EP1941017A1

EP1941017A1 - Method for stabilizing liquid detergent preparations and corresponding liquid detergent preparations

Info

Publication number: EP1941017A1
Application number: EP06806991A
Authority: EP
Inventors: Tanja Seebeck; Helmut GÜMBEL
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2005-10-14
Filing date: 2006-10-05
Publication date: 2008-07-09
Also published as: CA2625927A1; WO2007042450A1; CN101287821A; JP2009511688A; US20080248987A1; DE102005049701A1

Abstract

The invention relates to a method for stabilizing liquid detergent preparations, characterized by adding to the liquid detergent preparation a copolymer which can be obtained by radical copolymerization of (A) 20 to 80 % by weight of at least one monomer from the group of the monoethylenically unsaturated monocarboxylic acids, dicarboxylic acids and dicarboxylic acid anhydrides, and (B) 20 to 80 % by weight of at least one monomer from the group of the aliphatic or aromatic monoolefins.

Description

Process for stabilizing liquid detergent compositions and liquid detergent compositions

description

The present invention relates to a process for the stabilization of liquid detergent compositions and liquid detergent compositions containing a radical copolymerization of

(A) 20 to 80 wt .-% of at least one monomer from the group of monoethylenically unsaturated monocarboxylic acids, dicarboxylic acids and dicarboxylic acid anhydrides

and

(B) 20 to 80 wt .-% of at least one monomer from the group of aliphatic or aromatic monoolefins

available copolymer.

In the formulation of liquid detergent compositions, the problem of phase separation regularly arises. This occurs especially in the presence of larger amounts of builder. Builders are water-soluble inorganic salts, e.g. Alkali metal, especially sodium silicates, carbonates and phosphates, and organic acids or their salts, e.g. Citric acid or sodium citrate, and complexing agents, such as methylglycine diacetic acid (MGDA), which are used to trap the hardness ions of the water. Larger amounts of builder lead to salting out of detergent active surfactants. Therefore, a balanced surfactant / builder ratio should be set for the liquid detergent formulation. In order to allow greater freedom from formulation, therefore, copolymers are added which stabilize the liquid detergent compositions.

In EP-A-346 995 and 727 479, so-called deflocculating polymers having a hydrophilic polymer main chain and hydrophobic side chains are used for this purpose. The backbone is based on unsaturated monocarboxylic acids, dicarboxylic acids and / or alcohols as monomer units. The side chains, which may contain polyalkylene oxide blocks, are attached to the backbone via ester, ether or amide functions.

WO-A-96/02622 discloses the stabilization of liquid detergents with copolymers of acrylic acid and alkoxylated allyl ethers. It is an object of the present invention to provide copolymers with which liquid detergent compositions can advantageously be stabilized against phase separation.

Accordingly, a process for the stabilization of liquid detergent compositions has been found, which is characterized in that one adds to the liquid detergent composition, a copolymer obtained by free-radical copolymerization of

and

is available.

In addition, liquid detergent compositions containing these copolymers have been found.

Finally, there has also been found a process for lowering the viscosity of liquid detergent compositions which is characterized by adding these copolymers to the liquid detergent composition.

The copolymers used according to the invention contain as copolymerized monomer (A) a monoethylenically unsaturated monocarboxylic acid or dicarboxylic acid or a mixture of these acids. The acids can be used in the form of their water-soluble salts, in particular the alkali metal salts, such as potassium and especially sodium salts, or ammonium salts, the dicarboxylic acids can also be wholly or partially in anhydride form. Of course, acid mixtures can also be used.

The monomers (A) preferably contain 3 to 10 carbon atoms.

Specific examples of suitable monomers (A) are: acrylic acid, methacrylic acid, crotonic acid, vinylacetic acid, maleic acid, maleic anhydride, fumaric acid, citraconic acid, citraconic anhydride and itaconic acid. Particularly preferred monomers (A) are acrylic acid, methacrylic acid and maleic acid (anhydride), with maleic acid (anhydride) being very particularly preferred.

The copolymers used according to the invention contain from 20 to 80% by weight, in particular from 30 to 70% by weight, of the monomer (A).

As copolymerized monomer (B), the copolymers used according to the invention contain at least one aliphatic or aromatic monoolefin.

Specific examples of suitable monomers (B) are: 1-butene, isobutene, 1-pentene, 1-hexene, diisobutene (2-methyl-4,4-dimethyl-1-pentene), 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, Ci8-C24-α-olefins such as 1-octadecene, 1-eicosene, 1-docoses and 1-tetracoses, C2o-C24-α-olefin mixtures, 1-hexacoses, polyisobutenes with im Average 12 to 100 carbon atoms and styrene.

The copolymers used according to the invention as component (B) preferably contain a mixture of (B1) at least one monoolefin having <8 carbon atoms and (B2) at least one monoolefin having> 10 carbon atoms.

In particular, isobutene, diisobutene and styrene are suitable as monoolefins (B1). Particularly suitable monoolefins (B2) are 1-dodecene, Ci8-C24-α-olefins, C20-C24-0C-olefin mixtures and polyisobutenes having an average of 12 to 100 carbon atoms.

The copolymers used according to the invention contain from 20 to 80% by weight, preferably from 30 to 70% by weight, of the monomer (B).

Very particularly preferred copolymers used according to the invention are by free-radical copolymerization of (A) 30 to 70 wt .-% maleic acid (anhydride), (B1) 20 to 40 wt .-% isobutene and (B2) 5 to 20 wt .-% of a Ci ₈ -C ₂ 4-α-olefin obtains lent.

The copolymers used according to the invention have an average molecular weight Mw of from 1,000 to 200,000 g / mol, preferably from 2,000 to 50,000 g / mol (determined by gel permeation chromatography at room temperature with aqueous eluent).

Their K values are accordingly from 10 to 150, preferably from 15 to 60 (measured at pH 7 in 1% strength by weight aqueous solution at 25 ° C., according to H. Fikentscher, Cellulose-Chemie, Vol. 13, pp. 58-64 and 71-74 (1932)).

The copolymers used according to the invention can be prepared by known processes. Usually, they are obtained in the form of, in particular, aqueous polymer solutions or dispersions which have a solids content of from 10 to 70% by weight, preferably from 25 to 60% by weight.

The copolymers used in the invention can effectively stabilize liquid detergent compositions against undesirable phase separation. In particular, the copolymers used in the invention may also contain structured surfactant phases, e.g. unilamellar and multilamellar vesicles, stabilize.

The liquid detergent compositions of the invention preferably contain

(a) 0.1 to 10% by weight, in particular 0.25 to 5% by weight, of at least one copolymer according to the invention,

(B) 5 to 70 wt .-%, in particular 15 to 55 wt .-%, especially 25 to 45 wt .-%, of at least one anionic, nonionic, cationic, amphoteric and / or zwitterionic surfactant

and

(C) 1 to 60 wt .-%, in particular 5 to 40 wt .-%, of at least one electrolyte.

Suitable nonionic surfactants (b) are, in particular:

Alkoxylated C 8 -C 22 -alcohols, such as fatty alcohol alkoxylates, oxo alcohol alkoxylates and Guerbet alcohol alkoxylates: The alkoxylation can be carried out using C 2 -C 20 -alkylene oxides, preferably ethylene oxide, propylene oxide and / or butylene oxide. There may be block copolymers or random copolymers. They usually contain from 2 to 50 mol, preferably from 3 to 20 mol, of at least one alkylene oxide per mole of alcohol. Preferred alkylene oxide is ethylene oxide. The alcohols preferably have 10 to 18 carbon atoms.

- Alkylphenolalkoxylate, in particular alkylphenol ethoxylates containing C6-Ci4-alkyl chains and 5 to 30 moles of alkylene oxide / mol.

Alkylpolyglucosides containing C8-C22, preferably Cio-Cis-alkyl chains and usually 1 to 20, preferably 1, 1 to 5, glucoside units.

N-alkylglucamides, fatty acid amide alkoxylates, fatty acid alkanolamide alkoxylates and block copolymers of ethylene oxide, propylene oxide and / or butylene oxide. Suitable anionic surfactants are, for example:

Sulfates of (fatty) alcohols having 8 to 22, preferably 10 to 18, carbon atoms, in particular CgCn alcohol sulfates, C 12 -C 14 -alcohol sulfates, C 12 -C 18 -alcohol sulfates, lauryl sulfate, cetyl sulfate, myristyl sulfate, palmitylsulfate, stearyl sulfate and tallow fatty alcohol sulfate.

Sulfated alkoxylated C 8 -C 22 -alcohols (alkyl ether sulfates): Compounds of this type are prepared, for example, by first obtaining a C 8 -C 22 -alcohol, preferably a C 10 -C 18 -alcohol, e.g. a fatty alcohol, alkoxylated and then sulfated the AIk oxylierungsprodukt. For the alkoxylation is preferably used ethylene oxide.

Linear C 8 -C 20 -alkylbenzenesulfonates (LAS), preferably linear C 9 -C 13 -alkylbenzenesulfonates and -alkyltoluenesulfonates.

Alkanesulfonates, in particular C8-C24-, preferably Cio-Ci8-alkanesulfonates.

- Fatty acid ester sulfonates of the formula R ¹ CH (SO ₃ M) CO ₂ R ² , in the R ¹ C ₆ -C ₂ O -AlkVl, preferably Cs-Ciβ-alkyl, and R ² Ci-C ₄ -AlkVl, preferably methyl or Ethyl, and M is hydrogen or a water-soluble cation, for example, alkali metal cation or ammonium ion.

- Olefinsulfonate having 8 to 22, preferably 12 to 18, carbon atoms.

Isethionates, in particular acyl isethionates and N-acyl taurates.

N-sarcosinates.

Sulfosuccinates (mono- or diesters of sulfosuccinic acid) and alkyl succinates.

Organic phosphate esters, in particular mixtures of mono- and diester phosphates of hydroxyl-terminated alkoxide condensates and their salts. Included therein are polyalkylated alkylaryl phosphate esters, e.g. based on alkoxylated Cs-C22 alcohols or alkoxylated phenol derivatives.

Soaps, such as the Na and K salts of C8-C24 carboxylic acids.

The anionic surfactants are preferably added to the detergent in the form of salts. Suitable salts are, for example, alkali metal salts, such as sodium, potassium and lithium salts, and ammonium salts such as hydroxyethylammonium, di (hydroxyethyl) ammonium and tri (hydroxyethyl) ammonium salts.

Particularly suitable cationic surfactants are:

C7-C25-alkyl amines;

N, N-dimethyl-N- (C7-C25-hydroxyalkyl) ammonium salts;

mono- and di- (C7-C25-alkyl) dimethylammonium compounds quaternized with alkylating agents;

Esterquats, especially quaternary esterified mono-, di- and trialkanolamines esterified with Cs-C22 carboxylic acids;

Imidazolinquats, in particular 1-Alkylimidazoliniumsalze of the formulas I or II

I II in which the variables have the following meaning:

R ³ Ci-C ₂₅ alkyl or C ₂ -C ₂₅ alkenyl;

R ^{4 is} C 1 -C ₄ -alkyl or C 1 -C ₄ -hydroxyalkyl;

R ^{5 is} C 1 -C ₄ -alkyl, C 1 -C ₄ -hydroxyalkyl or a radical R ³ - (CO) -X- (CH ₂ ) _P - (X: -O- or

-NH-; p: 2 or 3), wherein at least one R ^{3 is} C 7 -C 22 alkyl.

Suitable amphoteric surfactants are derivatives of aliphatic or heterocyclic secondary and tertiary amines in which the aliphatic radicals preferably have from 8 to 18 carbon atoms and at least one radical contains one or more anionic water-soluble groups, e.g. one or more carboxylate, sulfonate, sulfate, phosphate or phosphonate groups.

Examples of suitable amphoteric surfactants are:

- 3- (alkylamino) propionates, (alkylamino) acetates, 3- (dialkylamino) propionates and (dialkylamino) acetates, wherein preferably at least one alkyl group contains 8 to 18 carbon atoms. 3 - [(3-alkylaminopropyl) amino] propionates and [(3-alkylaminopropyl) amino] acetate, wherein the alkyl group preferably contains 8 to 18 carbon atoms.

- [(2-Acylaminoethyl) (2-hydroxyethyl) amino] acetate, wherein the acyl group preferably contains 8 to 18 carbon atoms.

(Alkylamino) propanesulfonates, wherein the alkyl group preferably contains 8 to 18 carbon atoms.

Suitable zwitterionic surfactants are, for example:

Amine oxides, in particular alkyldimethylamine oxides and alkyldiethylamine oxides, wherein the alkyl group preferably contains 8 to 18 carbon atoms.

Betaines, in particular carbobetaines, sulfobetaines and phosphobetaines, such as:

R ⁶ (R ⁷ ) 2 N ⁺ (CH 2) n COO with the following preferred meaning of the variables: R ⁶ : Cβ-Ciβ-alkyl; R ⁷ : C ₁ -C ₃ -alkyl; n: 1 to 5.

R ⁶ CONH (CH ₂ ) _m (R ⁷ ) ₂ N ⁺ (CH ₂ ) n COO- with the following preferred meaning of the variables: R ⁶ : C 7 -C 17 -alkyl; R ⁷ : C 1 -C ³ -alkyl; n, m: independently 1 to 5.

R ⁶ (R ⁷ ) 2 _N ⁺ (CH 2) _n SO 3 "with the following preferred meaning of the variables: R ⁶ : Cβ-C 16 -alkyl; R ⁷ : C ₁ -C ₃ -alkyl; n: 1 to 5.

Cocoamidopropyl.

Detailed descriptions of amphoteric and zwitterionic surfactants can be found further in EP-A-851 023 and in Die Tenside, Carl Hanser Verlag, 1993.

As component (c), the liquid detergent compositions according to the invention contain at least one electrolyte. The term "electrolyte" is intended to mean all ionic water-soluble substances. Examples of suitable electrolyte are water-soluble inorganic builders and organic (co) builders.

As electrolyte, in particular:

Carbonates and bicarbonates: These can be used in the form of their alkali metal, alkaline earth metal or ammonium salts. Preferred are Na, Li and

Mg carbonates and hydrogencarbonates, in particular sodium carbonate and / or sodium bicarbonate. Polyphosphates, such as pentasodium triphosphate, pyrophosphates and orthophosphates.

- Low molecular weight carboxylic acids, such as citric acid, hydrophobically modified citric acid, z. , Agaricic acid, malic acid, tartaric acid, gluconic acid, glutaric acid, succinic acid, imidodisuccinic acid, hydroxydisuccinic acid, oxydibrenic acid, propane tricarboxylic acid, butanetetracarboxylic acid, cyclopentanetetracarboxylic acid, alkyl and alkenyl succinic acids and aminopolycarboxylic acids, e.g. Nitrilotriacetic acid, .beta.-alaninediacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, serinediacetic acid, isoserinediacetic acid, glutamic acid diacetic acid, N- (2-hydroxyethyl) iminodiacetic acid, ethylenediamine disuccinic acid and methyl- and ethylglycinediacetic acid and salts thereof.

Crystalline and amorphous silicates, in particular disilicates, metasilicates and

Phyllosilicates, e.g. δ- and ß-Na2Si2θs The silicates can be used in the form of their alkali metal, alkaline earth metal or ammonium salts, preferred are the Na, Li and Mg silicates.

- Alkali metal hydroxides, especially sodium and potassium hydroxide.

Other inorganic salts such as alkali metal and alkaline earth metal chlorides, sulfates and borates.

The liquid detergent compositions of the invention may also contain other ingredients, such as

Crystalline and amorphous aluminosilicates with ion-exchanging properties, in particular zeolites: Various types of zeolites are suitable, in particular the zeolites A, X, B, P, MAP and HS in their Na form or in forms in which Na partially opposes other cations such as Li, K, Ca, Mg or ammonium are exchanged.

Oligomeric and polymeric carboxylic acids, such as homopolymers of acrylic acid and aspartic acid, oligomaleic acids, copolymers of maleic acid with acrylic acid,

Methacrylic acid or C 2 -C 22 -olefins, for example isobutene or long-chain α-olefins, vinyl-C 1 -C 8 -alkyl ethers, vinyl acetate, vinyl propionate, (meth) acrylic esters of C 1 -C 5 -alcohols and styrene. Preferred are the homopolymers of acrylic acid and copolymers of acrylic acid with maleic acid. The oligomeric and polymeric carboxylic acids are used in acid form or as the sodium salt. Other common ingredients such as enzymes, perfume, corrosion inhibitors, bleaches, bleach activators, bleach catalysts, dye transfer inhibitors, scorch inhibitors, anti-redeposition polymers, soil release polyesters, fiber and color protective additives, optical brighteners, silicones, dyes, bactericides, preservatives , organic solvents, solubilizers, hydrotropes, thickeners and alkanolamines.

Detergent ingredients are well known. Detailed descriptions are e.g. in WO-A-99/06524 and 99/04313 as well as in Liquid Detergents, Editor: Kuo-Yann Lai, Surfactant Sei. Ser., Vol. 67, Marcel Decker, New York, 1997, p. 272-304, to find.

Examples

The stability of various liquid detergent compositions was examined in the presence and absence of the copolymer P.

The copolymer P was a copolymer of maleic anhydride, isobutene and 1-octadecene in a weight ratio of 65: 26: 9, having an average molecular weight M _w of 3000 g / mol and a K value of 24 (measured at pH 7 in 1% strength by weight aqueous solution at 25 ° C.). The copolymer was used in the form of a 40 wt .-% aqueous solution.

To test their stability, the liquid detergent compositions were stored for 4 weeks at room temperature.

Their composition is tabulated below. The amounts given for the polymeric ingredients are based on the solids.

Sokalan ^® : registered trademark of BASF Aktiengesellschaft

C ⁾ acrylic acid / maleic acid copolymer; Graying and incrustation inhibitor

< ² > modified polycarboxylate, Na salt; antiredeposition

⁽³⁾ copolymer of nonionic character; Anti-redeposition polymer

< ⁴ > vinylpyrrolidone / vinylimidazole copolymer; Color transfer inhibitor

All liquid detergent compositions showed no phase separation after storage.

For comparison, liquid detergent compositions which did not contain polymer P showed marked separation after just a few hours.

Claims

claims

A process for the stabilization of liquid detergent compositions, which comprises adding to the liquid detergent composition a copolymer obtained by free-radical copolymerization of

(A) 20 to 80 wt .-% of at least one monomer from the group of monoethylenically unsaturated monocarboxylic acids, dicarboxylic acids and dicarboxylic anhydrides

and

is available.

2. The method according to claim 1, characterized in that one uses a copolymer based on at least one monomer (A) from the group of maleic acid, maleic anhydride and acrylic acid.

3. The method according to claim 1 or 2, characterized in that a copolymer based on at least one monomer (B) from the group isobutene, diisobutene, 1-dodecene, Ci8-C24-α-olefins, C2o-C24-α -Olefingemische, polyisobutenes having an average of 12 to 100 carbon atoms and styrene.

4. Process according to claims 1 to 3, characterized in that one uses a copolymer which comprises on a mixture of (B1) at least one monoolefin having <8 carbon atoms and (B2) at least one monoolefin having> 10 carbon atoms as component ( B).

5. Process according to claims 1 to 4, characterized in that one uses a copolymer obtained by free-radical copolymerization of (A) 30 to 70 wt .-% maleic acid or maleic anhydride, (B1) 20 to 40 wt .-% isobutene and (B2) 5 to 20 wt .-% of a Ci ₈ -C ₂ 4-α-olefin is available.

6. Process according to claims 1 to 5, characterized in that the liquid detergent compositions have structured surfactant phases.

7. Liquid detergent compositions containing a copolymer according to claims 1 to 5.

8. Liquid detergent compositions containing

(a) 0.1 to 10% by weight of at least one copolymer according to claims 1 to 5,

(B) 5 to 70 wt .-% of at least one anionic, nonionic, cationic, amphoteric and / or zwitterionic surfactant

and

(c) 1 to 60% by weight of at least one electrolyte.

9. A process for lowering the viscosity of liquid detergent compositions, characterized in that the liquid detergent composition is added to a copolymer according to claims 1 to 5.