EP0743358A1 - Composition for washing and cleaning of textile materials - Google Patents

Abstract

- A compsn. contg. (A) 5-95 wt.% dicarboxylic ester(s) of the formula R1-OOC-R-COO-R2 (R1, R2 = 1-15 C alkyl, 5-7 C cycloalkyl or aryl; R = a divalent bridging gp.), (B) 95-5 wt.% washing-active surfactant(s) (II) and (C) opt. water and/or other additives is claimed. Also claimed are (a) aq. washing liquors contg. 0.5-5.0 wt.% of this compsn., in addn. to usual washing ancillaries; (b) a method of producing the compsn.; and (c) a process for washing textile substrates.

Description

The invention relates to a new composition for washing and cleaning textile materials and their production, and their use especially for washing and cleaning textile substrates, as well as a washing liquor containing the new composition, and a method for washing and cleaning textile substrates under Use or add the new composition.

Washing and cleaning textile substrates from an aqueous washing liquor is a well-known process. Depending on the detergent additives, more or less well washed or cleaned textile substrates are obtained. The detergent additives are mostly surface-active substances, especially anionic and nonionic in nature, optionally together with conventional solvents such as terpenes. Especially in the case of heavily soiled textile substrates, these detergent additives often do not lead to the desired success, especially not if they are heavy, e.g. with greases, polydimethylsiloxanes and machine oil, dirty textile substrates.

It was therefore an object of the invention to develop an additive to an aqueous washing liquor, according to which textile substrates can be washed and cleaned in aqueous systems, the disadvantages indicated above being overcome, i.e. an additive that is able to wash and clean even a heavily stained textile substrate from an aqueous washing liquor.

The solution to this problem lies in the use of a new washing and cleaning composition which contains, as essential components, a combination of at least one specific dicarboxylic acid ester and a detergent-active, surface-active substance.

• A) 5 bis 95 Gew.% mindestens eines Dicarbonsäureesters der allgemeinen Formel I
  
          R₁―OOC―R―COO―R₂     (I)
  
  worin bedeuten:
  R₁ und R₂ unabhängig voneinander einen C₁-C₁₅ Alkylrest, einen C₅-C₇ Cycloalkylrest oder einen aromatenhaltigen Rest und R ein bivalentes Brückenglied;
• B) 95 bis 5 Gew.% mindestens einer waschwirksamen grenzflächenaktiven Substanz, und
• C) gegebenenfalls Wasser und/oder weitere Zusätze.

The invention thus relates to a composition comprising:

• A) 5 to 95% by weight of at least one dicarboxylic acid ester of the general formula I
  
  R ₁ ―OOC ― R ― COO ― R ₂ (I)
  
  in which mean:
  R ₁ and R ₂ independently of one another are a C ₁ -C ₁₅ alkyl radical, a C ₅ -C ₇ cycloalkyl radical or an aromatic-containing radical and R is a bivalent bridge member;
• B) 95 to 5% by weight of at least one detergent surfactant, and
• C) optionally water and / or other additives.

Furthermore, the invention relates to processes for producing this composition and its use, above all for washing and cleaning textile substrates, and also to a washing liquor containing the new composition and a process for washing and cleaning textile substrates with the addition of the new composition.

Cleaning compositions which contain dicarboxylic acid esters of the formula I are known (for example EP-A-0 351 810, EP-A-0 412 475, WO 94/29392 and WO 90/08603), but do not contain a detergent surfactant in combination, but instead rather a terpene (e.g. EP-A-0351 810) or a specific solvent (e.g. EP-A-0 412 475 or WO 94/29392) and / or are used entirely for other substrates, especially electronic circuits (e.g. WO 90 / 08603).

Component A) of the composition according to the invention corresponds to formula I.

R in the meaning of a bivalent bridge member provides especially a C ₁ - C ₂₀ alkylene is a C ₂ -C ₂₀ alkenylene, a C ₅ -C ₇ Cycloalkylenbrücke or an aromatic bridge member.

If it is a C ₁ -C ₂₀ alkylene bridge, the bivalent alkylene radical can be straight-chain or branched-chain. Examples of such bridge members are: methylene, ethylene, n- and iso-propylene, n-, iso- and tert-butylene, n- and iso-amylene, n- and iso-hexylene, n- and iso-heptylene, n - And iso-octylene, n- and iso-decylene, n- and iso-undecylene, n- and iso-dodecylene, n- and iso-tridecylene and n- and iso-pentadecylene. R can also represent a polyalkylene oxide radical.

All these C ₁ -C ₂₀ alkylene radicals R can be unsubstituted or substituted one or more times, identically or differently. Examples of suitable substituents are: a C ₁ -C ₄ alkoxy group (straight or branched, such as the methoxy, ethoxy or n-butoxy group); an amino group; a monoalkyl (C ₁ -C ₆ ) amino group (e.g. -NH (CH ₃ )); a dialkyl (C ₁ -C ₆ ) amino group (eg -N (C ₂ H ₅ ) ₂ ); a carboxyl group; a carboxylic acid C ₁ -C ₄ alkyl ester group; SO ₂ NH ₂ ; the sulfonic acid group, hydroxy and halogen (such as F, Cl and Br).

Preferred alkylene bridges R are straight-chain, unsubstituted or substituted one or more times by hydroxyl and in particular have 2 to 4 carbon atoms. For example, they represent the - (CH ₂ ) ₂ -, - (CH ₂ ) ₃ -, or the - (CH ₂ ) ₄ - residue.

If R is a C ₂ -C ₂₀ alkenylene bridge, both straight-chain and branched-chain alkenylene bridges are suitable. Examples are the residues of unsaturated dicarboxylic acids, especially the β-dicarboxylic acids such as cis and trans - (CH = CH) -, cis and trans - (C (CH ₃ ) = CH) - and - (C (= CH ₂ ) -CH ₂ ) -.

If R is a C ₅ -C ₇ cycloalkylene bridge, it is, for example, the bivalent radical of cyclopentane, cyclohexane or cycloheptane; these radicals can be substituted, for example by one or more C ₁ -C ₅ alkyl groups; it is preferably cyclohexylene or cyclohexylene-C ₁ -C ₄ -alkylene, such as cyclohexylmethylene, for example trimethylcyclohexylmethylene.

If R is an aromatic bridge member, there is above all a bivalent arylene radical, such as phenylene, which is unsubstituted or substituted, for example, by C ₁ -C ₆ alkyl or C ₁ -C ₆ alkoxy, in particular the 1,3-phenylene or 1,4-phenylene radical or Arylenalkylenearylene radical, especially phenylene-C ₁ -C ₄ -alkylene-phenylene such as phenylene-ethylene-phenylene, into consideration.

For example, R is the residue

R ₁ and R ₂ in the meaning of a C ₁ -C ₁₅ alkyl radical represents a straight-chain or branched-chain alkyl radical which is unsubstituted or can be substituted one or more times, identically or differently. The following radicals are mentioned, for example: methyl, ethyl, n- and iso-propyl, n-, iso- and tert-butyl, n- and iso-amyl, n- and iso-octyl, n- and iso-decyl and the Tridecyl residue.

Examples of substituents are the same in question which are mentioned under the symbol R, one of the two valences e.g. is saturated by H.

If R ₁ and R _{2 are} a C ₅ -C ₇ cycloalkyl radical, it is the cyclopentyl, cyclohexyl or cycloheptyl radical. These cycloalkyl radicals can be substituted, for example by C ₁ -C ₄ alkyl.

If R ₁ and R _{2 are} an aromatic-containing radical, it is primarily the benzyl, phenyl or α- or β-naphthyl radical, which radicals are, for example, by C ₁ -C ₄ alkyl or halogen or sulfonic acid or salts thereof can be substituted.

In the preferred dicarboxylic acid esters of the formula I, R ₁ and R ₂ independently of one another denote a C ₁ -C ₄ alkyl radical.

Component A) can be a single connection, e.g. act the dimethyl adipate, dimethyl glutarate, dimethyl succinate, dimethyl maleate or the corresponding n-butyl ester or tridecyl methyl ester, or also a mixture of different ester compounds of formula I. A preferred mixture is e.g. a technical mixture of 15-20% by weight dimethyl adipate, 60-70% by weight dimethyl glutarate and 15-20% by weight dimethyl succinate.

Component A) is present in the composition in a total amount of about 5 to 95% by weight, especially about 8 to 67% by weight and in particular 20 to 35% by weight.

All components A) are known and can be produced in a known manner.

Suitable wash-active, surface-active substances according to component B) are, in particular, those which have a lipophilic hydrocarbon radical and one or more hydrophilic functional groups; they are both cationic and anionic, nonionic and ampholytic compounds.

As cationic, surface-active substances, e.g. called: tetraalkylammonium salts, imidazolinium salts and amine oxides.

Anionic, surface-active substances are, for example, those of the sulfonate and sulfate type, such as, in particular, linear alkylbenzenesulfonates with advantageously 10 to 18 carbon atoms, in particular 10 to 13 carbon atoms in the alkyl group, and branched-chain alkylbenzenesulfonates, then olefin sulfonates, ie mixtures of alkene and Hydroxyalkanesulfonates and disulfonates; also alkanesulfonates, especially secondary alkanesulfonates; Lignin sulfonates; Petroleum sulfonates, aryl ether disulfonates; Esters of sulfonated fatty acids such as sulfosuccinic acid esters; Alkyl sulfates; Alkyl ether sulfates; also fatty acid esters, such as α-sulfofatty acid methyl ester; Mono- and diphosphoric acid esters such as alkyl phosphates and alkyl ether phosphates; anionic, surface-active substances based on higher fatty acids, eg pages with 8 to 22 carbon atoms; Pages that are derived from mixtures of fatty acids that are made from coconut oil and day are particularly advantageous, then sarcosinates of the general formula R ₃ CO-N (CH ₃ ) CH ₂ COONa wherein R _{3 is} a C ₁ -C ₂₂ saturated or a one or means polyunsaturated alkyl radical; Asparaginates of the general formula R ₃ CO-NH (COONa) (CH ₂ ) ₂ COONa, fatty alkyl ether carboxylates of the general formula R ₃ (OCH ₂ CH ₂ ) n-1-OCH ₂ COONa, in which n is 1-30; also sulfated fats and oils.

All of these anionic, surface-active substances can be used individually or as mixtures; technical products can also be used.

The anionic surfactants can e.g. in the form of their sodium, potassium and ammonium salts as well as soluble salts of organic bases, e.g. as the triethanolamine salt.

Examples of suitable nonionic, surface-active substances (nonionics) are: -alkylene oxide condensation products or addition products to fatty alcohols, such as, for example, condensation products from a C ₁₀ -C ₂₂ alcohol with 3 to 20 moles of ethylene oxide, for example: a condensation product of 5,7,9 or 12 moles of ethylene oxide to isotridecyl alcohol; Addition products of alkylphenol (advantageously C ₆ -C ₁₈ alkyl), fatty acid, fatty amine, fatty acid amide or alkanesulfonamide with 3 to 25 mol of alkylene oxide, especially ethylene oxide, for example nonylphenol, condensed with about 9.5 mol of ethylene oxide or dodecylphenol condensed with about 12 mol of ethylene oxide; also polyhydroxy compounds such as fatty acid glycerides (normal and mixed), sorbitan esters, alkyl polyglycosides and fatty acid amides such as coconut fatty acid diethanolamide.

Mixtures of nonionic, surface-active substances are also useful.

All of these nonionic, surface-active substances are known and can be obtained in a known manner.

Examples of ampholytic, surface-active substances are: derivatives of aliphatic quaternary ammonium compounds in which one of the aliphatic radicals consists of a C ₈ -C ₂₂ radical and another contains an anionic water-solubilizing carboxy, sulfo or sulfato group. Typical representatives of such surface-active betaines are, for example, the compounds 3- (N-hexadecyl-N, N-dimethylammonio) propane sulfonate; 3- (N-tallow alkyl-N, N-dimethyl-ammonio) -2-hydroxypropanesulfonate; 3- (N-hexadecyl-N, N-bis (2-hydroxyethyl) ammonio) -2-hydroxypropyl sulfate; 3- (N-cocoalkyl-N, N-bis (2,3-dihydroxypropyl) ammonium) propane sulfonate; N-tetradecylN, N-dimethyl-ammonioacetate and N-hexadecyl-N, N-bis (2,3-dihydroxypropyl) ammonium acetate. Glycine or aminopropionic acid substituted with fatty alkyl radicals and reaction products of N-fatty acylhydroxyethyl-1,2-diaminoethane with chloroacetic acid can also be used.

Preferred are nonionic and / or anionic surfactants, i.e. single compounds or mixtures of two or more different surface-active substances can be considered, e.g. a mixture of different nonionic surfactants or e.g. a mixture of one or more nonionic compounds with a mixture of one or more anionic compounds.

Particularly useful as a result of the high cleaning power are a nonionic, surface-active substance such as, in particular, an alkylene oxide condensation product from a C ₁₀ -C ₂₂ alcohol with 3 to 20 moles of ethylene oxide, in particular a condensation product of 5, 7, 9 or 12 moles of ethylene oxide with isotridecyl alcohol or one Mix of two or more non-ionic, Surface-active substances, such as a mixture of 80 to 100 moles, preferably 90 moles, of an adduct of 5, 7, 9 or 12 moles of ethylene oxide with isotridecyl alcohol, preferably together with 1 to 20 moles, in particular 10 moles, of coconut fatty acid diethanolamide. The total surface-active substance is present in the composition according to the invention in an amount of about 95 to 5% by weight, especially 92 to 10% by weight, in particular 15 to 25% by weight or in an amount of 50 to 65% by weight.

In addition to the mandatory components A) and B), the composition can also contain water and / or other additives such as e.g. Solubilizers, buffer substances, solvents and / or foam suppressants, in total in an amount of about 0.1% by weight to 80% by weight based on the composition.

Solubilizers are understood to mean substances which, by their presence, make other compounds which are practically insoluble in a particular solvent soluble or emulsifiable in this solvent.

Examples of suitable solubilizers are:
Monohydric alcohols, such as ethanol; dihydric alcohols, such as ethanediol, hexylene glycol (2-methyl-2,4-pentanediol), 1,2-propylene glycol, 1,4-butanediol; trihydric alcohols such as glycerin; (Polyglycols, e.g. polyethylene glycol; polypropylene glycol); Ethers from reactions of short-chain alcohols with epoxides such as ethylene oxide, propylene oxide, butylene oxide in different molar ratios, such as butyl glycol and butyl diglycol.

The solubilizers can be present in amounts of about 3% by weight to 20% by weight, based on the total amount of component C).

Possible buffer substances are, for example:
Synergistic systems of individual components or a wide variety of blends; such as phosphates; Salts of halogen acids with amines; Alkali metal carboxylates such as sodium acetate; Sodium citrate; Free mono-, di- and polycarboxylic acids such as acetic acid; Glutaric acid, adipic acid; Succinic acid; Citric acid; Tartaric acid; Maleic acid; Phthalic acid; Alkali metal carbonates and bicarbonates; Borates; Aminocarboxylic acid such as amino acetic acid.

The buffer substances can be present in amounts of about 0.5% by weight to 20% by weight, based on the total amount of component C).

Examples of solvents which can be added to the composition are those which are compatible with component A), the dicarboxylic acid ester, such as terpenes; Pine oils; aliphatic or aromatic hydrocarbons, hydrocarbons on a heterocyclic basis such as N-methylpyrrolidone;
Esters (with the exception of those which come under component A) from short-chain carboxylic acids with different alcohols (such as acetic acid ester, lactic acid ester) or glycols, glycol ethers or glycol ether esters (such as methoxybutyl acetate, butyl diglycol acetate); then ketones such as acetone; Butanone; Cyclohexanone, methylcyclohexanone; Alcohols such as ethanol; 1-propanol; 1-butanol; 2-butanol; higher alcohols and substituted amides such as dimethylformamide.

These solvents can be present in amounts of about 5% by weight to 80% by weight, based on the total amount of component C).

Examples of foam suppressants are emulsions from mineral oils; Polydimethylsiloxanes; Fatty acid esters; micronized waxes (amide waxes, oxidized polyethylenes); Block polymers based on different polyethers such as poly-ethylene oxide-propylene oxide, poly-ethylene oxide-butylene oxide; higher alcohols, especially branched oxo alcohols with C ₈ -C ₁₅ (such as 2-ethylhexanol; isodecyl alcohol; isotridecyl alcohol) and trialkyl phosphates (such as tributyl phosphate, triisobutyl phosphate, and tri-2-ethylheryl phosphate).

These foam damping agents can be present in amounts of approximately 0.1% by weight to 30% by weight, based on the total amount of component C).

Furthermore, other conventional additives for detergents, such as enzymes, dirt carriers, fabric softeners, antimicrobial agents, colorants and fragrances, and graying inhibitors, e.g. Carboxymethyl cellulose can be added to the composition.

All these additives mentioned are known to the person skilled in the art.

• A) 8 bis 67 Gew.% einer technischen Mischung aus etwa 17 Gew.% Adipinsäuredimethylester, etwa 66 Gew.% Glutarsäuredimethylester und etwa 17 Gew.% Bernsteinsäuredimethylester,
• B) 15 bis 25 Gew.% einer Mischung eines Kondensationsproduktes aus einem C₁₀-C₂₂ Alkohol mit 3 bis 20 Mol Ethylenoxid und Kokosfettsäurediethanolamid, und
• C) gegebenenfalls Wasser und/oder weitere Zusätze, oder
• A) 20 bis 35 Gew.% einer technischen Mischung aus etwa 17 Gew.% Adipinsauredimethylester, etwa 66 Gew.% Glutarsäuredimethylester und etwa 17 Gew.% Bernsteinsäuredimethylester,
• B) 50 bis 65 Gew.% einer Mischung eines Kondensationsproduktes aus einem C₁₀-C₂₂ Alkohol mit 3 bis 20 Mol Ethylenoxid und Kokosfettsäurediethanolamid, und
• C) 10 bis 15 Gew.% Wasser und gegebenenfalls weitere Zusätze, oder
• A) 8 bis 67 Gew.% einer technischen Mischung aus etwa 17 Gew.% Adipinsäuredimethylester, etwa 66 Gew.% Glutarsäuredimethylester und etwa 17 Gew.% Bernsteinsäuredimethylester,
• B) 15 bis 25 Gew.% einer Mischung eines Kondensationsproduktes aus einem C₁₀-C₂₂ Alkohol mit 3 bis 20 Mol Ethylenoxid, und
• C) 40 bis 50 Gew.% Wasser und gegebenenfalls weitere Zusätze.

Particularly interesting compositions due to their very good washing and cleaning action, especially on textile substrates, contain above all

• A) 8 to 67% by weight of an industrial mixture of about 17% by weight dimethyl adipate, about 66% by weight dimethyl glutarate and about 17% by weight dimethyl succinate,
• B) 15 to 25% by weight of a mixture of a condensation product of a C ₁₀ -C ₂₂ alcohol with 3 to 20 moles of ethylene oxide and coconut fatty acid diethanolamide, and
• C) optionally water and / or other additives, or
• A) 20 to 35% by weight of an industrial mixture of about 17% by weight dimethyl adipate, about 66% by weight dimethyl glutarate and about 17% by weight dimethyl succinate,
• B) 50 to 65% by weight of a mixture of a condensation product of a C ₁₀ -C ₂₂ alcohol with 3 to 20 moles of ethylene oxide and coconut fatty acid diethanolamide, and
• C) 10 to 15% by weight of water and optionally further additives, or
• A) 8 to 67% by weight of an industrial mixture of about 17% by weight dimethyl adipate, about 66% by weight dimethyl glutarate and about 17% by weight dimethyl succinate,
• B) 15 to 25% by weight of a mixture of a condensation product from a C ₁₀ -C ₂₂ alcohol with 3 to 20 mol of ethylene oxide, and
• C) 40 to 50 wt.% Water and optionally other additives.

The compositions according to the invention are produced, for example, by homogeneously mixing and stirring components A), B) and C) at a temperature of about 5 to 100 ° C.

The compositions according to the invention are liquid and represent a solution, emulsion or dispersion, are stable on storage at a temperature of about 0 ° to 50 ° C. over a period of more than 6 months; they are also low-odor, very good biologically, more than 80% in the biological purification stages of the sewage treatment plants, degradable and difficult to volatile.

The compositions according to the invention are used above all in an aqueous washing liquor for cleaning and removing impurities and stains from textile substrates.

They can thus be used in a washing and cleaning process which serves to remove dirt and stains from an aqueous washing liquor.

This use represents a further object of the invention. It is surprising that the composition can be used in an aqueous washing liquor, since it had to be assumed that hydrolysis of the dicarboxylic acid esters took place; however, this is not the case. The compositions according to the invention are stable to hydrolysis in the intended application.

A wide variety of substrates, in particular soiled and / or heavy stains or dirt edges, can be considered as textile substrates; in particular, there are substrates which can be subjected to an aqueous wet-washing treatment, such as textile fibers, textile semi-finished and finished products and finished products made therefrom, such as brands of the clothing industry, the household industry, carpets and textiles used for technical purposes Structures such as underwear, shirts, socks, stockings, skirts, pants, pullovers, professional underwear etc.

All of these substrates can be printed or colored, and can be in the form of fibers, yarns, fabrics or knits.

Soiling mainly consists of natural dust, skin fat, sweat and dander.

Stains are e.g. the oil smudges from machines, then lime soap stains, drip stains, foam stains, wet stains, smudges from e.g. Greases, mold stains, water stains, beverage stains, fruit stains, grease stains, sweat stains, blood stains, rust stains, paint stains (e.g. from ink, copy pens, crayons, pens), grass stains, and stains from printing pastes and chocolate masses.

The fibers are primarily natural fibers of vegetable origin such as Cotton, flax, hemp, jute, coconut, manila or sisal; natural fibers of animal origin such as Wool, (angora, alpaca, camel, cashmere, goat hair, etc.) and silk; then chemical fibers such as copper silk, viscose fibers, modal fibers, acetate, triacetate, polyisoprene, elasto fibers, polyacrylic fibers, polyamide fibers, polyvinyl chloride fibers, polyester fibers, polyolefin fibers, polyvinyl alcohol fibers as well as textile fabrics such as woven goods (fabrics, carpets), knitted fabrics (knitted and knitted fabrics) , Needle felt and needle pile carpets, as well as nonwovens.

But it can also be mixed fabrics such as around mixtures of natural fibers with artificial fibers such as a PES / wool blend.

The compositions according to the invention are also used as cleaning agents for hard and mechanically solid surfaces such as metals and alloys in the form of, for example, semi-finished products such as sheets, plates, sheets, strips, rods, profiles, wires, tubes, hoses, ropes or components such as window profiles, Window sills, roller shutter slats, shutters, doors, door leaves, frames; Packaging such as bottles, barrels, cans, lids, storage containers and consumer goods such as consumer goods and office furniture. Suitable metals are, for example, light metals and heavy metals such as iron, steel, copper, zinc or aluminum and their alloys. Furthermore, the composition according to the invention is used to clean mechanically firm polymeric surfaces such as plastics, for example thermoplastics such as polyethylene, polypropylene, polystyrene, polyamides, polycarbonates, polyacrylates, polymethacrylates, polyesters, polyvinyl chloride, then thermosets such as phenol-formaldehyde resins, melamine and Urea-formaldehyde resins and also as a cleaning agent for mechanically solid painted surfaces.

The invention further relates to an aqueous wash liquor containing 0.05 to 5.0% by weight of the composition according to the invention in addition to customary washing aids, and to a process for washing textile substrates by adding 0.05 to 5.0% by weight of the composition mentioned to the aqueous wash liquor before or during the washing process and a method for washing textile substrates by adding at least one dicarboxylic acid ester of the general formula I before or during the washing process in such an amount that the wash liquor contains 0.01 to 30% by weight of the dicarboxylic acid ester of the formula I.

The liquor ratio of the wash liquor is approximately 1: 7 to 1:50 and especially 1:20 to 1:30.

• A) 8 bis 67 Gew.% einer technischen Mischung aus etwa 17 Gew.% Adipinsäuredimethylester, etwa 66 Gew.% Glutarsäuredimethylester und etwa 17 Gew.% Bernsteinsäuredimethylester,
• B) 15 bis 25 Gew.% einer Mischung eines Kondensationsproduktes aus einem C₁₀-C₂₂ Alkohol mit 3 bis 20 Mol Ethylenoxid und Kokosfettsäurediethanolamid, und
• C) gegebenenfalls Wasser und/oder weitere Zusätze, oder
• A) 20 bis 35 Gew.% einer technischen Mischung aus etwa 17 Gew.% Adipinsäuredimethylester, etwa 66 Gew.% Glutarsäuredimethylester und etwa 17 Gew.% Bernsteinsäuredimethylester,
• B) 50 bis 65 Gew.% einer Mischung eines Kondensationsproduktes aus einem C₁₀-C₂₂ Alkohol mit 3 bis 20 Mol Ethylenoxid und Kokosfettsäurediethanolamid, und
• C) 10 bis 15 Gew.% Wasser, und gegebenenfalls weitere Zusätze, oder
• A) 8 bis 67 Gew.% einer technischen Mischung aus etwa 17 Gew.% Adipinsäuredimethylester, etwa 66 Gew.% Glutarsäuredimethylester und etwa 17 Gew.% Bernsteinsäuredimethylester,
• B) 15 bis 25 Gew.% einer Mischung eines Kondensationsproduktes aus einem C₁₀-C₂₂ Alkohol mit 3 bis 20 Mol Ethylenoxid, und
• C) 40 bis 50 Gew.% Wasser und gegebenenfalls weitere Zusätze.

Washing liquors according to the invention, which have a particularly good washing ability at a bath temperature of 5 ° -100 ° C., contain a composition according to the invention, containing

• A) 8 to 67% by weight of an industrial mixture of about 17% by weight dimethyl adipate, about 66% by weight dimethyl glutarate and about 17% by weight dimethyl succinate,
• B) 15 to 25% by weight of a mixture of a condensation product of a C ₁₀ -C ₂₂ alcohol with 3 to 20 moles of ethylene oxide and coconut fatty acid diethanolamide, and
• C) optionally water and / or other additives, or
• A) 20 to 35% by weight of an industrial mixture of about 17% by weight dimethyl adipate, about 66% by weight dimethyl glutarate and about 17% by weight dimethyl succinate,
• B) 50 to 65% by weight of a mixture of a condensation product of a C ₁₀ -C ₂₂ alcohol with 3 to 20 moles of ethylene oxide and coconut fatty acid diethanolamide, and
• C) 10 to 15% by weight of water, and optionally further additives, or
• A) 8 to 67% by weight of an industrial mixture of about 17% by weight dimethyl adipate, about 66% by weight dimethyl glutarate and about 17% by weight dimethyl succinate,
• B) 15 to 25% by weight of a mixture of a condensation product from a C ₁₀ -C ₂₂ alcohol with 3 to 20 mol of ethylene oxide, and
• C) 40 to 50 wt.% Water and optionally other additives.

A particularly good washing action is achieved if component B) of the composition according to the invention is a mixture of alkylene oxide, especially ethylene oxide, condensation products with different degrees of ethoxylation with isotridecyl alcohol.

The washing of the textile materials using the composition according to the invention or a dicarboxylic acid ester of the general formula I alone, especially a technical mixture of about 17% by weight dimethyl adipate, about 66% by weight dimethyl glutarate and about 17% by weight dimethyl succinate is carried out in such a way that the items to be washed (e.g. textile material) are moved manually or mechanically in an aqueous washing liquor at a temperature of 0 ° C to 100 ° C, especially 30 ° C to 60 ° C, and the items are then separated from the washing liquor and washed with water until they are complete Removal of the wash liquor rinses.

The laundry thus washed has, compared to a laundry washed with conventional solvents, instead of the dicarboxylic acid esters of the formula I which can be used according to the invention, substantially better washing effects, such as fabric brightness.

The following examples serve to illustrate the invention. These examples are not intended to limit the invention in any way, for example within the scope of the examples.

example 1

82.0 g of 5-mole ethylene oxide adduct of isotridecyl alcohol are placed in a 1 liter glass beaker with an anchor stirrer while stirring. Subsequently, 68.4 g of isotridecyl alcohol 7 mol ethylene oxide adduct, 37.8 g isotridecyl alcohol 9 mol ethylene oxide adduct and 50.0 g coconut fatty acid diethanolamide (coconut fatty acid chain length distribution: C ₈ : 8%, C ₁₀ : 7%, C ₁₂ : 46%, C ₁₄ : 18%, C ₁₆ : 8%, C ₁₈ : 13%) with stirring and stirred until a homogeneous distribution is reached. With stirring, a mixture of 80.0 g of 2-methyl-2,4-pentanediol and 670.0 g of a completely biodegradable dicarboxylic acid ester mixture with the following typical composition is obtained within 30 minutes: 17% dimethyl adipate, 66% dimethyl glutarate, 16.5% Dimethyl succinate, 0.2% methanol and 0.1% water added. To stabilize the hydrolysis, a solution of 2.0 glutaric acid and 9.8 g of demineralized water is also introduced and stirred until a clear homogeneous solution is reached. A composition is obtained which contains about 67% by weight of the dicarboxylic acid ester mixture and 23.8% by weight of the surface-active substances.

Example 2 (comparative example)

82.0 g of 5-mole ethylene oxide adduct of isotridecyl alcohol are placed in a 1 liter glass beaker with an anchor stirrer while stirring. Then 68.4 g of isotridecyl alcohol-7 mol ethylene oxide adduct, 37.8 g of isotridecyl alcohol-9 mol ethylene oxide adduct and 50.0 g of coconut fatty acid diethanolamide (Coconut fatty acid chain length distribution: C ₈ : 8%, C ₁₀ : 7%, C ₁₂ : 46%, C ₁₄ : 18%, C ₁₆ : 8%, C ₁₈ : 13%) and stirred until a homogeneous distribution is reached. A mixture of 80.0 g of 2-methyl-2,4-pentanediol and 670.0 g of terpenes (typical analysis: 96.2% dl-limonene, 1.9% myrcene, 0.5% α-pinene) is added with stirring within 30 minutes , 0.4% β-pinene, 1.0% residual components).

11.8 g of demineralized water are introduced into this mixture and the mixture is stirred until a homogeneous solution is reached.

Example 3 (comparative example)

104.0 g of 2-mole ethylene oxide adduct of isotridecyl alcohol are placed in a 1 liter glass beaker with an anchor stirrer while stirring. Then 92.8 g of isotridecyl alcohol-7 mol ethylene oxide adduct, 116.8 g of isotridecyl alcohol-9 mol ethylene oxide adduct and 40.0 g of 2-methyl-2,4-pentanediol are added and the mixture is stirred until homogeneous distribution is achieved. A solution of 52.5 g of a linear C ₁₀ -C ₁₃ alkylbenzene sulfonate (75% sodium salt) and 25.4 g of coconut fatty acid diethanolamide (composition analogous to Example 1) in 568.5 g of demineralized water is then added dropwise with stirring over the course of 20 minutes and until a homogeneous, light mixture is reached pseudoplastic phase stirred.

Example 4

In a 1 liter four-necked flask with stirring device and distillation bridge, 328.12 g (2 mol) of dicarboxylic acid esters (composition: 17% dimethyl adipate, 66% dimethyl glutarate, 16.5% dimethyl succinate), 296.48 g (4 mol) 1-butanol and 5.00 g (0.015 mol) Tetra-1-butyl titanate entered with vigorous stirring.

This mixture is slowly heated to 140 ° C. over 5 hours and 138.2 g of distillate are removed. By evacuating at 100 hPh absolute pressure and 140 ° C a further 25.3g distillate are obtained. The total amount of distillate is 163.5 g (128% of theory). The reaction mixture is then cooled to 20 ° C. A mixture of the corresponding dibutyl esters is obtained as the main component.

Example 5

328.12 g (2 moles) of dicarboxylic acid esters (composition: 17% dimethyl adipate, 66% dimethyl glutarate, 16.5% dimethyl succinate), 400.66 g (2 moles) of isotridecyl alcohol and 5.00 g (0.015) 1-butyl titanate entered with vigorous stirring.

This mixture is slowly heated to 180 ° C. for 3 hours and 71.0 g of distillate (110% of theory) are removed under normal pressure.
The reaction mixture is cooled to 20 ° C. A mixture of the corresponding isotridecyl-methyl-dicarboxylic acid esters is obtained as the main component.

Example 6 (comparative example)

120.0 g of 5-mole ethylene oxide adduct of isotridecyl alcohol are placed in a 1 liter glass beaker with an anchor stirrer while stirring. Then 194.4 g of isotridecyl alcohol-7 mol ethylene oxide adduct, 210.6 g of isotridecyl alcohol-12 mol ethylene oxide adduct and 48.0 g of coconut fatty acid diethanolamide (coconut fatty acid chain length distribution: C ₈ : 8%, C ₁₀ : 7%, C ₁₂ : 46%, C ₁₄ : 18 %, C ₁₆ : 8%, C ₁₈ : 13%) and stirred until a homogeneous distribution is reached. With stirring, a mixture of 48.0 g of 2-methyl-2,4-pentanediol and 285.0 g of terpenes (typical analysis: 96.2% dl-limonene, 1.9% myrcene, 0.5% α-pinene, 0.4% β -Pinene, 1.0% residual components).

94.0 g of demineralized water are introduced into this mixture and stirred until a homogeneous solution is reached.

Example 7

The procedure is analogous to Example 6. The 285.0 g terpenes are replaced by 285.0 g of a dicarboxylic acid ester mixture of the following composition: 17% dimethyl adipate, 66% dimethyl glutarate, 16.5% dimethyl succinate, 0.2% methanol, 0.1% water. The result is a clear solution containing about 28.5% of the above dicarboxylic acid ester mixture, about 57.3% of a mixture of nonionic surfactants, and about 9.4% water.

Example 8

The procedure is analogous to Example 6. The 285.0 g terpenes are replaced by 285.0 g of a dicarboxylic acid butyl ester mixture according to Example 4. The result is a homogeneous emulsion.

Example 9

The procedure is analogous to Example 6. The 285.0 g terpenes are replaced by 285.0 g of a dicarboxylic acid isotridecyl methyl ester mixture according to Example 5. The result is a homogeneous emulsion.

Example 10

The procedure is analogous to Example 6. The 285.0 g terpenes are replaced by 285.0 g dimethyl maleate.

The result is a clear solution.

Example 11

The procedure is analogous to Example 6. The 285.0 g terpenes are replaced by 285.0 g di-n-butyl maleic acid.

The result is a clear solution.

Example 12 (comparative example)

In a 1 liter glass beaker with anchor stirrer, with stirring, 60.0 g of isotridecyl alcohol-5 mol ethylene oxide adduct, 50.4 g isotridecyl alcohol 7 mol ethylene oxide adduct, 56.7 g isotridecyl alcohol 12 mol ethylene oxide adduct, 38.0 g 2-methyl 2,4-pentanediol, 36.0 g 1,2-ethanediol monobufyl ether, 34.0 g isobutanol, 34.0 g of a commercial aliphatic hydrocarbon mixture (boiling range 192 - 254 ° C), 143.0 g of a commercial aromatic hydrocarbon mixture (predominantly C ₉ -C ₁₀ , boiling range 164 - 188 ° C), 86.0 terpene (composition analogous to Example 2) and 461.9 g of demineralized water mixed together. The result is a slightly cloudy solution.

Example 13

The procedure is analogous to Example 12. The 86.0 g terpenes are replaced by 86.0 g of a dicarboxylic acid ester mixture of the following composition: 17% dimethyl adipate, 66% dimethyl glutarate, 16.5% dimethyl succinate, 0.2% methanol, 0.1% water. The result is a slightly cloudy solution containing approximately 8.6% of the above dicarboxylic acid ester mixture, approximately 16.7% of a mixture of nonionic surface-active substances, approximately 46.1% water and approximately 28.5% further additives.

Example 14

An aqueous washing liquor (liquor ratio 1:30) is obtained as follows: 10 g of a composition according to Example 3 or 10 g are added to 1000 g of demineralized water according to Example 7 entered with stirring. With heating to 80 ° C., 33 g of laundry (mixed fabric, 45% polyester fiber / 55% wool fiber, heavily soiled with different amounts of impurities in machine mineral oil) are treated with stirring for 2 minutes. The laundry is then separated from the wash liquor, rinsed twice with water at 80 ° C. and then air-dried. The washing effect is determined by determining the amount of machine mineral oil applied by hot extraction of the laundry on the Soxtec System 1043 with 1,1,1-trichloroethane before and after washing. The results of the individual washing processes obtained can be seen from Table 1 below. Table 1 Washing liquor containing the composition according to the example Quantity before washing Quantity after washing % Distance 3rd 0.71% 0.48% 32 3rd 7.84% 2.57% 67 3rd 10.88% 4.14% 62 7 0.71% 0.11% 85 7 7.84% 0.20% 97 7 10.88% 0.42% 96

As can be clearly seen from Table 1, the composition according to the invention according to Example 7 has a significantly better washing effect compared to the composition from Example 3, which leads to almost complete removal even with large amounts of machine mineral oil, while the washing effect with the washing liquors contains one The composition from Example 3 is even sharply declining for circulation quantities greater than 7.84%.

Example 15

An aqueous washing liquor (liquor ratio 1:30) is obtained as follows: 1.50 g of a 10% aqueous solution of the composition according to Example 6 are added to 148.5 g demineralized water with stirring. While heating to 60 ° C, 5.0 g of standard dirt fabric No. 107 (material: 100% wool, soiled with soot / olive oil, source: Federal Material Testing and Research Institute, CH-9001 St. Gallen, Unterstrasse 11) is treated with stirring for 30 minutes. The laundry is then separated from the wash liquor, rinsed twice with cold water and then air-dried. The procedure of Example 7 is analogous to the composition of Example 6. As a blank value, the corresponding standard dirt fabric was carried without washing aids.

The washing effect was determined by determining the brightness of the goods using the color coordinate system according to CIE Lab (data color system, light type D 65 = daylight, average of 4 individual measurements at 3 measuring points). Table 2 shows the results obtained for the individual washing processes. Table 2 Washing liquor containing composition according to example: Goods brightness Starting goods unwashed 52.9 The raw material is washed in water alone 55.2 Example 6 Comparative Example 67.5 Example 7 70.6

As can be seen from Table 2, Example 7, containing the composition according to the invention, shows improved washing results or an improved brightening of the goods.

Example 16

An aqueous washing liquor (liquor ratio 1:30) is obtained as follows: 1.50 g of a 10% aqueous solution according to Example 1 and 1.50 g of a 10% aqueous sodium carbonate solution are added to 147 g demineralized water with stirring. With heating to 98 ° C, 5.0 g of standard dirt fabric No. 101 (material: 100% cotton, soiled with soot / olive oil, source: Federal Material Testing and Research Institute, CH-9001 St. Gallen, Unterstrasse 11) is treated with stirring for 30 minutes. The laundry is then separated from the wash liquor, rinsed twice with cold water and then air-dried. The compositions according to Examples 2, 6, 7, 12 and 13 are used analogously.

The washing effect was determined as described in Example 15 and is documented in Table 3. Table 3 Washing liquor containing composition according to example: Goods brightness Starting goods unwashed 49.6 example 1 64.3 Example 2 (comparative example) 59.6 Example 6 (comparative example) 61.7 Example 7 67.1 Example 12 (comparative example) 56.5 Example 13 64.4

Examples 1, 7 and 13 with the composition according to the invention have improved washing results in all cases compared to the corresponding comparative examples.

Example 17

The compositions of Examples 6, 7, 8, 10 and 11 were tested and evaluated for their washing performance analogously to that described in Example 16. Table 4 documents the results obtained. Table 4 Washing liquor containing composition according to example: Goods brightness Starting goods unwashed 49.6 Example 6 (comparative example) 68.5 Example 7 71.0 Example 8 70.1 Example 10 71.7 Example 11 73.5

Examples 7, 8, 10 and 11 with the composition according to the invention show improved washing results in all cases compared to the corresponding comparative example 6.

Claims (21)

Composition containing: A) 5 to 95% by weight of at least one dicarboxylic acid ester of the general formula I

R ₁ ―OOC ― R ― COO ― R ₂ (I)

in which mean:
R ₁ and R ₂ independently of one another are a C ₁ -C ₁₅ alkyl radical, a C ₅ -C ₇ cycloalkyl radical or an aromatic-containing radical and R is a bivalent bridge member; B) 95 to 5% by weight of at least one detergent surfactant; and C) optionally water and / or other additives. Composition according to Claim 1, containing as component A) at least one dicarboxylic acid ester of the general formula I in which: R ₁ and R ₂ independently of one another are a C ₁ -C ₁₅ alkyl radical and R is a C ₁ -C ₂₀ alkylene, C ₂ -C ₂₀ alkenylene, C ₅ -C ₇ cyclo-alkylene or an aromatic bivalent bridge member, and in which the other components B) and C) have the meaning given. A composition according to claim 2 comprising as component A) at least one dicarboxylic acid ester of the general formula I in which: R ₁ and R ₂ independently of one another are a C ₁ -C ₄ alkyl radical and R is a bivalent C ₂ -C ₄ alkylene bridge member and in which the other components B ) and C) have the meaning given in claim 1. A composition according to claim 3 containing as component A) a technical mixture of 15-20% by weight dimethyl adipate, 60-70% by weight dimethyl glutarate and 15-20% by weight dimethyl succinate. Composition according to claims 1 to 4 containing as component B) at least one nonionic and / or anionic surfactant. A composition according to claim 5 containing as component B) a mixture of two or more nonionic surfactants. A composition according to claim 6 containing an alkylene oxide condensation product as the nonionic surfactant. A composition according to claim 7, containing as the alkylene oxide condensation product a condensation product of a C ₁₀ -C ₂₂ alcohol with 3 to 20 moles of ethylene oxide. Composition according to claims 1 to 8, containing as further additives according to component C) solubilizers, buffer substances, solvents and / or foam suppressants. Composition according to claims 1 to 9, containing A) 8 to 67% by weight of at least one dicarboxylic acid ester of the general formula I according to claim 1; B) 10 to 92% by weight of at least one detergent, nonionic and / or anionic surfactant; and C) optionally water and / or other additives. Containing composition according to claim 10 A) 8 to 67% by weight of at least one dicarboxylic acid ester of the formula I, in which: R ₁ and R ₂ each represent a C ₁ -C ₁₄ alkyl radical and R is a C ₂ -C ₄ alkylene or a C ₂ alkenylene, B) 10 to 92% by weight of at least one condensation product from a C ₁₀ -C ₂₂ alcohol with 3 to 20 moles of ethylene oxide and optionally coconut fatty acid diethanolamide, and C) optionally water and / or other additives. A composition according to claim 11 containing A) 8 to 67% by weight of at least one dicarboxylic acid ester of the formula I, in which; R ₁ and R _{2 are} each a C ₁ -C ₄ alkyl radical and R is a C ₂ -C ₄ alkylene or a C ₂ alkenylene, and B) 10 to 92% by weight of at least one condensation product from a C ₁₀ -C ₂₂ alcohol with 3 to 20 moles of ethylene oxide and optionally coconut fatty acid diethanolamide, and C) optionally water and / or other additives. Composition according to claim 12, containing A) 8 to 67% by weight of an industrial mixture of about 17% by weight dimethyl adipate, about 66% by weight dimethyl glutarate and about 17% by weight dimethyl succinate, B) 15 to 25% by weight of a mixture of a condensation product of a C ₁₀ -C ₂₂ alcohol with 3 to 20 moles of ethylene oxide and coconut fatty acid diethanolamide, and C) optionally water and / or other additives. Composition according to claim 12, containing A) 20 to 35% by weight of an industrial mixture of about 17% by weight dimethyl adipate, about 66% by weight dimethyl glutarate and about 17% by weight dimethyl succinate, B) 50 to 65% by weight of a mixture of a condensation product of a C ₁₀ -C ₂₂ alcohol with 3 to 20 moles of ethylene oxide and coconut fatty acid diethanolamide, and C) 10 to 15% by weight of water and optionally further additives. Composition according to claim 12, containing A) 8 to 67% by weight of an industrial mixture of about 17% by weight dimethyl adipate, about 66% by weight dimethyl glutarate and about 17% by weight dimethyl succinate, B) 15 to 25% by weight of a mixture of a condensation product from a C ₁₀ -C ₂₂ alcohol with 3 to 20 mol of ethylene oxide, and C) 40 to 50 wt.% Water and optionally other additives. A process for the preparation of the composition according to claims 1 to 15 by homogeneously mixing and stirring components A), B) and C) at a temperature of about 5 to 100 ° C. Use of the composition according to claims 1 to 15 or of the composition obtained according to claim 16 in an aqueous washing liquor for cleaning and removing impurities and soiling from textile substrates. Use of the composition according to claims 1 to 15 or the composition obtained according to claim 16 as a cleaning agent for hard metal surfaces, polymeric surfaces and painted surfaces. An aqueous-based washing liquor containing, in addition to conventional washing aids, 0.05 to 5.0% by weight of a composition according to claims 1 to 15. Process for washing textile substrates by adding 0.05 to 5.0% by weight of a composition according to claims 1 to 15 to the aqueous washing liquor before or during the washing process. Process for washing textile substrates by adding at least one dicarboxylic acid ester of the general formula I according to Claims 1 to 4, an aqueous washing liquor before or during the washing process in such an amount that the washing liquor contains 0.01 to 30% by weight of this dicarboxylic acid ester.