EP0066915B1

EP0066915B1 - Detergent composition containing performance additive and copolymeric compatibilizing agent therefor

Info

Publication number: EP0066915B1
Application number: EP82200602A
Authority: EP
Inventors: Robertus J.C. Koster; André Baeck
Original assignee: Procter and Gamble European Technical Center; Procter and Gamble Co
Current assignee: Procter and Gamble European Technical Center; Procter and Gamble Co
Priority date: 1981-05-30
Filing date: 1982-05-17
Publication date: 1987-11-11
Also published as: ATE30738T1; EP0066915A2; CA1187373A; DE3277630D1; EP0066915A3

Abstract

Detergent compositions containing surface-active agents, builders, performance additives and a narrowly defined class of carboxylic copolymers are disclosed. Preferred copolymers contain maleic acid and (meth)acrylic acid monomers. Preferred detergent additives are hydrocarbon detergent suds regulants, photoactivators. amine or oxidized amine soil release agents, silicone detergent suds regulants and bleach activators/peracids.

Description

This invention relates to the detergent utilization of certain copolymeric ingredients in a compatibilizing functionality in conjunction with performance additives. The copolymeric ingredient is prepared from an ethylenically unsaturated carboxylic acid and an ethylenically unsaturated dicarboxylic acid. Preferred monomers are acrylic and methacrylic acids on one hand and maleic and citraconic acids on the other hand. The copolymeric agent was found to be especially suitable for enhancing the compatibility of detergent additives which are known to be sensitive to various conditions inclusive of prolonged storage, temperature, alkalinity, and/or laundry conditions. In more detail, the copolymeric compatibilizing agent is capable of procuring, in contradistinction to their art-established functionality, unexpected transfer properties in relation to specific detergent additives. These transfer properties go against the prevailing opinion according to which comparable copolymeric adjuvants serve as deposition inhibitors, and consequently diminish the physical contact between detergent ingredients and e.g. the fiber.
The use of low levels of (co)polymeric additives for detergent application has been known for a long time and has found application in commercial detergent products. European Patent Application 0009171, BASF AG, published April 2, 1980 relates to the incorporation of polymaleic acid as a builder ingredient and/or as an incrustation inhibitor in detergents. European Patent Application 0025551, BASF AG, published March 25, 1981 discloses the utilization of (meth)acryIic · acid-maleic acid copolymeric ingredients as incrustation inhibitors in detergent compositions. The copolymer comprises a large majority of the (meth)acrylic acid monomer FR-A-2388045, The Procter & Gamble Company, published November 17, 1978, pertains to detergent compositions containing surface-active agents, builders and a binary system based on not more than 4% of a polyphosphonate and not more than 4% of a polymeric ingredient which can be represented by the copolymers obtained from the polymerization of (meth)-acrylic acid and maleic anhydride.
German Patent Application DOS 19 59 272, Procter & Gamble European Technical Center, published July 23, 1970, relates to solid oxygen-bleach detergent compositions containing a copolymeric ingredient based on vinyl methylether and maleic anydride. The copolymeric ingredient is claimed to provide effective active oxygen regulation.
It has now been discovered that the particular copolymeric ingredient of the invention herein can be used beneficially with a view to secure very desirable performance benefits upon use in combination with particular detergent additives with the proviso that the copolymeric ingredient is preferably used in excess levels in relation to a given performance additive.
It is an object of this invention to formulate detergent compositions having desirable performance characteristics containing specific detergent additives.
It is a further object of this invention to formulate laundry products capable of providing superior overall performance in presence of specific additives.

Brief description of the invention

It has now been discovered that markedly improved detergent compositions can be formulated containing a conventional detergent matrix in combination with detergent performance additives and a copolymeric ingredient. The performance additives are present in an amount from 0.002% to 5% by weight. The copolymeric ingredient is prepared from an ethylenically unsaturated carboxylic acid monomer having not more than five carbon atoms and from an ethylenically unsaturated dicarboxylic acid monomer having not more than six carbon atoms, whereby these monomers are copolymerized in a molar proportion of 1:4 to 4:1. The weight ratio of the copolymeric ingredient to the performance additives is from 500:1 to 1:5. Performance additives for use in combination with the copolymeric ingredients are selected from water-soluble porphine photoactivators such as mixtures of sulfonated metal phthalocyanines; and renewable polyamine or amine oxide soil release agents.

Detailed description of the invention r:'.

The invention herein comprises at least three major parameters, namely: a conventional detergent matrix comprising surface-active agents and builders; a detergent performance additive; and a specific copolymeric ingredient. The major parameters of the invention are described in more detail hereinafter.
Unless indicated to the contrary, the "percent" indications represent "percent by weight" indications.
Qualitatively and quantitatively suitable surface-active agents for use herein are disclosed in U.S. Patent 4,192,761, column 3, line 49 to column 5, line 42. Qualitatively and quantitatively suitable detergent builder materials can also be taken from U.S. Patent 4,192,761, column 8, line 56 to column 9, line 68.
It goes without saying that the detergent matrix of the compositions of this invention can also contain other major components according to the particular needs and/or the physical state of the invention. In this respect, the compositions herein can be solid, pasty or liquid. Major amounts of pH regulants, inert fillers like sodium sulfate, water and/or organic solvents like hydrocarbons and/or lower alcohols can be applied as is well-known in the art. The detergent matrix can also contain major levels of bleaching agents, for example, oxygen bleach agents such as perborate, percarbonate, perpyrophosphate, persilicate or, more in general, all oxygen-bleach agents which are known to be suitable for use in detergent compositions in the established levels.
The copolymeric ingredient consists of an ethylenically unsaturated monocarboxylic acid monomer having not more than 5, preferably 3 or 4, carbon atoms, and an ethylenically unsaturated dicarboxylic acid monomer having not more than 6, preferably 4 carbon atoms, whereby the molar ratio of the monomers is in the range from 1:4 to 4:1 (i.e., monocarboxylic acid:dicarboxylic acid). Suitable examples of the monocarboxylic acid monomer are: acrylic acid, methacrylic acid and vinyl acetic acid. Acrylic and methacrylic acids are preferred. Suitable examples of the dicarboxylic acid monomers are: maleic acid; fumaric acid; citraconic acid; and mesaconic acid. Preferred dicarboxylic acids are maleic acid and citraconic acid.
The copolymeric ingredient can be further defined with the aid of the calcium sequestration value. These values can be measured by nephelometric titration methods (as described in literature

-S. Chaberek and A. E. Martell, Organic Sequestering Agents, Wiley, New York, 1959;
-R. L. Smith, The Sequestration of Metals, Chapman and Hall, London, 1959):
- a calcium nitrate solution is added to a solution containing sequestrant and sodium oxalate until turbidity is produced; the titration is being carried out at constant pH=10 and room temperature.

The sequestration value is expressed in mgCaC0₃/gram of copolymeric ingredient.
The calcium sequestration value of the copolymeric ingredient is preferably in the range from 300-900 mgCaC0₃/g.
The performance additives herein are present in an amount from 0.002% to 5%. Depending upon the particular functionality of the additive and the planned use of the final detergent composition, the preferred usage ranges for the individual additives vary from additive to additive. The term performance additive as used herein is meant to express that the specific ingredient is added either to cure a deficiency of the general detergent matrix and/or to provide special laundry and cleaning benefits.
A class of performance additives that can be utilized beneficially in combination with the copolymeric agent is represented by a photoactivator, also frequently termed a photosensitizer. The photoactivator is a porphine of a mono-, di-, tri-, or tetraaza porphine solubilized with anionic, nonionic, and/or cationic substituent groups and metal free or metallated with Zn(II), Ca(II), Cd(II), Mg(II), Sc(III), AI(III), or Sn(IV). Preferred metal-ions forthe photoactivator are zinc and aluminum. The photoactivator is frequently used in low levels, e.g., in the level from about 20 ppm to 2000 ppm. In solid detergent compositions, the photoactivator is generally used in combination with a carrier material such as polyphosphates, sulfates, a.s.o. Generally, the level of such photoactivator particles (containing a carrier material) represents from 0.1 % to 1% of the detergent composition. The photoactivator is believed to exhibit its activity in the direct environment of the fiber possibly in combination with perborate. The copolymeric ingredient favors this transfer of photoactivator to the fiber in presence of the other components in the laundry liquor at the applicable temperatures, e.g., laundry temperatures in the range from up to about 60°C or up to the boil.
As an example, a water-soluble photoactivator used in the specified levels can be represented by the porphine activators of European Patent Application 0003149. The weight ratio of copolymer to photoactivator performance additive is frequently in the range from 500:1 to 7:1.
The copolymeric ingredient was also found to be effective in combination with additive levels of renewable soil release agents as described in EP-A-0042187 and EP-A-0042188. The copolymeric ingredient enhances and contributes to a more quantitative deposition of the renewable soil release agent, specifically the polyamines oxidized or not and/or the oxidized monoamines.
The renewable soil release agent which frequently is used in levels from 0.1% to 1.5% is represented by polyamines having the formula:
wherein R is an alkyl or alkenyl group having 10 to 22 carbon atoms, the R_i's, which are identical or different, are ethylene oxide or propylene oxide, R₂ is hydrogen, C₁-₄ alkyl or (R_i)y, where x, y, and z are numbers such that the sum (x+y+z) is in the range from 2 to 25, n is a number from 1 to 6 and m is a number from 1 to 9; or
amine oxides having the formula:
wherein R is an alkyl or alkenyl group having 10 to 22 carbon atoms, the R₃'s which are identical or different are selected from C_'-₄ alkyl, ethylene oxide and propylene oxide, k is an integer from 1 to 6, is an integer from 0 to 6, p is 0 or 1, u, v, and w are each 1 for alkyl substituents, and integers in the range from 1 to 10 for ethylene oxide or propylene oxide substituents such that the sum of (u+v+w) is not greater than 25, with the proviso that a 1 % aqueous solution of the detergent composition has an alkaline pH (20°C).
A preferred polyamine for use herein is N-hydrogenated tallow C₁₆―C₁₈-N,N',N'-tri-(2-hydroxyethyl)-propylene-1,3-diamine. Preferred amine oxide species are N-C₁₂-₁₄-coconutalkyl-N,N-dimethyl-N-amine oxide; N-tallow C_16-18-alkyl-N,N',N-tri-(2-hydroxyethyl)-propylene-1,3-diamine-N,N'-dioxide; N-C_12-14- alkyl-N,N',N'-tri-(2-hydroxyethyl)-propylene-1,3-diamine-N,N'-dioxide; N-C_16-18-tallow-alkyl-N, N-dimethyl-N-amine oxide; N-C_12-14-coconutalkyl-N,N-di(2-hydroxyethyl)-N-amine oxide; or N-C_16-18- tallowalkyl-N,N-di-(2-hydroxyethyl)-N-amine oxide. The weight ratio of copolymer to soil release additive is preferably in the range from 10:1 to 1:1.
In addition to the essential components described herreinbefore, the compositions of this invention can comprise a series of supplementary components to perfect and complement the performance advantages derived from the compositions. These additional components include brighteners, dyes, perfumes, bactericides, and antioxidants, processing aids, corrosion inhibitors, enzymes and so on. These further ingredients are used for their known functionality in the art established levels, i.e., frequently in the range from 0.1% to 5%.
The following examples illustrate the invention and facilitate its understanding.
The abbreviations for the individual ingredients have the following meaning:

LAS: Sodium salt of linear dodecyl benzene sulfonate
TAS: Sodium salt of tallow alcohol sulfate
FAE₃S: Sodium salt of fatty alcohol (C_12-18) (ethoxy)3 sulfate
AO: C₁₂-₁₄ alkyl dimethylamine oxide
HLAS: Linear dodecyl benzene sulfonic acid
TAE₁₁: Tallow alocohol ethoxylated with about 11 moles of ethylene oxide
FA₂₅E₇: Fatty alcohol (C_12―C₁₅) ethoxylated with about 7 moles of ethylene oxide
FA₂₅E₄: Fatty alcohol (C_12―C₁₅) ethoxylated with about 4 moles of ethylene oxide
CFA: C₁₂-₁₄ coconut fatty acid
HFA: Hydrogenerated C₁₆-₂₂ fatty acid
STPP: Sodium tripolyphosphate
Zeolite A: Sodium salt of zeolite 4A (average particle size between 2-6 pm)
NTA: Sodium salt of nitrilotriacetate
Copolymer: AA⁴⁰/MA⁶⁰=copolymer of acrylic acid 40 mol-% and maleic acid 60 mol-% MAA⁵⁰/MA⁵⁰=copolymer of methyacrylic acid 50 mol-% and maleic acid 50 mol-%
CMC: Sodium salt of carboxymethyl cellulose
MHPC: Sodium salt of methyl hydroxypropyl cellulose
Silicate 1.6: Sodium silicate Si0₂/Na₂0=₁.6
TEA: triethanolamine
STS: Sodium salt of toluene sulfonate
EDTA: Sodium salt of ethylene diamine tetra-acetate
Perborate: NaBO2. H₂O₂ · 3H₂0
P.A.: Photoactivator sulfonated Zn phthalocyanine
SRS III: oil in water emulsion
- -9% polydimethylsiloxane
- -1% amorphous hydrophobic silica
- -5% coconut fatty acid ethoxylated with 7 moles of ethylene oxide
- -85% water

The following granular detergent compositions are prepared by conventional spray-drying of a slurry of individual ingredients and subsequent dry-mixing of this base powder with spray-drying sensitive ingredients.
Solid detergent compositions are prepared having the following formulae.
A liquid detergent composition is made by mixing the following individual ingredients.

Claims

1. A detergent composition with a conventional matrix on basis of surface-active agents, builders, performance additives and a copolymeric ingredient, characterized in, that the performance additive is present in an amount from 0.002% to 5% by weight, and is selected from:

(a) a water-soluble photoactivator from the group of porphine or mono-, di-, tri-, or tetraaza porphine solubilized with anionic, nonionic, and/or cationic substituent groups and metal free or metallated with Zn(ll), Ca(ll), Cd(ll), Mg(ll), Sc(lll), AI(III) or Sn(IV); and

(b) a soil release agent which is a polyamine having the formula

wherein R is an alkyl or alkenyl group having 10 to 22 carbon atoms, the R₁'s, which are identical or different, are ethylene oxide or propylene oxide, R₂ is hydrogen C_1-4 alkyl or (R₁)y, where x, y, and z are numbers such that the sum (x+y+z) is in the range from 2 to 25, n is a number from 1 to 6 and m is a number from 1 to about 9; or
an amine oxide having the formula:

wherein R is an alkyl or alkenyl group having 10 to 22 carbon atoms, the R₃'s which are identical or different are selected from C_1-4 alkyl, ethylene oxide and propylene oxide, k is an integer from 1 to 6, I is an integer from 0 to 6, p is 0 or 1, u, v, and w are each 1 for alkyl substituents, and integers in the range from 1 to 10 for ethylene oxide or propylene oxide substituents such that the sum of (u+v+w) is not greater than 25, and that the copolymeric ingredient consists of an ethylenically unsaturated monocarboxylic acid monomer having not more than 5, preferably 3 or 4, carbon atoms, and an ethylenically unsaturated dicarboxylic acid monomer having not more than 6, preferably 4, carbon atoms, whereby the molar ratio of the monomers is in the range from 1:4 to 4:1; and whereby the weight ratio of the copolymer to the performance additive is in the range of from 500:1 to 1:5.

2. The detergent composition in accordance with Claim 1 wherein the copolymeric ingredient is comprised of (meth)-acrylic acid and maleic acid monomers.

3. The detergent composition in accordance with Claim 1 wherein the photoactivator is present in an amount from 20 ppm to 2000 ppm and wherein the weight ratio of copolymer to photoactivator is in the range from 500:1 to 7:1.

4. The detergent composition in accordance with Claim 1 wherein the soil release agent is present in an amount from 0.1 % to 1.5% by weight in a weight ratio of copolymer to performance additve in the range from 10:1 to 1:1, whereby a 1% aqueous solution of the detergent composition has an alkaline pH (20°C).