JP2001517730A - Water-soluble dye-complexed polymer as dye transfer inhibitor in laundry detergent and fabric softener compositions - Google Patents

Abstract

This invention relates to dye complexing polymers, and, more particularly, to water soluble poly(vinylpyridine betaines) containing a quaternary nitrogen and a carboxylate salt. The polymers herein have effective dye transfer inhibitor (DTI) properties for use, for example, in laundry detergent and fabric softener compositions.

Description

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to dye-complexed polymers, and more particularly to water-soluble poly (vinylpyridine betaine) containing quaternary nitrogen and carboxylated salts. The polymers herein are, for example, dye transfer inhibitors (DTIs) useful for laundry detergent and fabric softener compositions.
It has the property of

Dye-complexed polymers have been used in laundry detergent and fabric softener compositions. In such applications, when washing a mixture of a colored fabric and a white fabric, some dyes may leach out of the colored fabric under the washing conditions. The extent of bleeding is affected by the structure of the dye, the type of fabric and the pH, temperature and mechanical efficiency of the stirring process. The dye oozing out in the washing liquid can be washed out into the washing liquid without any harm. However, in practice, this fugitive dye tends to redeposit on the same fabric as on other fabrics, resulting in a patchy or ugly appearance of the laundry material. This redeposition of the exuding dye can be suppressed in several ways. One method is to introduce a DTI compound that can complex the escaping dye with a complex and thus wash away those that have suppressed redeposition.

[0003] Polyvinylpyrrolidone (PVP) has been used to suppress dye redeposition when washing colored fabrics under washing conditions because of its dye complexing ability. However, P
The performance of VP as DTI is counteracted by the presence of an anionic surfactant in the washing process.

[0004] Other polymers that have been used as DTI in laundry detergent compositions include:
Polyvinyl pyridine-N-oxide (PVPNO); polyvinyl imidazole (
PVI) and a copolymer of polyvinyl pyridine and polyvinyl imidazole (P
VP-PVI). Prior art in this field is represented by the following patents and publications.

Patent subject matter (1) JP 53-50732 Formulas 3, 6 and (1) are water-insoluble compounds and polymers used in printing ink compositions; (2) PCT / US94 / 06849 PVP, polyamine-N -Oxide, WO 95/03390 Vinylimidazole Dye Inhibiting Composition Polymers are used in laundry detergent compositions; (3) USP 5,460,752 Polyamine-N described for use in laundry detergent compositions. (4) EPA 664335 A1 polysulfoxide polymer; (5) PCT / US93 / 10542 laundry composition comprises polyamine-N-oxo WO 94/11473 sid and brightener and surfactant; (6) PCT / EP93 / 02851 PVP and PVI in laundry compositions WO 94 / (7) PCT / US94 / 11509 poly (4-vinylpyridine-N-WO 95/13354 oxide) (PVPNO) and copolymers of VP and VI are described; (8) EP754748 A1 vinylpyridine (9) EP 0 664 332 A1 polyamine oxide polymer; (10) USP 5,604,197 PVPNO + clay softening; (11) USP 5,458,809 PVPNO; (12) USP 5,466,802 PVPNO and PVP-VI; 13) USP 5,627,151 copolymers of VP and VI; vinylpyridine containing up to 20% vinyl acetate or dimethylaminoethyl methacrylate or dimethylaminopropyl methacrylamide; (14) PCT / US 95/04019 PVPNO, PVP, PVP-P Copolymers of WO 95/27038 I and WO 95/27038 VP with VI; (15) PVPNO with EPA 628624 A1 protease; (16) DE 4224762 A1 VP polymer; (17) J . Polymer Water-insoluble poly (4-vinylpyridyl Sci, 26 , N) compound and polymer no. 113, p. 25-254 (1957) (18) PCT / US93 / 10451 Fabric softener composition containing PVP as DTI (19) USP 2,977,341 Betaine in plastic

A feature of the present invention is to provide a water-soluble poly (vinylpyridine betaine) compound comprising quaternary nitrogen and a carboxyl salt in a laundry detergent and fabric softener composition, the compound comprising: Even in the presence of anionic surfactants, they exhibit exceptionally effective dye transfer inhibition during the washing process.

[0007] The water-soluble poly (vinylpyridine betaine) polymer of the present invention contains quaternary nitrogen and a carboxyl salt. The polymer has the formula:

[0008]

Embedded image Here, m represents the degree of polymerization; X is an anion; R ₁ and R ₂ are independently hydrogen, alkyl or aryl; n is 1-5; and M is a cation.

A preferred embodiment of the present invention is that X is halide; most preferably chloride or bromide; R ₁ and R ₂ are both hydrogen; n is 1; M is an alkali metal; Potassium; and the polymer is quaternized at 25-100%; most preferably at 75-100%.

[0010] Preferred polymers have a weight average molecular weight of about 5,000-1,000,000, preferably 20,000-200,000, where m is about 30-5000, preferably 100-1000. Also useful herein are water-soluble copolymers of polymerizable monomers such as vinylpyrrolidone, vinylimidazole, acrylamide and vinylcaprolactam with the polymers defined above.

A preferred use of the polymers and copolymers is in laundry detergents and fabric softener compositions containing a dye transfer inhibiting amount. Usually, this amount is about 2 to about 2% of the polymer or copolymer.
1000 ppm.

In a preferred embodiment of the present invention, the water-soluble polymer of the present invention is obtained by polymerizing vinyl pyridine under suitable polymerization conditions to form a poly (vinyl pyridine) intermediate and then converting the intermediate polymer to an aqueous polymer. It is made by reacting with sodium chloroacetate in a medium.
The reaction product is a poly (vinyl pyridine betaine) polymer containing quaternary nitrogen and a carboxyl salt.

In the polymerization step, any suitable solvent can be used, such as solution polymerization, precipitation polymerization or emulsion polymerization, for example alcohols such as methanol, ethanol or isopropanol; water; or a mixture of water and alcohol. May be. Reaction temperatures are from about 40 ° to 150 ° C, preferably from 50 ° to 90 ° C, most preferably from about 60 ° to 85 ° C. As the polymerization initiator, a free radical initiator such as a perester, a peroxide, a percarbonate, or a Vazo® type initiator can be used. The polymerization is carried out at a solids level of about 5 to 80%, preferably 20 to 50%.

The preferred polymer * made here is poly (4-vinylpyridine) sodium carboxymethyl betaine chloride having the formula:

Embedded image * Polymer A surfactant system; the composition of the present invention comprises, in addition to the water-soluble poly (vinylpyridine betaine) polymer, a surfactant system, wherein the surfactant is nonionic and / or anionic. And / or cationic and / or amphoteric and / or zwitterionic and / or semipolar surfactants.

[0015] Anionic surfactants can be used in the compositions of the present invention without being affected by the presence of the DTI polymer therein.

Anionic surfactants: Suitable anionic surfactants are alkylalkoxylated sulfate surfactants
Agent, formula RO (A)_mSO₃M water-soluble salts or acids. Where R is C₁₀-C ₂₄ Alkyl component, preferably C₁₂-C₂₀Alkyl or hydroxyal
Kill, more preferably C₁₂-C₁₈Having an alkyl or hydroxyalkyl
Unsubstituted C₁₀-C₂₄An alkyl or hydroxyalkyl group;
Xy or propoxy units, where m is greater than zero, typically between about 0.5 and about
6, more preferably between about 0.5 and about 3, and M is H or
Thion (eg, sodium, potassium, lithium, calcium, magnesium
Etc.), ammonium or substituted-ammonium cations. Alkyl ethoxy
Sulfated sulfates are intended here, as are alkylpropoxylated sulfates.
Is done. Particular examples of substituted-ammonium cations are methyl, dimethyl, trime
Tylammonium cations and quaternary ammonium cations such as tetramethyi
Ammonium and dimethylpiperidinium cations, and ethylamine and die
Derived from alkylamines such as tylamine, triethylamine, and mixtures thereof
And so on. A typical surfactant is C₁₂-C₁₈Alkylpolyet
Xylate (1.0) sulfate (C₁₂-C₁₈E (1.O) M), C₁₂ -C₁₈Alkyl polyethoxylate (2.25) sulfate (C₁₂-C_{1 8} E (2.25) M), C₁₂-C₁₈Alkyl polyethoxylate (3.0)
Sulfate (C₁₂-C₁₈E (3.0) M), and C₁₂-C₁₈Alkyl
Polyethoxylate (4.0) sulfate (C₁₂-C₁₈E (4.0) M)
Where M is conveniently selected from sodium and potassium.

Preferred anionic surfactants used are sulfonic acid alkyl ester surfactants, including linear esters of C ₈ -C ₂₀ carboxylic acids (ie, fatty acids), which are described in “The Journal. of di American oil Kemisutsu Society ", Vol. 52 (1975), it is obtained by sulfonating with gaseous SO ₃ according to pages 323-329. Suitable starting materials include natural fatty substances derived from tallow, coconut oil and the like.

Preferred sulfonic acid alkyl ester surfactants, especially for laundry applications, include sulfonic acid alkyl ester surfactants of the following structural formula:

Embedded image Wherein R ³ is a C ₈ -C ₂₀ hydrocarbyl, preferably alkyl, or a combination thereof, R ⁴ is a C ₁ -C ₆ hydrocarbyl, preferably alkyl, or a combination thereof, and M is a sulfonic acid alkyl ester. It is a cation that forms a water-soluble salt. Suitable salt forming cations include metals such as sodium, potassium, lithium, and substituted or unsubstituted ammonium cations such as monoethanolamine, diethanolamine, triethanolamine. Preferably,
R ³ is C ₁₀ -C ₁₆ alkyl, and R ⁴ is methyl, ethyl, or isopropyl. Particularly preferred are sulfonic acid methyl ester is an alkyl of ^{R 3} is _C 10 _{-C 16.}

[0019] Other suitable anionic surfactants are alkyl sulfate surfactants,
Formula ROSO a ₃ M water-soluble salts or acids of the hydrocarbyl of the formula R is preferably _C 10 _{-C 24,} preferably an alkyl or hydroxyalkyl having an alkyl component of _C 10 _{-C 20,} more preferably _{C 12} - C ₁₈ alkyl or hydroxyalkyl, and M is H or a cation, such as an alkali metal cation (eg, sodium, potassium, lithium), or ammonium or substituted ammonium (eg, methyl, dimethyl, and trimethylammonium cations and ethylamine). Quaternary ammonium cations derived from alkylamines such as, for example, diethylamine, triethylamine, and mixtures thereof. _Typically, alkyl chains lower wash temperatures of C 12 _{-C 16} (e.g., temperatures below about 50 ° C.)
Preferably, C ₁₆ -C ₁₈ alkyl chains are preferred for high wash temperatures (eg, temperatures above about 50 ° C.).

Other anionic surfactants useful for cleaning purposes are also included in the laundry detergent compositions of the present invention.
Can be included in adult products. These are soap salts (eg, sodium, potassium,
Ammonium, and substituted salts such as mono-, di-, and triethanolamine salts.
Ammonium salt), C₉-C₂₀Linear alkyl benzene sulfonate, C ₉ -C₂₂A first or second alkane sulfonate, C₈-C₂₄Olefins
Lufonates are described, for example, in GB 1,082,179.
Made by the sulfonation of pyrolysis products of alkaline earth metal citrate
Sulfonated polycarboxylic acid, C₈-C₂₄Alkyl polyglycol ethers
Rufonate (containing up to 10 moles of ethylene oxide); alkyl glycerol
Sulfonate, fatty acyl glycerol sulfonate, fatty oleyl glycerol
Rusulfate, alkylphenol ethylene oxide ether sulfate,
Such as paraffin sulfonate, alkyl phosphate, acyl isothionate
Isothionates, N-acyl taurates, alkyl succinates and sulfos
Succinate, monoester of sulfosuccinate (especially saturated or unsaturated C₁₂−
C₁₈Monoesters) and diesters of sulfosuccinates (especially saturated or unsaturated).
Saturated C₆-C₁₂Diester), acyl sarcosinate, alkyl polysaccharide
Lid sulfates, such as alkyl polyglucoside sulfates (non-a
On-unsulfated compounds), branched primary alkyl sulfates, and
Lkylpolyethoxycarbonate such as the formula RO (CH₂CH_2O)_k-CH₂C
OO-M +, (where R is C₈-C₂₂Alkyl, k is an integer from 0 to 10
And M is a soluble salt-forming cation). Rosin, hydrogenation logistics
Such as resin acids and hydrogenated resin acids present in or derived from
Resin acids and hydrogenated resin acids are also suitable. A more specific example is “Surface Acty
Bu Agents and Detergents ”(Schwartz, Perry and Birch
Authors, Vol. I and Vol.). Various of such surfactants are also disclosed in U.S. Pat. No. 3,929,6, issued Dec. 30, 1975 to Rollin et al.
No. 78, column 23, line 58 to column 29, line 23 are generally disclosed.
(Added here as a reference).

When included therein, the laundry detergent compositions of the present invention typically comprise from about 5% to about 50%, preferably from about 10% to 40%, by weight of such anionic surfactant. Become.

The laundry detergent compositions of the present invention also include non-ionic, cationic, amphoteric, zwitterionic and semi-polar surfactants, as well as other non-ionic surfactants already described herein. May be.

Nonionic: Oxide condensates of alkylphenols of polyethylene, polypropylene, and polybutylene are suitable for use as nonionic surfactants in the surfactant systems of the present invention, and are used with condensates of polyethylene oxide Is preferred. These compounds form a condensation product of the condensation product of an alkyl phenol with an alkylene oxide containing an alkyl group having from about 6 to about 14 carbon atoms, preferably from about 8 to about 14 carbon atoms. Or in the form of a branched chain. In a preferred embodiment, the ethylene oxide is present in an amount equal to about 1 to about 25 moles, more preferably about 3 to about 15 moles of ethylene oxide per mole of alkylphenol. Commercially available non-ionic surfactants of this type include Triton® X-45, X-114, X-100 and X-10.
2, all marketed by Rohm and Haas. These surfactants are commonly referred to as alkylphenol alkoxylates (eg, alkylphenol ethoxylates).

The condensation products of primary and secondary aliphatic alcohols with from about 1 mole to about 25 moles of ethylene oxide are suitable for use as nonionic surfactants in the nonionic surfactant systems of the present invention. The alkyl chain of the aliphatic alcohol can be straight or branched, primary or secondary, and can usually contain from about 8 to about 22 carbon atoms. Preferred is an alcohol having an alkyl group containing from about 8 to about 20 carbon atoms, more preferably from about 10 to about 18 carbon atoms, and from about 2 to about 10 moles per mole of alcohol. It is a condensation product with ethylene oxide. Examples of commercially available nonionic surfactants of this type are:
Tergitol® 15-S-9 (condensation product of a C ₁₁ -C ₁₅ linear alcohol with 9 moles of ethylene oxide), Tergitol® 24
_{-L-6 NMW (C 12 -C} 14 condensation products with narrow molecular weight distribution of the primary alcohol and 6 moles of ethylene oxide), are both marketed by Union Carbide Corporation; marketed by Shell Chemical Company Neodol® 45-9 (condensation product of a C ₁₄ -C ₁₅ linear alcohol with 9 moles of ethylene oxide), Neodol® 23-
6.5 _(the condensation product of linear alcohol with 6.5 moles of ethylene oxide C 12 _{-C 13),} Neodol _{(TM) 45-7} (linear alcohol with 7 moles of ethylene oxide C 14 _{-C 15} With Neodol (trade name) 4
5-4 (condensation product of a linear alcohol of C ₄ -C ₁₅ with 4 moles of ethylene oxide), and Kyro® EOB (C ₁₁ ) marketed by The Procter & Gamble Company including -C condensation products of alcohols with 9 moles of ethylene oxide _15).

Also useful as nonionic surfactants in the surfactant system of the present invention are 1
An alkyl polysaccharide disclosed in Lenado U.S. Pat. No. 4,565,647 issued Jan. 21, 986. It comprises a hydrophobic group containing from about 6 to about 30 carbon atoms, and from about 1.3 to about 10, preferably from about 1.3 to about 3,
Most preferably, it has a polysaccharide having a hydrophilic group containing about 1.3 to 2.7 saccharide units, such as a polyglycoside. Any reductive saccharide containing 5-6 carbon atoms can be used, for example, the glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties (optionally, if the hydrophobic groups are 2-, 3-, 4- -, Thereby giving glucose or galactose as opposed to glucoside or galactoside). Intermediate saccharide linkages are, for example, one position of an additional saccharide unit and two positions on the preceding saccharide unit.
It can be between the-, 3-, 4-, and / or 6-position.

Optionally and less preferably, there can be a polyalkylene oxide chain connecting the hydrophobic component and the polysaccharide component. The preferred alkylene oxide is ethylene oxide. Representative hydrophobic groups include alkyl groups, containing about 8 to about 18, preferably about 10 to about 16 carbon atoms, which can be saturated or unsaturated, branched or unbranched. Preferably, the alkyl group is a straight-chain saturated alkyl group. The alkyl group can include up to about 3 hydroxy groups and / or the polyalkylene oxide chain can include up to about 10, preferably less than 5, alkylene oxide moieties. Suitable alkyl polysaccharides are octyl, nonyldecyl, undecyldodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl, gee, tree, tetra, penter, hexaglucoside, galactoside, lactoside, glucose, fructoside, fructose, and And / or galactose. Suitable mixtures include coconut oil alkyl, gee, tree, tetra, pentaglucoside, and tallow alkyl tetra, penter, hexaglucoside.

Preferred alkyl polyglycosides have the formula: R ² O (C _n H _2n O) _t (glycosyl) _x where R ² is alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and the like. Selected from the group consisting of mixtures, wherein the alkyl group contains from about 10 to about 18, preferably from about 12 to about 14, carbon atoms; n is 2 or 3, preferably 2, and t is X is from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7. Glycosyl is preferably derived from glucose. To make these compounds, an alcohol or alkylpolyethoxy alcohol is first formed and then reacted with glucose or a glucose source to form a glucoside (attached at the 1-position). Additional glycosyl units are then
The-position and the 2-, 3-, 4- and / or 6-position, preferably most of the preceding glycosyl units can be attached between the 2-position.

Although not preferred, the condensation product of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol is also preferred as the additional nonionic surfactant of the nonionic surfactant system of the present invention. Suitable for use as an agent. The hydrophobic portion of these compounds is preferably from about 1500 to about 1800
And will be water insoluble. The addition of a polyoxyethylene moiety to this hydrophobic moiety tends to increase the water solubility of the molecule as a whole, and the liquid nature of the product results in a polyoxyethylene content of about 50% of the total condensation product. Up to a point, which corresponds to the condensation of up to about 40 mol of ethylene oxide. Examples of compounds of this type include some of the commercially available Pluronic (TM) surfactants marketed by BASF.

Also suitable for use as nonionic surfactants in the nonionic surfactant systems of the present invention are condensation products of ethylene oxide with products obtained from the reaction of propylene oxide with ethylenediamine. Things. The hydrophobic component of these products consists of the reaction product of ethylene diamine and excess propylene oxide and usually has a molecular weight of about 2500 to about 3000. This hydrophobic component is
The condensation product condenses with ethylene oxide to an extent containing from about 40% to about 80% by weight of the polyoxyethylene and has a molecular weight from about 5,000 to about 11,000. Examples of this type of nonionic surfactant include some of the commercially available Tetronic® compounds marketed by BASF.

Suitable for use as the nonionic surfactant in the surfactant system of the present invention are polyethylene oxide condensates of alkyl phenols, primary and secondary aliphatic alcohols with about 1 to about 25 moles. Condensation products of ethylene oxide with
Alkyl polysaccharides, and mixtures thereof. Most preferred are alcohol ethoxylates (preferably _{C 10} of _C 8 _{-C 18} with alkyl phenol ethoxylates and 2 to 10 ethoxy groups of _C 8 _{-C 14} having 15 ethoxy groups from three ; Average), and mixtures thereof.

A highly preferred nonionic surfactant is a polyhydroxy fatty acid amine surfactant. Also suitable as the nonionic surfactant are polyhydroxy fatty acid amide surfactants of the following formula.

Embedded image Wherein R ¹ is H, or R ¹ is C _1-4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, R ² is C _5-31 hydrocarbyl, and Z is linear hydrocarbyl A polyhydroxyhydrocarbyl having a chain and having at least three hydroxyls directly attached to the chain, or an alkoxylated derivative thereof. Preferably, R ¹ is methyl, R ² is a linear C _1-15 alkyl or alkenyl chain such as coconut oil alkyl or a mixture thereof, and maltose in a reductive amination reaction, lactose.

[0032] Preferably, the level of nonionic surfactant is 1 wt% to 35 wt%. The ratio of anionic to nonionic surfactant is from 7: 3 to 90: 1, preferably from 3: 1 to 60: 1. The total amount of surfactant present will also depend on the intended use, and can be as high as 65 wt%. However, for machine laundry fabrics, an amount of 5-40 wt% is most appropriate.

[0033] Preferred cationic surfactant systems include nonionic and amphoteric surfactants.
No. Cationic detersive surfactant suitable for use in the laundry detergent compositions of the present invention
The agent has one long-chain hydrocarbyl group. Such cationic surfactant
Examples of surfactants include ammonium salts such as alkyldimethylammonium halides.
Surfactants and surfactants having the formula: [R²(OR³)_y] [R⁴(OR³)_y]₂R⁵N + X- where R²Is an alkyl or alkyl having about 8 to about 18 carbon atoms in the alkyl chain.
Is an alkylbenzyl group, and each R³Is -CH₂CH₂-, -CH ₂ CH (CH₃)-, -CH₂CH (CH₂OH)-, -CH₂CH₂CH₂−
, And mixtures thereof; each R⁴Is C₁-C₄A
Luquil, C₁-C₄Hydroxyalkyl, two R⁴The base formed by the
Ring structure, -CH₂CHOHCHOHCOR⁶CHOHCH₂OH-
R⁶Is a hexose or hexose polymer having a molecular weight of less than about 1000.
Selected from the group consisting of any one of the above, and hydrogen when y is not 0;⁵Is R⁴When
Same or alkyl chain, provided that R²+ R⁵The total number of carbon atoms in the
Each y is from 0 to about 10 and the sum of y values is from 0 to about 15.
X is any of the compatible anions.

[0034] The detergent compositions of the present invention usually also contain one or more detergency builders. The total amount of detergency builders in the composition should be in the appropriate range of 5 wt% to 80 wt%, preferably 10 wt% to 60 wt%.

The inorganic builder that may be included is sodium carbonate, if desired, British Patent No. 143795
No. 0 (Unilever) in combination with a crystal seed for calcium carbonate; crystalline and amorphous aluminosilicates, for example, British Patent No. 14732
No. 01 (Henkel), GB 1473202
Aluminosilicate as disclosed in Henkel and British Patent No. 1
470250 (Procter & Gamble), including mixed crystalline / amorphous aluminosilicates; and layered silicates as disclosed in EP164514B (Hoechst). Inorganic phosphate builders, such as sodium orthophosphate, pyrophosphate and tripolyphosphate, are also suitable for use in the present invention.

The detergent composition of the present invention preferably contains an alkali metal, preferably sodium, an aluminosilicate builder. Sodium aluminosilicate is usually 10
% To 70% by weight (on an anhydrous basis), preferably 25% to 50% by weight
It is good to add in the amount of.

The alkali metal aluminosilicate may be crystalline or amorphous or a mixture thereof and has the following general formula: 0.8-1.5 Na ₂ O.Al ₂ O ₃ .0.8-6 SiO ₂ These materials must contain some bound water and have a calcium ion exchange capacity of at least 50 mg CaO / g. Preferred sodium aluminosilicates contain 1.5-3.5SiO ₂ units (in the formula above). Both amorphous and crystalline materials can easily be made by the reaction of sodium silicate and sodium aluminate, as described in detail in the literature.

A suitable crystalline sodium aluminosilicate ion exchange detergency builder is
For example, it is described in British Patent No. 1429143 (Procter & Gamble). Suitable sodium aluminosilicates of this type are the well-known commercially available zeolites A and X, and mixtures thereof. The zeolite can be a commercially available zeolite 4A, which is currently widely used in laundry detergents. However, according to a preferred embodiment of the present invention, the zeolite builder added to the compositions of the present invention is Maximum Aluminum Zeolite P (Zeolite MAP) as described and claimed in EP 384070A (Unilever). Zeolite MAP has a silicon to aluminum ratio of 1
. Not exceeding 33, preferably in the range of 0,90 to 1.33, more preferably in the range of 0.90 to 1.20.

Particularly preferred are zeolite MAPs having a silicon to aluminum ratio not exceeding 1.07, more preferably not exceeding about 1.00. The calcium binding capacity of zeolite MAP is usually at least 150 mg CaO / g of anhydrous material.

Organic builders that may be included are polycarboxylic acid polymers, such as polylylic acid,
Acrylic acid / maleic acid copolymer and acrylic phosphinate;
Monomeric polycarboxylic acids such as citrate, gluconate, oxydisuccinate, glycerol mono-, di-, and trisuccinate, carboxymethyloxysuccinate, carboxymethyloxymalonate, dipicolinate, hydroxyethyliminodiacetate , Alkyl- and alkenyl malonates and succinates; and sulfonated fatty acid salts. This list is not meant to be exhaustive.

A particularly preferred organic builder is citrate, from 5 wr% to 30 wt%,
Preferably it is suitably used in an amount of 10% to 25% by weight; acrylic polymers, more particularly acrylic acid / maleic acid copolymers, from 0.5% to 15% by weight.
% by weight, preferably from 1 to 10% by weight. Builders are present both inorganic and organic, preferably in the form of alkali metal salts, especially sodium salts.

[0042] The detergent composition of the present invention can be in liquid, paste or granular form. Such compositions can be prepared in a conventional manner by combining the essential and optional ingredients in the appropriate sequence to the required concentrations.

The granule composition is typically prepared as a slurry, for example, by combining the base granule components (eg, surfactants, builders, water, etc.) and the resulting slurry is treated with low residual moisture (5-12%). ) Spray dry to make. The remaining dry ingredients can be combined with the spray-dried granules in a rotary mixing drum in the form of a granular powder, and the liquid ingredients (eg, yeast, binder and flavor) can be sprayed onto the resulting granules. It can be a finished product of the detergent composition.

The granular compositions of the present invention can also be in “compact form”, ie, they have a relatively higher density than conventional granular detergents, ie from 550 g / l to 950 g. / L. In such a case, the granular detergent composition of the present invention contains a smaller amount of "inorganic bulking agent salt" as compared to conventional granular detergents; typical bulking agent salts are sulfates and chlorides. Alkaline earth metal salts, typically sodium sulfate; "compact" detergents typically comprise up to 10% of a filler salt.

A liquid detergent composition can be made by mixing the essential and optional ingredients in a desired order that will result in a composition containing the ingredients in the required concentration. The liquid compositions of the present invention can also be in "compact form", in which case the liquid detergent compositions of the present invention will contain less water than conventional liquid detergents.

The present invention will be described with reference to the following examples. Example 1 An anchor stirrer, a nitrogen purge adapter, a thermometer, two inner layer supply pipes connected to two supply pumps, and a reflux condenser were attached to a 1-liter volume, 4-neck resin container. The vessel was charged with 150 g of 4-vinylpyridine and 150 g of isopropanol. Initiate a nitrogen purge and continue this throughout the process at 200 rpm
With stirring. The reaction was then heated to 80 ° C. in 20 minutes and held at that temperature for 30 minutes. Then 390 microliters of t-butyl peroxypivalate (Lupersol
Registered trademark 11) was added. The solution polymerization reaction was performed at 80 ° C. for 2 hours. Then 195
Microliters of Lupersol® 11 were added and the reaction continued at 80 ° C. for another 2 hours. The latter step was repeated six more times. Then 150 g of water and 166.2
g of sodium chloroacetate and the contents were rinsed with 100 g of water. The resulting mixture was heated to remove 100 g of distillate and then 100 g of water was added to the mixture and the process was repeated to remove another 50 g of distillate. Then the mixture was cooled to room temperature. The product is obtained as a solution, the solids level of which is about 48%
Was adjusted to.

Example 2 The procedure of Example 1 was repeated using 125 g of sodium chloroacetate. A similar product was obtained.

Example 3 The procedure of Example 1 was repeated using 83 g of sodium chloroacetate. The product was obtained similarly.

Example 4 A 1-liter, 4-neck resin container equipped with an anchor stirrer, a nitrogen purge adapter, a thermometer and a reflux condenser was charged with 50 g of 4-vinylpyridine and 50 g of vinylpyrrolidone. . A nitrogen purge was started which continued during the reaction and the stirrer was set at 20 rpm. The reaction was then heated to 80 ° C. in 20 minutes and held at that temperature for 30 minutes. Then 0.1% (based on the total weight of the monomers) of t-butyl peroxypivalate (Lupersol® 11) is added and the reaction temperature is raised to 80 ° C.
For 2 hours. Then 0.05% (based on the total weight of monomers) of Lupersol® 11 is added every 2 hours until the level of residual 4-vinylpyridine is less than 2%, and the reaction temperature is raised to 80 ° C. Held. Then, 250 g of water and 55.4 g of sodium chloroacetate were mixed and added. The mixture was heated to remove distillate. More water was added during distillate removal until all ethanol was removed at about 105 ° C. The final solids level was adjusted by adding water to the final product.

Example 5 Example 4 was repeated using 25 g of 4-vinylpyridine, 75 g of vinylpyrrolidone and 27.7 g of sodium chloroacetate, with similar results.

Example 6 Example 1 was repeated using 186.5 g of sodium 2-chloropropionate instead of sodium chloroacetate with similar results.

Example 7 Example 1 was repeated using 186.5 g of sodium 1-chloropropionate with similar results.

Example 8 150 g of 4-vinylpyridine and 150 g in a 1-liter, 4-neck resin container equipped with an anchor stirrer, a nitrogen purge adapter, a thermometer and a reflux condenser
Of isopropanol. The reaction was heated from ambient temperature (20-25 ° C) to 80 ° C in 20 minutes and held at that temperature for 30 minutes. Then 0.1% (based on the total weight of the monomers) of t-butyl peroxypivalate (Lupersol® 1)
1) was added to the vessel, and the reaction temperature was maintained at 80 ° C. for 2 hours. Then 0.05% (based on the total weight of monomers) of Lupersol® 11 is added every 2 hours until the level of residual 4-vinylpyridine is less than 2%, and the reaction temperature is raised to 80 ° C. Held. The reaction mixture was cooled to 40 ° C. and mixed with 250 g of water and 57.2 g of sodium hydroxide and added. Then 135.1 g of chloroacetic acid was pumped into the reactor by melting the chloroacetic acid. The mixture was heated to remove distillate, and then more water was added during distillate removal until all ethanol was removed.

Test Results The effectiveness of the polymers of the present invention as DTI additives in laundry detergent compositions containing at least 1% by weight of a suitable surfactant was aimed at in tests to simulate actual laundry conditions. Tested in comparison to DTI polymer and other known polymers. The test was carried out on a composition containing 1 g / l of a detergent containing a mixture of both anionic and nonionic surfactants, 10 ppm of dye and 10 ppm of polymer. The solution was diluted to 1 liter by using water.

Three pieces of white cotton cloth # 400 (bleached and desized) were immersed in the test vessel at 100 ° F. and the solution was immersed for 10 minutes in a Terg-o. -tometer) (Instrument Marketing Services). The fabric was then removed, excess solution was squeezed out, the fabric was washed again in clean water for 3 minutes, squeezed again and dried. Reflectance measurements were performed on such test materials using a colorimeter. The reading of the reflectivity was recorded as ΔE. ΔE is a composite of the degree of white index, red index, and blue index in the dried fabric; these readings can be considered as a direct measure of the degree of dye deposition under test wash conditions. The results of the test are shown in Tables 1 and 2 below.

[0056]

[Table 1]

[0057]

[Table 2]

Test Results for Soil Redeposition Resistance The effectiveness of the polymers of the present invention to control redeposition of soil in laundry detergent compositions was determined by tests that simulate actual laundry conditions. , Aiming DTI polymers and other known polymers. The test was carried out in solution with a composition containing 2 mg / L Dust Sebum and 50 ppm polymer. The solution was diluted to 1 L with water.

Three pieces of white polycotton cloth (polyester-cotton (cotton) 65:35) were immersed in a test vessel maintained at 100 ° F., and the solution was immersed for 10 minutes in a targ autometer (Instrument Marketing Services, Inc.). ). The fabric was then removed, the excess solution was squeezed out, the fabric was washed again with clean water for 3 minutes, squeezed again and dried. Reflectance measurements were performed on such test materials with a colorimeter. Reflectance readings were recorded at 460 nm and the deviation relative to the blank was recorded. As the reflectance approaches the white cloth, the ability of the polymer to inhibit soil redeposition increases. These readings can be considered as a direct measure of the degree of soil deposition under test wash conditions. The test results are shown in Tables 3 and 4 below.

[0060]

[Table 3]

[0061]

[Table 4]

Preferably, and more particularly, the fabric softener composition is desirably in the form of a liquid composition, more preferably in the form of an aqueous composition, From about 3 to about 50%, preferably from about 4% to about 30%, of the fabric softener; II. From about 0.03% to about 25%, preferably from about 0.1% to about 15%, as shown by the above formula. A water-soluble polymer migration inhibitor (DTI), III. A liquid carrier, preferably a balance comprising water, wherein the liquid composition is substantially free of aerosol propellants.

The present invention further includes a fabric softener composition to which a dryer has been added, the composition comprising: About 50% to about 90%, preferably about 70% to 99% of fabric softener; II. About 0.2% to about 50%, preferably about 1% to about 30% of the above (A), (B)
), (C) and (D), a polymer migration inhibitor selected from the group consisting of: III. And optionally, a dispersant that provides an effective amount of the composition to release into the fabric. .

The solid, particulate fabric softener composition of the present invention typically comprises: About 20% to about 90%, preferably about 30% to about 70%, fabric softener; II. About 0.1% to about 80%, preferably about 0.3% to about 50%, more preferably about And 0.5% to about 25% of a dye transfer inhibitor selected from the group consisting of (A), (B), (C) and (D).

Fabric Softener The amount of fabric softener in the liquid compositions of the present invention typically ranges from about 3% to about 50%, preferably from about 4% to about 30%, by weight of the composition. %. The lower limit is an amount necessary for effectively exhibiting fabric softness when added to a washing rinsing bath according to the procedure of washing performed at home. The upper limit is an amount suitable for a concentrated product that can provide a more economical way for consumers to use by reducing packaging and cost.

Examples of Liquid Fabric Softener Composition The following liquid softener composition, when added to the rinsing cycle of the automatic washing process, exhibits a dye transfer inhibiting action in the subsequent washing cycle.

[0067]

[Table 5]

Example 9 The composition of Example 9 is prepared by the following procedure. While mixing Polymer A (75% quaternary salt) (average molecular weight of about 10,000: either as a powder or as an aqueous solution), add into a container containing deionized water and heat to about 65 ° C. I do. Melted DTDMAC / MTTMAC formulation (about 80 ° C.
Is added to the aqueous solution with high shear mixing. After the incorporation of the softener, the mixture is cooled and minor components are added during the cooling step.

Examples of Fiber Conditioning Substrate Products The following fiber conditioning compositions and substrate products, when added to a tumble dryer with a wet roundly load, inhibit dye transfer during subsequent washing cycles. Show.

[0070]

[Table 6]

Example 10 Preparation of a Coating Mix A batch of about 200 grams of the coating mix was prepared as follows.
An amount of about 160 g of ditallow dimethyl ammonium chloride (DTDMAC) is melted at 80 ° C. Calcium bentonite clay (about 8g bentonite
L; available from Southern Clay Corporation) at high shear mixing to the mixture slowly. During mixing, the mixture is kept in a boiling water bath in the molten state. Then, about 32 g of Polymer A (75% quaternary salt) is slowly added to the mixture under high shear mixing and the formulation is mixed until the mixture is smooth and uniform.

(Preparation of Fiber Conditioning Sheet) The coating mixture was weighed to a size of about 9 inches × 11 inches (about 23 c
mx 28 cm) on a non-woven substrate. The substrate sheet is composed of 70% 3 denier, 1-9 / 16 inch (about 4 cm) long rayon fibers and 30% polyvinyl acetate binder. The substrate weighs about 16 g per square yard (about 1.22 g / sheet). A small amount of the formulation is placed on a heated metal plate with a spatula and then spread evenly with a metal wire rod. A non-woven substrate sheet is placed on a metal plate to absorb the coating mixture. The sheet can then be removed from the heated metal plate and cooled to room temperature to solidify the coating mixture. The sheet is weighed and the amount of the coating mixture on the sheet is measured. The target coating is 1
2.0 g per sheet. If this weight is greater than the desired weight, the sheet is repositioned on a heated metal plate and the coating mixture is again melted to remove any excess. If this weight falls below the desired weight, the sheet is also placed on a heated metal plate and the coating mixture is added.

[0073]

[Table 7]

Example 11 Preparation of Coating Mixture and Fiber Conditioning Sheet About 11.89 parts of octadecyldimethylamine (Ethyl Corporation),
A first formulation consisting of 8.29 parts of a C14-C14 fatty acid (Procter & Gamble Corporation) and 10.69 parts of a C16-C18 fatty acid (Emery Industries, Inc.) was melted together at 80C. And a second formulation consisting of about 19.32 parts sorbitan monostearate (Maser Chemical Inc.) and 19.32 parts ditallow dimethyl ammonium methyl sulfate, DTDMAMS (Sherex Chemical Corporation) was melted together. The softener component of the composition is formed, during which time the mixture is kept in a molten state in a boiling water bath. Calcium bentonite clay (3.86 parts of bentonite L; available from Southern Clay Corporation) is then slowly added to the mixture while mixing with high shear. Then, an amount of about 26.62 parts of Polymer A is added in small portions and the formulation is mixed until the mixture is smooth and completely homogeneous. This coating mixture is applied to a pre-weighed non-woven substrate sheet as in Example 10. The desired coating is 2.33 g per sheet. Each sheet has about 1.62 g softener, about 0.09 g clay, and about 0.6 g.
2 g of polymer A.

Although the polymers of the present invention have been described as additives in roundle detergent and fabric softener compositions, it will be appreciated that they can be utilized in other applications requiring anti-sediment performance. Thus, the water-soluble polymer of the present invention can be effectively used to prevent dust or soil redeposition in, for example, engine, household and industrial cleaners, and clothing applications. The following is a list of suitable uses for the polymers and copolymers of the present invention.

Soil anti-redeposition; Digital printing ink application; Garment dye decolorization; Garment dye strike rate control; Flocculant; Adhesive; Ion exchange / membrane; Trace metals from water (Hg,
Removal of Cd, Cu, Ni) / softener of water; colloid stabilization; pumping of oil from underground warehouses; personal care market, shampoos and hair conditioners;
Detergents for cleaning cleaners and dishes, cleaning aids; water treatment to prevent hot water from settling on the surface of the wall; pigment dispersion.

──────────────────────────────────────────────────続 き Continued on the front page (31) Priority claim number 09 / 105,666 (32) Priority date June 26, 1998 (June 26, 1998) (33) Priority claim country United States (US) ( 81) Designated countries EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, K, EE, ES, FI, GB, GE, GH, GM, HU, ID, IL, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, UG , VN, YU, ZW (72) Inventor Bara Srinivas, United States of America New Jersey 07604 Hasbrocks Heights Woodland Drive 13 (72) Inventor John Sea Hornby, United States of America New Jersey 07675 Washington Township Sika More Lane 885 F-term (reference) 4H003 AE05 DA01 EA03 EB28 ED02 FA06 FA22 4L033 AA02 AA07 AA08 AB04 AC02 AC15 CA13

Claims (11)

[Claims] 1. The following formula comprising quaternary nitrogen and a carboxyl salt: Wherein m represents the degree of polymerization, x is an anion, R 1 and R 2 are independently hydrogen, alkyl or aryl, n is 1-5, and M represents a cation. A laundry detergent composition or a fabric softener composition comprising at least 1% by weight of a surfactant containing a water-soluble poly (vinylpyridine betaine) or a copolymer thereof in a migration inhibiting amount. 2. The laundry detergent composition according to claim 1, wherein X is a halide such as chloride or bromide. 3. The laundry detergent composition according to claim 2, wherein the polymer has a polymerization average molecular weight of about 5,000 to 1,000,000. 4. The laundry detergent composition according to claim 1, wherein R ₁ and R ₂ are both hydrogen and n is 1. 5. The laundry detergent composition according to claim 2, wherein M is an alkali metal such as sodium or potassium. 6. The laundry detergent composition according to claim 1, wherein m is from 30 to 5,000, preferably from 100 to 1,000. 7. The laundry detergent composition according to claim 1, wherein 25 to 100% of the polymer is quaternized. 8. The laundry detergent according to claim 1, wherein the polymer is a water-soluble copolymer with a polymerizable monomer such as vinylpyrrolidone, vinylcaprolactam, vinylimidazole, N-vinylformamide or acrylamide. Composition. 9. The laundry detergent composition according to claim 1, wherein the polymer is poly (4-vinylpyridine) sodium carboxymethyl betaine chloride. 10. The laundry detergent composition or softener composition according to claim 1, comprising 2 to 1000 ppm of the polymer. 11. The laundry detergent composition or softener composition according to claim 1, which contains 2 to 50 ppm of a polymer.