DE2504276A1 - Detergent compsns. contg. n-alkane-sulphonates - and sulphonated bis-styryl-diphenyl brightener(s) for colour stability on storage - Google Patents

Abstract

Detergent compsn. comprises (a) 1-20 wt. % 10-20C n-alkanesulphonates (I), esp. 2-15 wt. % as Na salts, and (b) 0.001-1 wt. % of >=1 optical brightener of formula (II): (>=1 of R1-4 is SO3M and the others are same or different H, SO2NR5R6, OCH3, CN, Cl, CO2CH3 and CONR5R6; M=alkali metal; R5 and R6 are H or 1-4C alkyl; esp. 1 or 2 are SO3Na and the others H or Cl). The compsn. can also contain other surfactants and/or inorg. or org. builders. Compsns. do not discolour on storage unlike those contg. (I) plus bis triazinylamino)stilbene-2,2'-sulphonic acid brighteners.

Description

"Laundry detergents with a content of n-alkanesulfonates and optical brighteners" Detergents containing detergent n-alkane sulfonates are known. Man Under washing-active n-alkanesulphonates means mixtures of paraffin monosulphonates and di- or polysulfonates with straight-chain 10 to 20 carbon atoms Hydrocarbon radicals, with the sulfonate groups statistically over the hydrocarbon chain are distributed. The content of technical mixtures of disulfonates or polysulfonates is generally 1 to 15 5 '. They are made from paraffinic hydrocarbons in known way by sulfochlorination and subsequent saponification or by sulfoxidation available with subsequent neutralization. They stand out for one special rapid and complete biological degradation in wastewater and a low one Toxicity to fish and microorganisms and exceed the known n-alkylbenzenesulfonates.

It has now been shown that powder detergents that more than 1 5 'of n-alkanesulfonates and optical brighteners of the 4,4'-bis (triazinylamino) stilbene-2,2'-disulfonic acid type contain discoloration when stored under the influence of atmospheric humidity suffer which are initially reversed by drying the powder can become irreversible after a long period of storage. These mostly yellow-greenish to yellow-gray discoloration make the powder unsightly and arouse the consumer the impression that the remedy has partially decomposed. This phenomenon is obvious not to be regarded as a consequence of the well-known "post-acidification" of the alkanesulfonates, because it also occurs in the presence of excess builder substances with an alkaline reaction and washing alkalis.

A means has now been found which does not have the disadvantages described. The invention relates to detergents with a content of 10 to 20 carbon atoms containing n-alkanesulfonates and optical brighteners, characterized in that their content of n-alkanesulfonates is 1 to 20 percent by weight and the optical brightener, which is in amounts of 0.001 to 1 wt. -% is present, consists of at least one 4,4t-distyryl-diphenyl compound of the following formula wherein at least one of the radicals R1, R2, R3 and R4 is a -S03Me group and the others can be the same or different and are -H, -SO2NRSR6, -OCH3, -CN, -Cl, -COOCH3 and -CONR5R6 and where Me represents an alkali metal and R5 and R6 represent H or alkyl radicals with 1 to 4 carbon atoms.

The alkanesulfonates can be used as alkali metal, alkaline earth metal or Ammonium salts and as salts of organic ammonium bases, e.g. of the mono-, di- or Triethanolamine. The sodium salts are preferably used in amounts of 2 to 15% by weight, based on detergent.

Compounds of the above are preferred as optical brighteners Formula in question in which one or two of the groups R1, R2, R3 and R4 represent -SO2Na d or Cl. Examples are 4,4'-bis- (2-sulfostyryl) -diphenyl, 4,4'-bis- (3-sulfostyryl) -diphenyl, 4,4'-bis- (2-chloro-5-sulfostyryl) -diphenyl, 4,4'-bis- (4-chloro-3-sulfostyryl) -diphenyl, 4- (2-chlorostyryl) -4 '- (2-chloro-5-sulfostyryl) diphenyl.

4- (2,4-dichlorostyryl) -4 '- (2-sulfostyryl) -diphenyl, 4- (4-chlorostyryl) -4' - (2-sulfostyryl) -diphenyl), 4- (3-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl and 4- (2,5-dichlorostyryl) -4' - (2-sulfostyryl) diphenyl. These brighteners are preferably used in amounts of 0.01 to 0.5 percent by weight In addition to the n-alkanesulfonates and the aforementioned optical brighteners, the Detergents further surface-active washing active substances, inorganic and / or organic structural substances or sequestering agents, optical brighteners of others Structure, graying inhibitors, neutral salts and possibly foam-improving or contain foam suppressants and other known detergent additives.

Suitable washing raw materials are those of the sulfonate or sulfate type; for example alkylbenzenesulfonates, in particular n-dodecylbenzenesulfonate, furthermore Olefin sulfonates, α-sulfo fatty acid esters, primary and secondary alkyl sulfates and the sulfates of ethoxylated or propoxylated higher molecular weight alcohols.

Further compounds of this class which may be present in the detergents are the higher molecular weight sulfated partial ethers and partial esters of polyhydric alcohols, such as the alkali metal salts of the monoalkyl ethers or the monofatty acid esters of glycerol monosulfuric acid ester or 1,2-dioxypropanesulfonic acid. Further Coinine sulfates of ethoxylated or propoxylated fatty acid amides and alkylphenols as well as Fettsäuretäuride und Fettsäureisäthionate in Frago. Other suitable anionic Detergent raw materials are alkali soaps made from natural or synthetic fatty acids Origin, E.g. the sodium soaps made from coconut, parent or tallow fatty acids.

As zwitterionic wash tubing materials, there are alkyl betaines and in particular Possible alkyl sulfobetaines, e.g. 3- (N, N-dimethyl-N-alkylammonium) propane-1-sulfonate and 3- (N, N-dimethyl-N-alkylammonium) -2-hydroxypropane-1-sulfonate.

The anionic detergent raw materials can be in the form of sodium, potassium and ammonium salts as well as organic rabbit salts; such as mono-, di- or triethanolamine, 1 Provided that the above-mentioned anionic and zwitterionic compounds have a aliphatic hydrogen carbon atoms, this should preferably be straight-chain and have 8 to 22 carbon atoms. In compounds with an araliphatic The preferably unbranched alkyl chains contain hydrocarbon radicals on average 6 to 16 carbon atoms.

As nonionic surface-active washing-active substances come in primarily polyglycol ether derivatives of alcohols, fatty acids and alkylphenols in question, the 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the hydrocarbon radical contain. Polyglycol ether derivatives in which the number of Ethylene glycol ether groups is 5 to 15 and their hydrocarbon radicals of straight-chain, primary alcohols with 12 to 18 carbon atoms or of alkylphenols derive with a straight-chain alkyl chain having 6 to 14 carbon atoms.

Other suitable non-ionic washing raw materials are the water-soluble, Containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups Polyethylene oxide adducts with polypropylene glycol, ethylene diamino polypropylene glycol and Alkyl polypropylene glycol with 1 to 10 carbon atoms in the alkyl chain. The mentioned Compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit. Also nonionic compounds of the amine oxide type and sulfoxides, which may also be ethoxylated can be are usable.

Suitable builder substances are the polymer phosphates, carbonates and silicates of potassium and especially of sodium, the latter being a ratio of SiO2 to Na2O from 1: 1 to 3.5: 1. As a polymer phosphate comes in particular the pentasodium triphosphate in question, which in a mixture with its hydrolysis products, the mono- and diphosphates, as well as more highly condensed phosphates, e.g. the tetraphosphates, may exist.

The polymer phosphates can also be wholly or partially replaced by organic, aminopolycarboxylic acids with a complexing action be replaced. These include in particular Alkali salts of nitrilotriacetic acid and ethylenediaminotetraacetic acid. Suitable are also the salts of diethylenetriaminopentaacetic acid and the higher homologues of the aminopolycarboxylic acids mentioned. These homologues can, for example, by Polymerization of an ester, amide or nitrile of N-acetic acid aziridine and subsequent Saponification to carboxylic acid salts or by reacting polyethyleneimine with chloroacetic acids or bromoacetic acid salts are produced in an alkaline environment. More suitable Aminopolycarboxylic acids are poly (N-succinic acid) -ethyleneimine, poly- (N-tricarballyic acid) -ethyleneimine and poly (N-butane-2,3,4-tricarboxylic acid) ethyleneimine, which are analogous to the N-acetic acid derivatives are available.

Polyphosphonic acid salts with a complexing action can also be present be, e.g. the alkali salts of aminopolyphosphonic acids, especially aminotri- (methylenephosphonic acid), 1-Hydroxyäthai- 1, 1 -dipho sphonic acid, methyl endipho 5-phonic acid, ethylene diphosphonic acid and salts of the higher homologues of the polyphosphonic acids mentioned. Mixtures too the aforementioned complexing agents can be used, of particular importance are nitrogen- and phosphorus-free and form complex salts with calcium ions Polycarboxylic acids, including polymers containing carboxyl groups. Suitable are citric acid, tartaric acid, bensol hexacarboxylic acid and tetrahydrofuran tetracarboxylic acid. Polycarboxylic acids containing carboxymethyl ether groups can also be used, such as 2,2'-oxydisuccinic acid and partially or completely etherified with glycolic acid polyhydric alcohols or hydroxycarboxylic acids, for example triscarboxymethylglycerin, Biscarboxymethylglyceric acid and carboxymethylated or oxidized polysaccharides, The polymeric carboxylic acids with a molecular weight of at least 350 in the form of the water-soluble sodium or potassium salts, such as polyacrylic acid, Polymethacrylic acid, polyoc-hydroxyacrylic acid, polymaleic acid, polyitaconic acid, Polymesaconic acid, polybutentricarboxylic acid and the copolymers of the corresponding monomeric carboxylic acids with one another or with ethylenically unsaturated compounds such as ethylene, propylene, isobutylene, vinyl methyl ether or furan.

Complexing agents which are insoluble in water can also be used. These include phosphorylated cellulose and graft polymers of acrylic acid or methacrylic acid on cellulose, which can be in the form of woven or non-woven fabrics. Furthermore are spatially crosslinked and thus water-insoluble copolymers of acrylic, methacrylic, Crotonic and maleic acids as well as other polymerizable polycarboxylic acids, optionally with other ethylenically unsaturated compounds in the form of sodium or Potassium salts suitable as sequestering agents. These insoluble copolymers can as a tile, sponge or in the form of finely ground, specifically light foams present with an open-cell structure.

Alkali aluminum silicates are also suitable as water-insoluble builder substances and alkali borosilicates, which may contain bound water and a calcium binding capacity have at least 50 mg CaO / g active substance. This includes connections in particular of the formula (Na 2 O) x Al 2 O 5 (SiO 2) y, where x is a number from 0.7 to 1.5 and y is a number from 1.3 to 4 mean. You can use the agents according to the invention as finely divided Powder can be added. Also mixtures of the aforementioned water-soluble and water-insoluble ones Framework substances are useful.

Oxygen-releasing bleaches are another component of the mixture, such as alkali perborates, percarbonates, perpyrophosphates and persilicates as well as urea perhydrate in question.

Sodium perborate is preferably used in anhydrous form or as tetrahydra. To stabilize the per compounds, the agents can contain magnesium silicate, for example in amounts of 3 to 20% by weight, based on the amount of perborate, Means to be used for washing textiles at temperatures below 70 ° C, so-called Cold detergents, bleach activators from the class of N- or O-acyl compounds, in particular tetraacetylethylenediamine or tetraacetylglycoluril, as a powder component contain.

Those consisting of the bleach activator or the per compound Powder particles can contain substances such as water-soluble polymers or fatty acids be coated to allow interaction between the per compound and the activator to avoid during storage.

The detergents can contain further optical brighteners, with however, derivatives of diaminostilbene disulfonic acid are not or only in amounts below 0.01 wt. 5 'should be present.

On the other hand, suitable brighteners can be used for polyamide fibers Type of diarylpyrazolines, for example 1 - (- p-sulfonamidephenyl) -3- (p-chlorophenyl) - t2-pyrazoline and similarly structured compounds that replace the sulfonamido group carry a carboxymethyl or acetylamino group. Substituted ones can also be used Aminocoumarins, e.g. 4-methyl-7-dimethylamino- or 4-methyl-7-diethylaminocoumarin. The compounds 1- (2-benzimidazolyl) -2- (1-hydroxyethyl-2-benzimidazolyl) -ethylene are also used as polyamide brighteners and 1-ethyl-5-phenyl-7-diethylamino-carbostyril can be used. As a brightener for polyester and polyamide fibers are the compounds 2,5-di- (2-benzoxazolyl) -thiophene, 2- (2-benzoxazolyl) ) naphtho-2,3-bthiophene and 1,2-di- (5-methyl-2-benzoxazolyl) -ethylene are suitable.

Mixtures of the abovementioned brighteners can also be used.

Particularly suitable graying inhibitors are carboxymethyl cellulose, Methyl cellulose and hydroxyethyl cellulose, as well as water-soluble polyesters and polyamides from polyvalent carboxylic acids and glycols or diamines, the free ones to form salts have capable carboxyl groups, betaine groups or sulfobetaine groups and Polymers or copolymers of vinyl alcohol, vinylpyrroldione, which are colloidally soluble in water, Acrylamides and acrylonitrile. Other ingredients in the invention Agents may be included are enzymes from the class of proteases, lipases and amylases, also neutral salts, especially sodium sulfate, bacteriostatic Substances such as halogenated phenol ethers and thioethers, halogenated carbanilides, halogenated Salicylanilides and halogenated diphenylmethanes, as well as dyes and fragrances. In Detergents to be used in washing machines may contain known foam suppressants, such as saturated fatty acids or their alkali metal soaps with 20 to 24 carbon atoms, higher molecular weight fatty acid esters or triglycerides, paraffins, trialkylmelamines and Silicone antifoam.

EXAMPLE Detergents of the following composition were produced by hot spraying an aqueous slurry prepared (5 'by weight): 0.3% optical brightener 7.0 % Sulfonate detergent 2.5% C16-C18 fatty alcohol 10 times ethoxylated 3.0% soap (Na tallow soap: Na behenate = 1: 1) 30.0% pentasodium tripolyphosphate 9.5% soda 0.5% sodium ethylenediaminetetraacetate 5.0% sodium silicate (Na2O: SiO2 = 1: 3.3) 2.5% magnesium silicate 1.5% sodium carboxymethyl cellulose 10.4% sodium sulfate 7.8% water.

The following were then also mixed in: 20.0% sodium perborate.

The optical brightener consisted of A) 4,4'-bis- (2-sulfostyryl) -diphenyl, (Na salt) B) 4,4'-bis (2-chloro-5-sulfostyryl) -diphenyl, (Na salt) and the sulfonate detergent raw material from n-alkanesulfonate C13-C18, average chain length C15.4.

In the comparative experiments A ') 4,4'-bis (2 "-anilino-4" -morpholino-1,3,5-triazinyl-6 "-amino) -stilbene-2,2'-disulfonic acid, (Na salt) B ') 4,4'-bis (2 "-anilino-4" -diethanolamino-1,3,5-triazinyl-6 "-amino) -stilbene-2,2'-disulfonic acid, (Na salt).

as well as n-dodecylbenzenesulfonate (sodium salt) as sulfonate detergent raw material.

In a further experiment, a 1: 1 mixture of n-alkanesulphonate and n-dodecylbenzenesulphonate used.

The detergents were put in 300 g cardboard boxes at 25 ° C. and 80% rel. Humidity kept. After 3 weeks the agents containing n-alkanesulphonate and brighteners A and B began to turn yellow-green. After 10 weeks the following picture emerged (1 = no discoloration, 2 = moderate discoloration (light yellow), 3 = severe discoloration (intense yellow-gray). valuation Gas raw material brightener AB A ' Alkanesulfonate 1 1 3 3 Alkanesulfonate + alkylbenzenesul- month 1: 1 1 1 2 2 n-dodecylbenzene sulfonate 1 1 1 1 It was found that the agents containing alkanesulphonates and brighteners of the triazinyl-stilbene-disulphonic acid type were more or less strongly discolored, while the mixtures according to the invention appeared pure white and did not differ from those containing alkylbenzenesulphonates.

Claims (4)

Claims Detergents with a content of 10 to 20 carbon atoms containing n-alkanesulfonates and optical brighteners, characterized in that their content of n-alkanesulfonates is 1 to 20 percent by weight and the optical brightener, which is present in amounts of 0.001 to 1 wt consists of at least one 4,4'-distyryl-diphenyl compound of the following formula wherein at least one of the radicals R1, R2, R3 and R4 is a -SO3Me group and the others can be the same or different and are -H, SO2NR5R6, -OCH3, -CN, -Cl, -COOCH3 and -CONR5R6 and where Me represents an alkali metal and R5 and R6 represent H or alkyl radicals having 1 to 4 carbon atoms. 2. Means according to claim 1, characterized in that it is 2 to 15 Contain 5 'by weight of n-alkanesulfonates in the form of the sodium salts. 3. Means according to claim 1 and 2, characterized in that in the Formula of the optical brightener for one or two of the groups R1, R2, R3 and R4 -SO3Na and the others represent H or Cl. 4. Means according to claim 1 to 3, characterized in that it further surface-active washing active substances and inorganic and / or organic builder substances contain.