (5 to 18)/(18 to 50)/(40 to 73), still more
preferably (5 to 16)/(20 to 49)/(43 to 70), and most preferably (5
to 16)/(30-45)/(40-55). The total of the proportions of the
structural units (a), (b), and (c) is 100% by mass.
[0093] Without being bound by any theory, it is believed that the
specific ratio by mass P of the structural unit (b) to the
structural unit (a), i.e., from about 1.2 to about 20, contributes
to the improved anti-soil redeposition properties of the copolymer
of the present invention, particularly its improved
anti-redeposition properties against hydrophilic soil under high
water hardness conditions. Further, when the ratio by mass P is
from about 3 to about 10, it is believed to improve the
compatibility of the copolymer with liquid detergents as well as
its anti-redeposition properties.
[0094] More preferably, the sulfonate group-containing copolymer
according to the present invention is characterized by a specific
ratio by mass P of the structural unit (b) to the structural unit
(a) that ranges from about 1.2 to about 20 and a specific weight
average molecular weight MW.sub.S of the copolymer that ranges from
about 20,000 to about 200,000, while the product of
P.times.MW.sub.S is from about 25,000 to about 2,000,000. An
improved effect is observed between the ratio by mass P of the
structural unit (b) to the structural unit (a) and the weight
average molecular weight MW.sub.S of the copolymer, when the
product of the ratio by mass P multiplied by the weight average
molecular weight MW.sub.S is in a specific range of from about
25,000 to about 2,000,000. The resulting sulfonate group-containing
copolymer exhibits significantly improved anti-soil redeposition
properties, particularly anti-redeposition properties against
hydrophilic soil under high water hardness conditions. Further,
such product of the ratio by mass P multiplied by the weight
average molecular weight MW.sub.S may lead to unexpected
improvement in the copolymer's compatibility with liquid detergents
as well as the anti-redeposition properties. Preferably, the
product of the ratio by mass P multiplied by the weight average
molecular weight MW.sub.S ranges from about 50,000 to about
1,500,000, more preferably from about 70,000 to about 1,200,000,
still more preferably from about 100,000 to about 1,000,000, yet
still more preferably from about 120,000 to about 1,000,000, and
most preferably from about 130,000 to about 1,200,000.
[0095] Further, the number n of alkylene oxide-derived structural
repeating units in the formula (II) of the structural unit (b) in
the sulfonate group-containing copolymer also contributes to
improvement of the anti-redeposition properties and liquid
detergent compatibility of the copolymer, especially when it is
provided within a specific range of from about 5 to about 100,
preferably from about 10 to about 80, and more preferably from
about 40 to about 60.
[0096] The sulfonate group-containing copolymers of the present
invention as described hereinabove have improved anti-soil
redeposition ability. Given their enhanced anti-soil redeposition
properties, the sulfonate group-containing copolymers of the
present invention are particularly useful for formulating laundry
detergent compositions with improved whiteness maintenance
performance and cleaning performance. Further, the sulfonate
group-containing copolymers of the present invention exhibit
satisfactory liquid detergent compatibility, which renders them
useful for formulating liquid laundry detergent products with
improved phase stability.
[0097] The cleaning composition of the present invention may
contain one or more of the above-described sulfonate
group-containing copolymers. The sulfonate group-containing
copolymer(s) may be present in such cleaning composition in an
amount ranging from about 0.01% to about 20%, preferably from about
0.05% to about 15%, more preferably from about 0.1% to about 10%,
and most preferably from about 0.5% to about 5%, by total weight of
such cleaning composition.
[0098] Method of Producing Sulfonate Group-Containing Copolymer
[0099] The method of producing the sulfonate group-containing
copolymer of the present invention is not particularly limited, and
any known polymerization method or a modified method based thereon
can be readily used.
[0100] The production method preferably involves copolymerizing
monomer components including a sulfonate group-containing monomer
(A), a polyoxyalkylene monomer (B), a carboxyl group-containing
monomer (C), and optionally a monomer (E), which are the same as
those described hereinabove.
[0101] In order to sufficiently exert the effects of the present
invention, the proportion of the sulfonate group-containing monomer
(A) is, but not particularly limited to, preferably from about 1%
to about 38% by mass, more preferably from about 2% to about 30% by
mass, still more preferably from about 3% to about 25% by mass,
further more preferably from about 4% to about 20% by mass,
particularly preferably from about 5% to about 18% by mass, and
most preferably from about 5% to about 16% by mass in acid form
equivalent in 100% by mass of all the monomers.
[0102] In order to sufficiently exert the effects of the present
invention, the proportion of the polyoxyalkylene monomer (B) is,
but not particularly limited to, preferably from about 9% to about
76% by mass, more preferably about 10% to about 70% by mass, still
more preferably from about 12% to about 65% by mass, further
preferably from about 15% to about 60% by mass, particularly
preferably from about 18% to about 50% by mass, yet more preferably
from about 20% to about 49%, and most preferably from about 30% to
about 45% by mass in acid form equivalent in 100% by mass of all
the monomers.
[0103] In order to sufficiently exert the effects of the present
invention, the proportion of the carboxyl group-containing monomer
(C) is preferably from about 20% to about 90% by mass, more
preferably from about 25% to about 85% by mass, still more
preferably from about 25% to about 80% by mass, further more
preferably from about 25% to about 75% by mass, particularly
preferably from 35% to 73% by mass, yet more preferably from about
35% to about 70%, still more preferably from about 35% to about
55%, and most preferably from about 40% to about 55% by mass in
acid form equivalent in 100% by mass of all the monomers.
[0104] The proportion of the monomer (E) is preferably from 0% to
about 30% by mass, more preferably from 0% to about 20% by mass,
still more preferably from 0% to about 10% by mass, and most
preferably 0% by mass in 100% by mass of all the monomers.
[0105] The monomer components preferably contain two or more of the
sulfonate group-containing monomer (A), the polyoxyalkylene monomer
(B), the carboxyl group-containing monomer (C), and optionally the
monomer (E) in the above preferred proportions. That is,
combination of the sulfonate group-containing monomer (A), the
polyoxyalkylene monomer (B), the carboxyl group-containing monomer
(C), and optionally the monomer (E) in the above preferred
proportions in all the monomers is also a preferred embodiment of
the method of producing the sulfonate group-containing copolymer of
the present invention.
[0106] During copolymerization of the monomer components, the
monomer components are preferably copolymerized using a
polymerization initiator. The amount of the polymerization
initiator to be used in the polymerization reaction may be
appropriately controlled depending on the amount of the monomer
components to be used, and is not particularly limited. Further, a
chain transfer agent, a reaction accelerator (for reducing the
amount of the initiator, which can be, e.g., heavy metal ions), a
catalyst (for decomposing a polymerization initiator), a reducing
compound (e.g., organic compounds such as ferrocene or metal
naphtenates, or inorganic reducing compounds), the like can be
preferably used in addition to the polymerization initiator.
[0107] The combination of polymerization initiator, chain-transfer
agent, and reaction accelerator is not particularly limited, and
these may be selected from any of those described hereinabove. A
most preferred combination of the initiator and the chain transfer
agent is the combination of one or more of persulfates and one or
more of sulfites.
[0108] The copolymerization may be carried out by any method, such
as the commonly used methods of solution polymerization, bulk
polymerization, suspension polymerization, or emulsion
polymerization. Solution polymerization is particularly preferred.
The copolymerization may be carried out either continuously or in
batches. Known solvents may be used in such copolymerization.
[0109] After completion of the polymerization reaction, a suitable
alkali component (e.g., alkali metal hydroxides, alkaline earth
metal hydroxides, and organic amines) may be appropriately added
for post treatment, if needed, and the degree of neutralization
(final degree of neutralization) of the resulting sulfonate
group-containing copolymer may be set within a predetermined range.
The final degree of neutralization is not particularly limited.
This is because the final degree of neutralization of the copolymer
varies depending on intended use. Accordingly, the final degree of
neutralization may be set to an extremely wide range of from about
1 to about 100 mol %.
[0110] A copolymer composition formed by the copolymerization
process described hereinabove essentially contains the sulfonate
group-containing copolymer of the present invention. In addition,
the copolymer composition may contain unreacted monomers, unreacted
or decomposed polymerization initiator, homopolymers formed by one
out of three of the monomers described hereinabove, binary
copolymers formed by two out of three of the monomers described
hereinabove, a hydrogen sulfite adduct (which is an impurity
derived from the carboxyl group-containing monomer which remains
unpolymerized although the above hydrogen sulfite and/or the
compound capable of producing a hydrogen sulfite as a chain
transfer agent is added thereto), and the like. It is preferred
that the copolymer composition so formed contains little or no
unreacted monomers or homopolymers.
Cleaning Compositions
[0111] The present invention provides a cleaning composition,
preferably a laundry detergent composition and more preferably a
liquid laundry detergent composition, that contains the alkoxylated
polyalkyleneimine(s) and the sulfonate group-containing copolymer
as described hereinabove and optionally other adjunct
ingredients.
[0112] The cleaning composition of the present invention can be in
any solid or liquid product form, and it can be a laundry detergent
composition, a hard surface cleaning composition, a hand
dishwashing composition, and an automatic dishwashing composition.
The cleaning composition is preferably a liquid, and even more
preferably it is in a single phase or multiphase unit dose form,
i.e., the liquid cleaning composition is contained in a single
compartment or multi-compartment water-soluble pouch. In a specific
embodiment, the cleaning composition is in a single phase or
multiphase unit dose form containing either a liquid automatic
dishwashing composition or a liquid laundry detergent composition
encapsulated in a single compartment or multi-compartment
water-soluble pouch, which is formed, for example, by a
water-soluble polymer such as polyvinvyl alcohol (PVA) and/or
polyvinylpyrrolidone (PVP).
[0113] When the cleaning composition is in the form of a liquid
laundry detergent composition, it may further comprise one or more
organic solvents, which can be present in an amount ranging from
about 1 wt % to about 80 wt %, preferably from about 10 wt % to
about 60 wt %, more preferably from about 15 wt % to about 50 wt %,
and most preferably from about 20 wt % to about 45 wt %, by total
weight of the composition.
[0114] Because phase separation is a constant challenge for liquid
laundry detergent compositions, especially when the salt content in
such compositions is high, the solvent system of the present
invention is particularly designed to stabilize the alkoxylated
polyalkyleneimine(s) and the sulfonate group-containing copolymer
of the present invention and minimize the risk of phase separation.
Specifically, the solvent system of the present invention is
composed mostly of diols, such as ethylene glycol, diethylene
glycol, propylene glycol, dipropylene glycol, butylene glycol,
pentanediols, and combinations thereof. The diols are present in
the liquid laundry detergent composition of the present invention
in a total amount ranging from about 2 wt % to about 50 wt %.
Preferably, the composition contains ethylene, diethylene glycol,
and/or propylene glycol in a total amount ranging from about 5 wt %
to about 40 wt %. More preferably, the composition contains
propylene glycol in the amount ranging from about 15 wt % to about
35 wt %. Other organic solvents may also be present, which include,
but are not limited to: methanol, ethanol, glycerin, sodium cumene
sulfonate, potassium cumene sulfonate, ammonium cumene sulfonate,
sodium toluene sulfonate, potassium toluene sulfonate, sodium
xylene sulfonate, potassium xylene sulfonate, ammonium xylene
sulfonate, or mixtures thereof. Other lower alcohols, such
C.sub.1-C.sub.4 alkanolamines, e.g., monoethanolamine and/or
triethanolamine, may also be used. In a particularly preferred
embodiment of the present invention, the liquid laundry detergent
compositions of the present invention also contain from about 5 wt
% to about 20 wt %, preferably from 6 wt % to 18 wt %, more
preferably from 8 wt % to 16 wt % of glycerin in addition to the
diol(s).
[0115] The liquid laundry detergent composition of the present
invention preferably contains water in combination with the
above-mentioned organic solvent(s) as carrier(s). In some
embodiments, water is present in the liquid laundry detergent
compositions of the present invention in the amount ranging from
about 20 wt % to about 70 wt %, preferably from about 25 wt % to 60
wt %, and more preferably from about 30 wt % to about 50 wt %. In
other embodiments, water is absent and the composition is
anhydrous. Highly preferred compositions afforded by the present
invention are clear, isotropic liquids.
[0116] The cleaning composition of the present invention contains
one or more surfactants, which may be present in amounts ranging
from about 1% to about 80%, more preferably from about 1% to about
50%, and more preferably from about 5% to about 30% by total weight
of the compositions. The specific forms of the surfactants and the
adjunct cleaning additives are not particularly limited, and are
appropriately selected based on common knowledge in the field of
detergents. For example, the surfactants are selected from the
group consisting of anionic surfactants, cationic surfactants,
nonionic surfactants, amphoteric surfactants, zwitterionic
surfactants, and mixtures thereof.
[0117] Anionic surfactants are preferred. Useful anionic
surfactants can themselves be of several different types. For
example, non-soap synthetic anionic surfactants are particularly
suitable for use herein, which 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 (included in the term "alkyl" is the alkyl portion of
acyl groups) containing from about 10 to about 20 carbon atoms and
a sulfonic acid or sulfuric acid ester group. Examples of this
group of synthetic anionic surfactants include, but are not limited
to: a) the sodium, potassium and ammonium alkyl sulfates with
either linear or branched carbon chains, especially those obtained
by sulfating the higher alcohols (C.sub.10-C.sub.20 carbon atoms),
such as those produced by reducing the glycerides of tallow or
coconut oil; b) the sodium, potassium and ammonium alkylethoxy
sulfates with either linear or branched carbon chains, particularly
those in which the alkyl group contains from about 10 to about 20,
preferably from about 12 to about 18 carbon atoms, and wherein the
ethoxylated chain has, in average, a degree of ethoxylation ranging
from about 0.1 to about 5, preferably from about 0.3 to about 4,
and more preferably from about 0.5 to about 3; c) the sodium and
potassium alkyl benzene sulfonates in which the alkyl group
contains from about 10 to about 20 carbon atoms in either a linear
or a branched carbon chain configuration, preferably a linear
carbon chain configuration; d) the sodium, potassium and ammonium
alkyl sulphonates in which the alkyl group contains from about 10
to about 20 carbon atoms in either a linear or a branched
configuration; e) the sodium, potassium and ammonium alkyl
phosphates or phosphonates in which the alkyl group contains from
about 10 to about 20 carbon atoms in either a linear or a branched
configuration, f) the sodium, potassium and ammonium alkyl
carboxylates in which the alkyl group contains from about 10 to
about 20 carbon atoms in either a linear or a branched
configuration, and combinations thereof; g) the sodium, potassium
and ammonium alkyl ester sulfonates, for example of formula
R--CH(SO.sub.3M)-CH.sub.2COOR', or the sodium, potassium and
ammonium alkyl ester sulfates, for example of formula
R--CH(OSO.sub.3M)-CH.sub.2COOR', where R represents a
C.sub.10-C.sub.20 and preferably C.sub.10-C.sub.16 linear or
branched alkyl radical, R' represents a C.sub.1-C.sub.6 and
preferably C.sub.1-C.sub.3 alkyl radical, and M represents a
sodium, potassium or the ammonium cation. The anionic surfactants
can be provided in the cleaning compositions of the present
invention at levels ranging from about 1% to about 80%, more
preferably from about 1% to about 50%, more preferably from about
5% to about 30%, and most preferably from 10% to 25%, by total
weight of the compositions.
[0118] In one particularly preferred embodiment, the cleaning
composition of the present invention is a liquid laundry or dish
detergent composition containing from about 1 wt % to about 50 wt %
of one or more anionic surfactants selected from the group
consisting of C.sub.10-C.sub.20 linear alkyl benzene sulphonates,
C.sub.10-C.sub.20 linear or branched alkylethoxy sulfates having an
average degree of ethoxylation ranging from 1 to 5,
C.sub.10-C.sub.20 linear or branched alkyl sulfates,
C.sub.10-C.sub.20 linear or branched alkyl ester sulfates,
C.sub.10-C.sub.20 linear or branched alkyl sulphonates,
C.sub.10-C.sub.20 linear or branched alkyl ester sulphonates,
C.sub.10-C.sub.20 linear or branched alkyl phosphates,
C.sub.10-C.sub.20 linear or branched alkyl phosphonates,
C.sub.10-C.sub.20 linear or branched alkyl carboxylates, and
combinations thereof. More preferably, said one or more anionic
surfactants are selected from the group consisting of
C.sub.10-C.sub.20 linear alkyl benzene sulphonates,
C.sub.10-C.sub.20 linear or branched alkylethoxy sulfates having an
average degree of ethoxylation ranging from about 1 to about 5,
methyl ester sulfonates with a C.sub.10-C.sub.20 linear or branched
alkyl group, and mixtures thereof, and are present in an amount
ranging from about 5 wt % to about 30 wt % of the liquid laundry or
dish detergent composition.
[0119] Water-soluble salts of the higher fatty acids, i.e.,
"soaps", are also useful anionic surfactants in the cleaning
compositions of the present invention. 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. However, the cleaning compositions of the
present invention preferably contains soaps at a relatively low
level, e.g., no more than about 3 wt %, more preferably not more
than about 2 wt % or 1 wt %, and most preferably said cleaning
composition is essentially free of soaps.
[0120] Nonionic surfactants can also be included into the
surfactant systems of the present invention, which include those of
the formula R.sub.1(OC.sub.2H.sub.4).sub.nOH, wherein R.sup.1 is a
C.sub.8-C.sub.18 alkyl group or alkyl phenyl group, and n is from
about 1 to about 80. Particularly preferred are C.sub.8-C.sub.18
alkyl alkoxylated alcohols having an average degree of alkoxylation
from about 1 to about 20. The nonionic surfactants can be provided
in the cleaning compositions at levels ranging from about 0.05 wt %
to about 20 wt %, preferably from about 0.1 wt % to about 10 wt %,
and most preferably from about 1 wt % to about 5 wt %. However, in
certain preferred embodiments of the present invention, the
cleaning compositions contains nonionic surfactants at a relatively
low level, e.g., no more than about 3 wt %, more preferably not
more than about 2 wt % or 1 wt %, and most preferably said cleaning
composition is essentially free of nonionic surfactants.
[0121] Other surfactants useful herein include amphoteric
surfactants, zwitterionic surfactants and cationic surfactants.
Such surfactants are well known for use in laundry or dish
detergents and are typically present at levels from about 0.2 wt %,
0.5 wt % or 1 wt % to about 10 wt %, 20 wt % or 30 wt %.
[0122] In a preferred but not necessary embodiment of the present
invention, the cleaning composition is a liquid dish detergent
composition containing from about 0.5 wt % to about 20 wt % of one
or more amphoteric and/or zwitterionic surfactants.
[0123] Preferred amphoteric surfactants are selected from the group
consisting of amine oxide surfactants, such as, for example, alkyl
dimethyl amine oxide or alkyl amido propyl dimethyl amine oxide,
more preferably alkyl dimethyl amine oxide and especially coco
dimethyl amino oxide. Amine oxide may have a linear or mid-branched
alkyl moiety. Typical linear amine oxides are characterized by a
formula R.sub.1--N(R.sub.2)(R.sub.3)--O, wherein R.sub.1 is a
C.sub.8-18 alkyl, and wherein R.sub.2 and R.sub.3 are independently
selected from the group consisting of C.sub.1-3 alkyls and
C.sub.1-3 hydroxyalkyls, such as methyl, ethyl, propyl, isopropyl,
2-hydroxethyl, 2-hydroxypropyl and 3-hydroxypropyl. As used herein
"mid-branched" means that the amine oxide has one alkyl moiety
having n1 carbon atoms with one alkyl branch on the alkyl moiety
having n2 carbon atoms. The alkyl branch is located on the .alpha.
carbon from the nitrogen on the alkyl moiety. This type of
branching for the amine oxide is also known in the art as an
internal amine oxide. The total sum of n1 and n2 is from about 10
to about 24 carbon atoms, preferably from about 12 to about 20, and
more preferably from about 10 to about 16. The number of carbon
atoms for the one alkyl moiety (n1) should be approximately the
same number of carbon atoms as the one alkyl branch (n2) such that
the one alkyl moiety and the one alkyl branch are symmetric. As
used herein "symmetric" means that |n1-n2| is less than or equal to
5, preferably 4, most preferably from 0 to 4 carbon atoms in at
least about 50 wt %, more preferably at least about 75 wt % to
about 100 wt %, of the mid-branched amine oxides for use herein.
Particularly preferred amphoteric surfactants are C.sub.10-C.sub.14
alkyl dimethyl amine oxides.
[0124] Preferred zwitterionic surfactants are betaine surfactants,
such as, for example, alkyl betaines, alkylamidobetaines,
amidazoliniumbetaines, sulfobetaines (also referred to as
sultaines) as well as phosphobetaines. A particularly preferred
betaine is cocoamidopropylbetaine.
[0125] The liquid detergent composition as described herein above
may also contain an external structurant, which may be present in
an amount ranging from about 0.001% to about 1.0%, preferably from
about 0.05% to about 0.5%, more preferably from about 0.1% to about
0.3% by total weight of the composition. Suitable external
structurants include those described, for example, in US2007/169741
and US2005/0203213. A particularly preferred external structurant
for the practice of the present invention is hydrogenated castor
oil, which is also referred to as trihydroxylstearin and is
commercially available under the tradename Thixin.RTM..
[0126] In yet another preferred embodiment of the present
invention, the liquid detergent composition further contains from
about 0.1 wt % to about 5 wt %, preferably from about 0.5 wt % to
about 3 wt %, more preferably from about 1 wt % to about 1.5 wt %,
of one or more fatty acids and/or alkali salts thereof. Suitable
fatty acids and/or salts that can be used in the present invention
include C.sub.10-C.sub.22 fatty acids or alkali salts thereof. Such
alkali salts include monovalent or divalent alkali metal salts like
sodium, potassium, lithium and/or magnesium salts as well as the
ammonium and/or alkylammonium salts of fatty acids, preferably the
sodium salt.
[0127] The balance of the cleaning composition of the present
invention typically contains from about 5 wt % to about 70 wt %, or
about 10 wt % to about 60 wt % adjunct ingredients.
[0128] Suitable adjunct ingredients for laundry detergent products
include: builders, chelating agents, dye transfer inhibiting
agents, dispersants, rheology modifiers, enzymes, and enzyme
stabilizers, catalytic materials, bleach activators, hydrogen
peroxide, sources of hydrogen peroxide, preformed peracids,
polymeric dispersing agents, clay soil removal/anti-redeposition
agents, brighteners, suds suppressors, dyes, photobleaches,
structure elasticizing agents, fabric softeners, carriers,
hydrotropes, processing aids, solvents, hueing agents,
anti-microbial agents, free perfume oils, and/or pigments. In
addition to the disclosure below, suitable examples of such other
adjunct ingredients and levels of use are found in U.S. Pat. Nos.
5,576,282, 6,306,812, and 6,326,348. The precise nature of these
adjunct ingredients and the levels thereof in the liquid laundry
detergent composition will depend on factors like the specific type
of the composition and the nature of the cleaning operation for
which it is to be used.
[0129] Suitable adjunct ingredients for dish detergent products
include: builders, chelants, conditioning polymers, cleaning
polymers, surface modifying polymers, soil flocculating polymers,
structurants, emmolients, humectants, skin rejuvenating actives,
enzymes, carboxylic acids, scrubbing particles, bleach and bleach
activators, perfumes, malodor control agents, pigments, dyes,
opacifiers, beads, pearlescent particles, microcapsules, organic
and inorganic cations such as alkaline earth metals such as
Ca/Mg-ions and diamines, antibacterial agents, preservatives and pH
adjusters and buffering means.
[0130] If the cleaning composition of the present invention is
provided in a powder form, it may also be especially preferred for
the powder to comprise low levels, or even be essentially free, of
builder. The term "essentially free" means that the composition
"comprises no deliberately added" amount of that ingredient. In a
preferred embodiment, the cleaning composition of the present
invention comprises no builder.
Processes of Making Cleaning Compositions
[0131] The cleaning compositions of the present invention can be
formulated into any suitable form and prepared by any process
chosen by the formulator. Such process typically involves mixing
the essential and optional ingredients in any desired order to a
relatively uniform state, with or without heating, cooling,
application of vacuum, and the like, thereby providing cleaning
compositions containing ingredients in the requisite
concentrations.
[0132] In one embodiment, the cleaning composition herein is a
liquid composition contained within a water-soluble film thereby
forming a water-soluble pouch. The pouch may be of such a size that
it conveniently contains either a unit dose amount of the
composition herein, suitable for the required operation, for
example one wash, or only a partial dose, to allow a user greater
flexibility to vary the amount used, e.g., depending on the size or
degree of soiling of the wash load.
[0133] The water-soluble film of the pouch preferably comprises a
polymer. The film can be obtained from methods known in the art,
e.g., by casting, blow molding, extrusion molding, injection
molding of the polymer. Non-limiting examples of the polymer for
making the water-soluble film include: polyvinyl alcohols (PVAs),
polyvinyl pyrrolidone, polyalkylene oxides, (modified) cellulose,
(modified) cellulose-ethers or -esters or -amides, polycarboxylic
acids and salts including polyacrylates, copolymers of
maleic/acrylic acids, polyaminoacids or peptides, polyamides
including polyacrylamide, polysaccharides including starch and
gelatine, natural gums such as xanthum and carragum. Preferably,
the water-soluble film comprises a polymer selected from the group
consisting of polyacrylates and water-soluble acrylate copolymers,
methylcellulose, carboxymethylcellulose sodium, dextrin,
ethylcellulose, hydroxyethyl cellulose, hydroxypropyl
methylcellulose, maltodextrin, polymethacrylates, polyvinyl
alcohols, hydroxypropyl methyl cellulose (HPMC), and a combination
thereof. Most preferably, the water-soluble film comprises
polyvinyl alcohol, e.g., M8639 available from MonoSol.
[0134] The pouch herein may comprise a single compartment or
multiple compartments, preferably comprise multiple compartments,
e.g., two compartments or three compartments. In the
multi-compartment execution, one or more of the multiple
compartments comprise the aforementioned anti-microbial laundry
detergent composition. Preferably, the pouch comprises multiple
films which form the multiple compartments, i.e., the inner volume
of the multiple films is divided into the multiple compartments.
The pouch of the present invention can be made by any suitable
processes known in the art.
Methods of Using Cleaning Compositions
[0135] The present invention includes methods of using the cleaning
compositions described hereinabove for cleaning soiled material. As
will be appreciated by one skilled in the art, the cleaning
compositions of the present invention are suited for use in laundry
pretreatment applications, laundry cleaning applications, and home
care applications.
[0136] Such methods include, but are not limited to, the steps of
contacting the cleaning compositions in neat form or diluted in
wash liquor, with at least a portion of a soiled material and then
optionally rinsing the soiled material. The soiled material may be
subjected to a washing step prior to the optional rinsing step.
[0137] For use in laundry pretreatment applications, the method may
include contacting the detergent or cleaning compositions described
herein with soiled fabric. Following pretreatment, the soiled
fabric may be laundered in a washing machine or otherwise
rinsed.
[0138] Machine laundry methods may comprise treating soiled laundry
with an aqueous wash solution in a washing machine having dissolved
or dispensed therein an effective amount of a machine laundry
cleaning composition in accord with the invention. An "effective
amount" of the cleaning composition means from about 20 g to about
300 g of product dissolved or dispersed in a wash solution of
volume from about 5 L to about 65 L. The water temperatures may
range from about 5.degree. C. to about 100.degree. C. The water to
soiled material (e.g., fabric) ratio may be from about 1:1 to about
30:1. The compositions may be employed at concentrations of from
about 500 ppm to about 15,000 ppm in solution. In the context of a
fabric laundry composition, usage levels may also vary depending
not only on the type and severity of the soils and stains, but also
on the wash water temperature, the volume of wash water, and the
type of washing machine (e.g., top-loading, front-loading,
top-loading, vertical-axis Japanese-type automatic washing
machine).
[0139] The cleaning compositions herein may be used for laundering
of fabrics at reduced wash temperatures. These methods of
laundering fabric comprise the steps of delivering a laundry
detergent composition to water to form a wash liquor and adding a
laundering fabric to said wash liquor, wherein the wash liquor has
a temperature of from about 0.degree. C. to about 20.degree. C., or
from about 0.degree. C. to about 15.degree. C., or from about
0.degree. C. to about 9.degree. C. The fabric may be contacted to
the water prior to, or after, or simultaneous with, contacting the
laundry detergent composition with water.
[0140] Another method includes contacting a nonwoven substrate
impregnated with an embodiment of the detergent or cleaning
composition with soiled material. As used herein, "nonwoven
substrate" can comprise any conventionally fashioned nonwoven sheet
or web having suitable basis weight, caliper (thickness),
absorbency, and strength characteristics. Non-limiting examples of
suitable commercially available nonwoven substrates include those
marketed under the tradenames SONTARA.RTM. by DuPont and
POLYWEB.RTM. by James River Corp.
[0141] Hand washing/soak methods, and combined handwashing with
semi-automatic washing machines, are also included.
Test Methods
[0142] Various techniques are known in the art to determine the
properties of the cleaning compositions of the present invention
comprising the alkoxylated polyalkyleneimines and the sulfonate
group-containing copolymers. However, the following assays
disclosed in this section are used to determine the respective
values of the parameters of the present invention.
[0143] Test 1: Measurement of Weight Average Molecular Weight
(Mw)
[0144] The weight average molecular weight of the sulfonate
group-containing copolymers (MW.sub.S) are determined by the
technique of Gel Permeation Chromatography (GPC) under the
following conditions. [0145] Measuring device: L-7000 series
(product of Hitachi Ltd.) [0146] Detector: RI (weight average
molecular weight), UV (residual monomer) [0147] Column: SHODEX
Asahipak GF-310-HQ, GF-710-HQ, GF-1G 7B (products of Showa Denko K.
K.) [0148] Column temperature: 40.degree. C. [0149] Flow velocity:
0.5 mL/min [0150] Calibration curve: Polyacrylic Standard (product
of Sowa Kagaku Co., Ltd.) [0151] Eluent: 0.1 N sodium
acetate/acetonitrile=3/1 (mass ratio)
[0152] Test 2: Measurement of Solids Content
[0153] A mixture of 1.0 g of a sulfonate group-containing polymer
composition of the present invention and 1.0 g of water is left in
an oven heated to 130.degree. C. in nitrogen atmosphere for one
hour so as to be dried. The solids content (%) and volatile
component content (%) are calculated from the weight difference
before and after the drying step.
[0154] Test 3: Whiteness Maintenance Assay
[0155] This test is intended to measure the ability of the laundry
detergent to prevent loss in whiteness (i.e., whiteness
maintenance) of fabrics. Whiteness maintenance of fabrics is
evaluated by image analysis after single or multi-cycle washes.
Typically, "whiteness" can be reported by its whiteness index,
which is conveniently converted from CIELAB (an internationally
recognized color scale system developed by CIE ("Commission
Internationale de I'Eclairage")). CIE color scale for whiteness is
the most commonly used whiteness index and refers to measurements
made under D65 illumination, which is the standard representation
of outdoor daylight. In technical terms, whiteness is a single
number index referencing the relative degree of whiteness (of
near-white materials under specific lighting conditions), and the
higher the number, the whiter the material. As an example, for a
perfect reflecting, non-fluorescent white material, the CIE
whiteness index (L*) would be 100.
[0156] The steps for assaying whiteness maintenance of sample
laundry detergents are as follows: [0157] (1) Dissolve 2.25 g of
raw materials of a base laundry detergent in 300 g of
triple-filtered (0.1 micron Millipore membrane filter is used with
a vacuum Buchner filtering apparatus) deionized water according to
the concentrations as provided in Table 1 herein to form a
1.5.times. concentrated base wash solution.
TABLE-US-00001 [0157] TABLE 1 FORMULATION OF CONCENTRATED BASE WASH
SOLUTION (1.5X) Raw Materials Amount (wt %) Water 76.21% NaOH (for
adjusting pH to 7.5%) 3.23% Propylene glycol 2.50% Citric Acid
1.70% Alkylethoxy sulfates with a weight average degree 9.84% of
ethoxylation of about 3 (AE3S) Linear alkyl benzene sulphonic acid
(HLAS) 6.52% Total 100.00%
[0158] (2) Transfer 10 ml of the prepared 1.5.times. concentrated
base wash solution into a 40 ml glass vial. [0159] (3) The 10 ml
wash solution is then mixed with 900 ul of a polymer solution that
contains 1% of the polymer blend according to the present invention
(i.e., containing an alkoxylated polyalkyleneimine and a sulfonate
group-containing copolymer at 1:1 ratio), or 1% of a comparative
polymer alone (i.e., either the alkoxylated polyalkyleneimine alone
or the sulfonate group-containing copolymer alone). [0160] (4) Add
Teflon-coated magnets into the 40 ml glass vial to provide
additional agitation. [0161] (5) Add 2.1 ml of deionized (DI) water
into the 40 ml glass vial. [0162] (6) Add 1 ml of a 225 gpg stock
hard water solution to the 40 ml glass vial. The 225 gpg stock hard
water solution is prepared by the following steps: (i) into a 1000
ml beaker, 4.24 g of CaCl.sub.2.2H.sub.2O and 1.96 g of
MgCl.sub.2.6H.sub.2O are added; (ii) add 993.8 ml of de-ionized
water; (iii) use a stirring bar and stirring plate to stir the
mixture until it is fully dissolved and the solution turns clear;
(iv) pour the solution into a 1 L volumetric flask and fill it to
the 1 L line; (v) add a stirring bar into the volumetric flask and
stir again for about 5 minutes; (vi) remove the stirring bar and
refill the volumetric flask with de-ionized water up to the 1 L
line; (vii) the resulting 225 gpg stock hard water solution is
stored in a plastic bottle for future use. [0163] (7) Add 1 ml of a
75% Arizona Dust clay solution into the solution in the 40 mL glass
vial to form a test solution having a total volume of about 15 ml.
Accordingly, the clay concentration in the test solution is about 5
wt %. The Arizona Dust clay solution is made by the following
steps: (i) add 7.5 g of Arizona Dust clay into a 100 ml beaker and
then add 92.5 g of de-ionized water thereinto; (ii) use a stirring
bar and a stirring plate to stir the mixture for at least 30 mins
until the clay is dissolved. [0164] (8) Fabrics used for conducting
this test are selected from 1.5 cm-diameter polyester fabrics
(PW19) and 1.5 cm-diameter cotton fabrics (CW98) purchased from
Empirical Manufacturing Company (Blue Ash, Cincinnati). Eight (8)
of the polyester fabrics or the cotton fabrics are added into the
test solution in the 40 mL glass vial to perform the whiteness test
via a fast wash cycle. [0165] (9) The 40 ml glass vial containing
the test solution and the test fabrics (either the PW19 polyester
fabrics or the CW98 cotton fabrics) are secured tightly to one
shaking arm of a Wrist Action Shaker Model 75 (Burrell Scientific,
Pittsburgh, Pa.) and shaken for about 20 minutes to mimic a wash
cycle. [0166] (10) At the end of the wash, the liquid contents of
the 40 ml glass vial are emptied through a Buchner funnel. [0167]
(11) The test fabrics remaining inside the 40 ml glass vial are
then transferred to another 40 ml glass vial, into which 15 mL of a
rinse solution is added. The rinse solution is prepared by adding 1
ml of the 225 gpg stock hard water solution as described
hereinabove in Step (6) into 14.00 ml of de-ionized filtered water.
[0168] (12) The 40 ml glass vial containing the rinse solution and
the test fabrics are secured tightly to one shaking arm of the
Wrist Action Shaker and shaken for about 3 minutes to mimic a rinse
cycle. [0169] (13) At the end of the rinse, the 40 ml glass vial is
removed from the Wrist Action Shaker, and the test fabrics are
taken out of the glass vial and placed on a black plastic board
template to air dry over night. [0170] (14) Two whiteness
measurements are carried out for each test fabric using the CIELab
color parameters with a Datacolor spectrometer, which include a
first whiteness measurement before the wash and rinse cycle (i.e.,
initial) and a second whiteness measurement after the wash and
rinse cycle (i.e., treated). [0171] (15) The difference between the
average whiteness measurement of the initial fabrics and that of
the treated fabrics is reported as delta W (i.e., .DELTA.W), which
is calculated for each test solution as follows:
[0171] .DELTA.W=Average Whiteness of Treated Fabrics-Average
Whiteness of Initial Fabrics, Typically, .DELTA.W is a negative
value, which is reflective of whiteness loss suffered by fabrics
after washing. [0172] (16) A Whiteness Index (.DELTA.WI) is
calculated for each polymer or polymer blend tested as
followes:
[0172] .DELTA.WI=.DELTA.W.sub.PT-.DELTA.W.sub.PR [0173] wherein:
[0174] .DELTA.W.sub.PT=.DELTA.W of the test solution containing the
test polymer or polymer blend; [0175] .DELTA.W.sub.PR=.DELTA.W of
the base wash solution nil polymer (i.e., reference);
.DELTA.W.sub.PT and .DELTA.W.sub.PR are typically measured in the
same test setting. Specifically, the test solution containing the
test polymer or polymer blend and the reference solution (i.e., the
base wash solution nil polymer) are added into different glass
vials, which are then placed on different but adjacent shaking arms
on the Wrist Action Shaker and shaken simultaneously to mimic the
wash and rinse cycles. [0176] (17) The Whiteness Index (.DELTA.WI)
of a test polymer or polymer blend represents the polymer or
polymer blend's relative effectiveness in preventing whiteness loss
of a fabric caused by washing, in comparison with that of the
reference solution (i.e., the base wash solution nil polymer). A
positive .DELTA.WI value indicates that the test polymer or polymer
blend is more effective in reducing or preventing fabric whiteness
loss than the reference solution. A negative .DELTA.WI value
indicates that the test polymer or polymer blend is less effective
than the reference solution. The higher the .DELTA.WI value, the
more effective is the test polymer or polymer blend.
EXAMPLES
[0177] Hereinafter, the present invention is described in more
detail based on examples. All percentages are by weight unless
otherwise specified.
A. Exemplary Alkoxylated Polyalkyleneimines
[0178] Following is a list of exemplary alkoxylated
polyalkyleneimines that can be used for practicing the present
invention:
TABLE-US-00002 TABLE 2 MW.sub.PEI EO # PO # Formula (Daltons) (b)
(c) PEI Polymer 1 (PEI).sub.5000(EO).sub.7 5000 7 0 PEI Polymer 2
(PEI).sub.5000(EO).sub.9.9 (PO).sub.3.5 5000 9.9 3.5 PEI Polymer 3
(PEI).sub.5000(EO).sub.9.9 (PO).sub.15.5 5000 9.9 15.5 PEI Polymer
4 (PEI).sub.600(EO).sub.10 (PO).sub.7 600 10 7 PEI Polymer 5
(PEI).sub.5000(EO).sub.10 (PO).sub.7 5000 10 7 PEI Polymer 6
(PEI).sub.600(EO).sub.20 600 20 0 PEI Polymer 7
(PEI).sub.1600(EO).sub.20 1600 20 0 PEI Polymer 8
(PEI).sub.600(EO).sub.24 (PO).sub.16 600 24 16 PEI Polymer 9
(PEI).sub.600(EO).sub.24 (PO).sub.24 600 24 24 PEI Polymer 10
(PEI).sub.600(EO).sub.30(PO).sub.5 600 30 5
B. Exemplary Sulfonate Group-Containing Copolymers
[0179] Following is a list of exemplary sulfonate group-containing
copolymers ("S Copolymers") that can be used for practicing the
present invention:
TABLE-US-00003 TABLE 3 Proportion of Structural IPN/ Units (% by
mass) HAPS MW.sub.s HAPS.sup.1 IPN.sup.2 AA.sup.3 (P) (Dalton) P
.times. MW.sub.s P .times. MW.sub.s .times. n S Copolymer 1 10 40
(n = 10) 50 4.0 27,000 108,000 1,080,000 S Copolymer 2 12 34 (n =
25) 54 2.8 32,000 90,667 2,266,000 S Copolymer 3 11 40 (n = 50) 49
3.6 42,000 153,000 7,640,000 S Copolymer 4 9 40 (n = 50) 51 4.4
72,000 320,000 16,000,000 S Copolymer 5 13 64 (n = 50) 23 4.9
44,000 217,000 10,800,000 S Copolymer 6 5 49 (n = 50) 46 9.8 68,000
666,000 33,300,000 S Copolymer 7 27 35 (n = 50) 38 1.3 15,000
19,400 972,000 S Copolymer 8 16 34 (n = 50) 50 2.1 12,000 25,500
1,280,000 S Copolymer 9 12 40 (n = 50) 48 3.3 25,000 83,333
4,166,000 S Copolymer 10 11 34 (n = 50) 55 3.1 57,000 176,182
8,809,000 S Copolymer 11 15 42 (n = 50) 44 2.8 70,000 196,000
9,800,000 .sup.1HAPS stands for sodium
3-allyloxy-2-hydroxypropanesulfonate. .sup.2IPN stands for an
isoprenol-ethylene oxide adduct, wherein the number "n" defines the
avearge number of repeating EO units in such adduct. .sup.3AA
stands for acrylic acid.
C. Improved Whiteness Maintenance Performance Achieved by Inventive
Polymer Blend
[0180] Whiteness maintenance performance of an inventive polymer
blend containing a PEI polymer and a sulfonate group-containing
polymer according to the present invention is compared with that of
a PEI polymer alone and with that of a sulfonate group-containing
polymer alone. Specifically, the Whiteness Index (.DELTA.WI) of the
inventive polymer blend, the PEI polymer alone, and the sulfonate
group-containing polymer alone, and are measured by using the
Whiteness Maintenance Assay as described hereinabove in Test 3, and
the corresponding results are tabulated hereinafter in Table 4.
TABLE-US-00004 TABLE 4 .DELTA.WI (PW19) .DELTA.WI (CW98) S
Copolymer 4 alone 18.21 22.77 PEI Polymer 6 alone 18.08 21.49 S
Copolymer 4 + PEI Polymer 6 20.45 28.32 (1:1 Ratio) S Copolymer 4
alone 18.21 22.77 PEI Polymer 8 alone 23.18 26.71 S Copolymer 4 +
PEI Polymer 8 25.14 30.81 (1:1 Ratio)
[0181] The whiteness maintenance assay test results hereinabove
clearly demonstrate that an inventive polymer blend according to
the present invention exhibits superior whiteness maintenance
performance over that of either a PEI polymer or a sulfonate
group-containing copolymer alone, when all are used at the same
total polymer concentration, which is both surprising and
unexpected.
D. Exemplary Cleaning Compositions
[0182] (1). Exemplary Liquid Laundry Detergent Compositions
[0183] The following liquid laundry detergent compositions are
prepared by traditional means known to those of ordinary skill in
the art by mixing the following ingredients.
TABLE-US-00005 TABLE 5 Ingredients (wt %) 1A 1B 1C AES.sup.1 17 2
11 LAS.sup.2 2.8 15 10 AE.sup.3 2.3 2.37 3.44 Citric Acid 5 1.98 --
Boric Acid -- 1 3 Amine Oxide 1.2 -- 0.5 Trimethyl Lauryl Ammonium
-- 1.5 -- Chloride PEI Polymer 1-10 of Example A 0.1~3.5 1 2 S
Copolymer 1-11 of Example B 0.1~3.5 1 2 Fatty Acids 1.2 1.2 1.2
Protease (54.5 mg/g).sup.4 7.62 7.98 2.08 Amylase (29.26
mg/g).sup.5 2.54 2.67 0.69 Xyloglucanase.sup.6 -- -- 0.15 Borax
4.72 4.94 -- Calcium Formate 0.15 0.16 0.16 Amphiphilic polymer
.sup.7 -- 1.5 4.36 Hexamethylene diamine, -- -- 1.68 ethoxylated,
quaternized, sulfated.sup.8 DTPA .sup.9 (50% active) 0.28 0.3 0.64
Tiron .RTM. 0.84 0.89 -- Optical Brightener.sup.10 0.34 0.37 0.36
Ethanol 0.97 4.1 2.99 Propylene Glycol 4.9 5.16 8.49 Diethylene
Glycol -- -- 4.11 Monoethanolamine (MEA) 1.12 1.17 0.23 Caustic
Soda (NaOH) 3.5 3.74 2.1 Na Formate 0.61 0.64 0.23 Na Cumene
Sulfonate -- -- 1 Suds Suppressor -- -- 0.18 Dye 0.01 -- 0.02
Perfume 0.85 -- 1 Preservative.sup.11 0.05 0.5 -- Hydrogenated
castor oil -- -- 0.27 Water Q.S. Q.S. Q.S. .sup.1AES can be
AE.sub.1.5S, AE.sub.2S, and/or AE.sub.3S, in the amount ranging
from 0-20%. .sup.2LAS can be provided in the amount ranging from
0-20%. .sup.3AE is a C12-14 alcohol ethoxylate, with an average
degree of ethoxylation of 7-9, supplied by Huntsman, Salt Lake
City, Utah, USA. It can be provided in the amount ranging from
0-10%. .sup.4Proteases may be supplied by Genencor International,
Palo Alto, California, USA (e.g., Purafect Prime .RTM., Excellase
.RTM.) or by Novozymes, Bagsvaerd, Denmark (e.g. Liquanase .RTM.,
Coronase .RTM.). .sup.5Available from Novozymes, Bagsvaerd, Denmark
(e.g., Natalase .RTM., Mannaway .RTM.). .sup.6Available from
Novozymes (e.g., Whitezyme .RTM.). .sup.7 Random graft copolymer is
a polyvinyl acetate grafted polyethylene oxide copolymer having a
polyethylene oxide backbone and multiple polyvinyl acetate side
chains. The molecular weight of the polyethylene oxide backbone is
about 6000 and the weight ratio of the polyethylene oxide to
polyvinyl acetate is about 40 to 60 and no more than 1 grafting
point per 50 ethylene oxide units, available from BASF as Sokalan
PG101 .RTM.. .sup.8A compound having the following general
structure:
bis((C.sub.2H.sub.5O)(C.sub.2H.sub.4O).sub.n)(CH.sub.3)--N.sup.+--C.sub.x-
H.sub.2x--N.sup.+--
(CH.sub.3)-bis((C.sub.2H.sub.5O)(C.sub.2H.sub.4O).sub.n), wherein n
= from 20 to 30, and x = from 3 to 8, or sulphated or sulphonated
variants thereof, available from BASF as Lutenzit Z 96 .RTM.
.sup.9DTPA is diethylenetriaminepentaacetic acid supplied by Dow
Chemical, Midland, Michigan, USA. .sup.10Suitable Fluorescent
Whitening Agents are for example, Tinopal .RTM. AMS, Tinopal .RTM.
CBS-X, Sulphonated zinc phthalocyanine Ciba Specialty Chemicals,
Basel, Switzerland. It can be provided in the amount ranging from
0-5%. .sup.11Suitable preservatives include methylisothiazolinone
(MIT) or benzisothiazolinone (BIT), which can be provided in the
amount ranging from 0-1%.
[0184] (2). Exemplary Liquid Detergent Compositions for Use in Unit
Dose (UD) Products
[0185] The following liquid detergent compositions are prepared and
encapsulated in a multi-compartment pouch formed by a polyvinyl
alcohol-film.
TABLE-US-00006 TABLE 6 A B Usage (g) 25.36 24.34 Usage (ml) 23.7
22.43 Wash Volume (L) 64 64 Anionic/Nonionic ratio 1.73 9.9
Ingredients (wt %) Linear C.sub.9-C.sub.15 Alkylbenzene sulfonic
acid 18.25 22.46 HC24/25 AE2/3S 90/10 blend 8.73 15.29 C.sub.12-14
alkyl 9-ethoxylate 15.56 3.82 Citric Acid 0.65 1.55 Fatty acid 6.03
6.27 Chelants 1.16 0.62 PEI Polymers 1-10 of Example A 1~6 3 S
Copolymers 1-11 of Example B 1~6 3 Enzymes 0.11 0.12 Brightener 49
0.18 0.19 Structurant 0.1 0.1 Solvent system* 20.31 17.96 Water
10.31 11.66 Perfume 1.63 1.7 Aesthetics 1.48 1.13 Mono-ethanolamine
or NaOH (or mixture 6.69 9.75 thereof) Other laundry
adjuncts/minors Q.S. Q.S. *May include, but not limited to
propanediol, glycerol, ethanol, dipropyleneglycol,
polyetheyleneglycol, polypropyleneglycol.
[0186] All percentages and ratios are calculated by weight unless
otherwise indicated. All percentages and ratios are calculated
based on the total composition unless otherwise indicated. It
should be understood that every maximum numerical limitation given
throughout this specification includes every lower numerical
limitation, as if such lower numerical limitations were expressly
written herein. Every minimum numerical limitation given throughout
this specification will include every higher numerical limitation,
as if such higher numerical limitations were expressly written
herein. Every numerical range given throughout this specification
will include every narrower numerical range that falls within such
broader numerical range, as if such narrower numerical ranges were
all expressly written herein.
[0187] 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."
[0188] 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.
[0189] 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.
* * * * *