Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
  • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines

Definitions

• phosphate-free detergents which contain a detergent as main constituent and alkali metal or ammonium polyacrylate as builder in an amount of about 10 to 40%, based on the total mixture, as builder.
• the ammonium salts of the homopolymers are derived, for example, from methylamine and triethylamine.
• Such scaffolding substances give the detergents a high sequestering capacity, but they have no graying-inhibiting effect.
• EP-PS 25 551 discloses the use of copolymers which contain 40 to 90% by weight of acrylic acid or methacrylic acid and 60 to 10% by weight of copolymerized maleic acid as a phosphate substitute in detergents.
• the copolymers are preferably used as the sodium or ammonium salt.
• the salts of these copolymers make a contribution to the primary washing action of a detergent and are very effective incrustation inhibitors, but make no contribution to the graying inhibition.
• the present invention is based on the object of providing an additive to detergents and cleaning agents which can completely or partially replace the polyphosphates in detergents or which supports the primary washing action of conventional detergents and also has a sufficient incrustation-inhibiting and graying-inhibiting action.
• Homopolymers of acrylic acid and methacrylic acid are known. They are produced, for example, by polymerizing acrylic acid or methacrylic acid in aqueous solution in the presence of polymerization initiators and, if appropriate, polymerization regulators at from 50 to 150 ° C. At temperatures above 100 ° C it is necessary to carry out the polymerization in pressure equipment.
• the molecular weights of the polyacrylic acids and polymethacrylic acids to be used according to the invention are 5,000 to 500,000 and are preferably in the range from 10,000 to 300,000. Copolymers of acrylic acid and methacrylic acid, which can contain the two monomers in any ratio, can also be used according to the invention .
• the molecular weight range of the copolymers of acrylic acid and methacrylic acid corresponds to that of the homopolymers.
• the copolymers contain as component b) at least one monomer from the group consisting of acrylic acid, methacrylic acid and / or a hydroxy-C2- to -C6-alkyl ester of an ethylenically unsaturated C3- to C5-carboxylic acid.
• Suitable hydroxyalkyl esters are obtained by reacting ethylenically unsaturated C3 to C5 carboxylic acids with C2 to C6 alkanediols.
• Suitable alkane diols are glycol, 1,3-propanediol, 1,2-propanediol and mixtures of propanediols, 1,4-butanediol, 1,3-butanediol and 2,3-butanediol and mixtures of the isomeric butanediols, 1-pentanediol, 5 and hexanediol-1,6.
• Suitable hydroxyalkyl esters are, for example, hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate and hydroxyhexyl acrylate.
• acrylic acid as monomer of group b) and of mixtures of acrylic acid or methacrylic acid and hydroxyethyl acrylate or hydroxypropyl acrylate is particularly preferred. These monomers can be copolymerized in any ratio with the monomers of components a) be settled. If at least 2 monomers of group b) are used in the copolymerization, these mixtures advantageously contain 5 to 70% acrylic acid and 95 to 30% by weight of a hydroxyalkyl ester of an ethylenically unsaturated C3- to C5-carboxylic acid.
• the hydroxyalkyl half-esters and esters of maleic acid, fumaric acid and itaconic acid are also suitable as group b) monomers.
• the monomers of group b) make up 90 to 30, preferably 80 to 40% by weight of the copolymers.
• the copolymers can optionally be modified by polymerizing up to 15% by weight, based on the monomers a) and b), of monomers of group c), for example acrylamide, methacrylamide, 2-acrylamido 2-methylpropanesulfonic acid, vinylsulfonic acid, allylsulfonic acid, vinylphosphonic acid, allylphosphonic acid, vinyl acetate, vinyl propionate, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminoethyl methacrylate and styrene. From this group of monomers, 2-acrylamino-2-methylpropanesulfonic acid, vinylphosphonic acid, vinyl acetate and vinyl propionate are preferably used.
• the weight average molecular weight of the copolymers of monomers a) and b) and optionally c) is 5,000 to 500,000 and is preferably in the range from 10,000 to 200,000.
• Suitable amines of the formula I are, for example, octylamine, nonylamine, decylamine, 6-methyl-2-heptylamine, 2-ethylhexylamine, tridecylamine, mono- (C12 / C14) amine, palmitylamine, stearylamine, tridecyloxypropylamine, isopentyloxypropylamine, n-butyloxypropoxyamine, n , N-methyl-N-tridecylamine, dimethyltridecylamine, stearyloxypropylamine, di-2-ethylhexylamine, N, N-dimethyl-2-ethylhexylamine, di-2-methoxyethylamine, 3-methoxypropylamine, 3-ethoxypropylamine, 3- (2-ethylhexoxy) propylamine, di-n-octylamine, di-isononylamine, di-
• Those amines of the formula I are preferably used in which the substituent R is a C10- to C16-alkyl group and the substituents R2 and R3 are hydrogen or a C1- to C4-alkyl group.
• the homo- and copolymers containing carboxyl groups described above are each partially or completely neutralized with amines of the formula I. If the copolymers are in the form of aqueous solutions, an amine of the formula I is added either directly or in solution in water. If the polymers containing carboxyl groups are in powder form, they are introduced into water and the amines of the formula I are then added. However, the procedure can also be such that a pulverulent polymer containing carboxyl groups and an amine of the formula I are simultaneously introduced into water, in which case the neutralization takes place.
• an aqueous solution or an aqueous dispersion of a polymer containing carboxyl groups to an amine of the formula I or an aqueous solution of the amine of the formula 1.
• the amount of amine of the formula I is chosen so that the carboxyl groups of the polymers are completely or partially neutralized therewith.
• the degree of neutralization of the carboxyl groups of the polymers is 1 to 100%, preferably 20 to 100%.
• the carboxyl group-containing polymers are neutralized with the amines of the formula I, either clear solutions, cloudy solutions or aqueous dispersions are obtained.
• the different solubility of the neutralized or partially neutralized carboxyl-containing polymers has practically no influence on the effectiveness of these products in detergents.
• the amides of the homopolymers and copolymers described above are obtained by reacting them with the exclusion of water with primary or secondary amines of the formula I, the amount of amine of the formula I being chosen so that 5 to 50, preferably 10 to 35 % of the carboxyl groups of the homopolymers and copolymers are converted into the corresponding amide.
• the amidation can be carried out, for example, in inert solvents such as xylene, toluene or tetrahydrofuran, dioxane or methyl tert-butyl ether at temperatures from 20 to 140, preferably 40 to 80 ° C.
• inert solvents such as xylene, toluene or tetrahydrofuran, dioxane or methyl tert-butyl ether at temperatures from 20 to 140, preferably 40 to 80 ° C.
• primary and secondary amines are suitable as amines of the formula I for the amidation.
• the radical R2 is preferably C1- to C4-alkyl, while the substituent R3 is hydrogen.
• copolymers containing amide groups are preferably prepared from copolymers of maleic anhydride as component a) and the compounds b) because maleic anhydride forms the acid amide in a smooth reaction with the primary or secondary amines of the formula I.
• Acid amides to be used according to the invention can, however, also be obtained by subjecting amides of ethylenically unsaturated dicarboxylic acids having 4 to 6 carbon atoms and primary or secondary amines of the formula I to copolymerization with the monomers b) and optionally c).
• Suitable monomaleamides are, for example, N- (isopentyloxypropyl) monomaleamide, N- (tridecyloxypropyl) monomaleamide, N- (n-butyloxypropyl) monomaleamide and N- (isopropyloxypropyl) monomaleamide.
• the homopolymers and copolymers described above which have been converted into the neutralized or amidated form by reaction with the amines of the formula I, are used as an additive to graying-inhibiting and promoting the primary washing action to detergents and cleaning agents in an amount, in each case based on the solids, from 0.5 to 10, preferably 1 to 5 wt .-% used.
• the salts or amides to be used according to the invention can be incorporated in the form of the aqueous solution, as an aqueous dispersion or as a powder in washing and cleaning agents. They support the primary washing action and secondary washing action of common detergents and cleaning agents and can also be used as a partial or complete replacement of polyphosphates in detergents.
• the homopolymers and copolymers neutralized or amidated with amines of the formula I to be used according to the invention are particularly suitable for the production of detergents based on surfactants, builders (polyphosphates, zeolites, nitrilotriacetic acid, soda and silicates) as well as bleaching agents (perborates) and, if appropriate, customary additives (e.g. defoamers, perfumes, optical brighteners, enzymes) and fillers such as sodium sulfate.
• Such detergents are either phosphate-free or contain up to a maximum of 25% by weight of polyphosphate, calculated as sodium tripolyphosphate, based on the total detergent formulation.
• the polymers to be used with the amines of the formula I neutralized or containing amidated carboxyl groups are present in the detergents in an amount of 0.5 to 10, preferably 1 to 5% by weight and, in addition to supporting the primary washing action, inhibit incrustation and at the same time inhibition of graying of the textile goods.
• These detergents have a special white washing effect and also protect the washed white material before graying.
• the substances to be used according to the invention thus have the effect that they improve the detachment of dirt from the soiled textile materials, but nevertheless largely prevent the dirt from being deposited again on the textile material even when there is a higher level of dirt in the washing liquor. It is of particular technical importance that the graying-inhibiting effect occurs not only with respect to pure cotton, but also to a considerable extent with the widespread cotton-polyester blends.
• K k ⁇ 103.
• the molecular weights (weight average) of the polymers containing carboxyl groups were determined by gel permeation chromatography (GPC) with aqueous eluents.
• the separation columns were calibrated using polystyrene sulfonates which had a narrowly distributed molecular weight and were manufactured by Pressure Chem. Comp. were obtained.
• the values thus obtained were based on the molecular weights of polysodium acrylate according to the universal calibration principle of BENOIT (J. Chim. Phys. 63 (1966) 1507) using the measurement data from SPATORICO and BEYER (J. Appl. Polym. Sci. 19 (1975) 2933) converted.
• a solution of 300 parts of maleic anhydride in 300 parts of xylene was added within 2 hours and at the same time 825 parts of acrylic acid were added over a period of 3 hours, and a solution of 12 parts of tert-butyl perethylhexanoate in 300 was metered in over a period of 4 hours Allocate xylene.
• the reactor contents are heated to boiling (133 ° C.). As soon as the boiling temperature is reached, a solution of 12 parts of di-tert-butyl peroxide in 150 parts of xylene is added over the course of an hour, the reaction mixture is then heated to boiling for a further hour and then allowed to cool.
• a copolymer of maleic anhydride and acrylic acid is obtained in the form of a slightly viscous, fine granular suspension.
• the K value of the copolymer is 42.
• the suspension has a solids content of 49.9% and is reacted with the amines given in Table 1 to prepare additives 1 to 9.
• the copolymer has a weight average molecular weight of 45,000.
• additives 1 to 9 For the preparation of additives 1 to 9, 200 parts of the suspension described above are placed in a 500 ml flask equipped with a stirrer and a nitrogen inlet and outlet. The suspension is stirred and heated to a temperature of 70 ° C. As soon as this temperature is reached, the amines given in Table 1 are added. The reaction mixture is then stirred for a further 2 hours at a temperature of 70 ° C. and then the amount of water likewise given in Table 1 is added. The suspension media (xylene and toluene) are then removed at 110 ° C. by introducing steam. After cooling, an aqueous dispersion of additives 1 to 9 is obtained, the solids contents of which are also given in table 1.
• the reactor contents are then heated to boiling, a solution of 12 parts of di-tert-butyl peroxide in 150 parts of xylene is added within one hour, and the mixture is then heated to boiling and cooled for a further hour.
• the weight average molecular weight is 75,000.
• the suspension has a solids content of 49.9%.
• Additives 9 to 11 are obtained by heating in each case 200 parts of the suspension described above in a 500 ml flask with stirring in a nitrogen atmosphere of 70 ° C. and within one hour with the amines given in Table 2 in the amount likewise given there transferred. After the amines have been added, the reaction mixture is heated at 70 ° C. for a further 2 hours and then, after the amount of water given in Table 2 has been added, the suspension medium is removed by introducing steam. A dispersion is obtained in each case, the solids content of which is also given in Table 2. The additives 10 and 11 were additionally neutralized with 50% aqueous sodium hydroxide solution, cf. Table 2.
• the K value of the copolymer is 17.4, the molecular weight by weight average 10,000.
• the detergent formulations 1 to VI shown in Table 3 are produced, which are phosphate-reduced or, in the case of formulation III, a phosphate-free detergent formulation.
• the effects which are achieved with these detergent formulations are given in the tables below for comparison with formulations according to the invention.
• the known formulations are additionally combined with 2 to 3% by weight of the additives to be used according to the invention, for example additives 1 to 14, and then washing tests are carried out with the detergent formulations I to VI modified in this way, for example, an increase of up to 7 points for the whiteness of WFK dirty fabric is measured for the primary washing effect, which documents the considerable increase in the primary washing effect.
• the detergent formulations I to VI are given in Table 3. The following test conditions were observed to test the effectiveness of the detergents:
• the EMPA dirty fabric 101 from the Swiss Federal Laboratory for Materials Testing in St. Gallen / Switzerland or the WFK dirty fabric 10 D can also be used.
• the dirt cloth rags were measured after each wash and replaced with fresh ones.
• the graying of the three test fabrics was determined after the 5th wash by measuring the reflectance.
• the whiteness of the unwashed WFK fabric 10 C was 40
• the whiteness of the unwashed WFK fabric 10 D was 42.5
• the whiteness of the unwashed pigment dirt fabric was 30, the whiteness of the unwashed EMPA fabric 101 was 17.5.
• Table 4 shows the different effects of the additives to be used according to the invention when using the detergent formulation IV and various soiling fabrics.
• Table 5 shows the effect of additive 3 in the detergent formulations I-III, V and VI using the WFK 1O C / pigment soiled fabric combination.

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• 1985
  • 1985-08-08 DE DE19853528460 patent/DE3528460A1/de not_active Withdrawn
• 1986
  • 1986-07-24 US US06/888,957 patent/US4702858A/en not_active Expired - Fee Related
  • 1986-07-24 CA CA000514584A patent/CA1265019A/fr not_active Expired - Lifetime
  • 1986-07-30 EP EP86110543A patent/EP0215251B1/fr not_active Expired
  • 1986-07-30 DE DE8686110543T patent/DE3665883D1/de not_active Expired
  • 1986-07-30 AT AT86110543T patent/ATE46716T1/de not_active IP Right Cessation
  • 1986-08-04 JP JP61182066A patent/JPS6234996A/ja active Pending
  • 1986-08-07 ES ES8600935A patent/ES2001072A6/es not_active Expired

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