DE1953519A1 - Textile treatment agents - Google Patents

Description

As is well known, brightener can accumulate on the textile fiber come when textile treatment agents containing optical brighteners, such as detergents or softeners, used very often and overdosed, especially over a long period of time. This accumulation of brightener leads to a greening of white tissues. The object was therefore to find such brightening agents which have these disadvantages do not own and deliver a neutral white even in the event of an overdose.

The invention relates to a textile treatment agent, characterized by a content of a mixture of optical brighteners of the formulas A) and B):

A)

C ₆ H ₅ NH

-Ν η

Vn- /

B)

C ₆ H ₅ NH
/

I Vn- /

HoC ^Nn ch ₀

2 | ι 2

H H

SO ^ M SO-. M.

HNC ₆ H ₅

2ϊ ■ γ

H _O C _V CHo

* 0

109830/1959

Henkel & Cie GmbH s.n ·

4018

in which M is an alkali metal or an ammonium group, preferably, however, sodium, η and m are integers from 1 to J5 and the weight ratio of the compound mentioned under A) to the compound mentioned under B) 2 = 1 to 1: 4, preferably 2: 1 to 1; 2 is.

Among the compounds of the formula A, preference is given to using those in which η = 1 or 2 and m = 2 or 3. Examples of such groups are the methoxyethyl, methoxypropyl, ethoxyethyl and kthoxypropyl groups.

Textile treatment agents are all used for treatment, i.e. for cleaning, bleaching, finishing and finishing agents suitable for textile fibers, yarns and fabrics, but preferably detergents, rinsing agents with a finishing effect as well as stiffening agents for textiles made of cellulose fibers. The textile detergents have a content of surface-active detergent raw materials as well as inorganic ones and / or organic non-surface-active builder salts and contain the brightener mixture according to the invention in an amount of 0.01 to 1 wt .- ^, based on the solids content. The fabric softening agents contain essentially a water-dispersible, higher molecular ammonium compound, especially a quaternary ammonium salt. the Stiffening and finishing agents essentially contain a polymer which is soluble or dispersible in water natural or synthetic origin. The one on solid proportion-related content of the whitening, stiffening and Finishing agent on the brightener mixture according to the invention is also from 0.01 to 1% by weight.

109830/1959

Henkel & Cie GmbH sä. 3 »w -» »ίο 4O18

The detergents and cleaning agents can contain customary anionic washing raw materials of the sulfonate or sulfate type. Primarily alkylbenzenesulfonates, for example n-dodecylbenzenesulfonate, come into consideration, furthermore olefin sulfonates, such as, for example, by sulfonation of primary or secondary aliphatic monoolefins with gaseous sulfur trioxide and then alkaline or acid hydrolysis, as well as alkyl sulfonates, such as those obtained from n-alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins. Also suitable are primary fatty acid esters 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 sulfated ones Partial ethers and partial esters of polyhydric alcohols, such as the alkali salts of the monoalkyl ethers or the Monofatty acid ester of glycerol monosulfuric acid ester or of 1,2-dioxypropanesulfonic acid. Sulphates also come from ethoxylated or propoxylated fatty acid amides and alkylphenols and fatty acid taurides and fatty acid isethionates in question.

Other suitable anionic washing raw materials are alkali soaps of fatty acids of natural or synthetic origin, e.g. the sodium soaps made from coconut, palm kernel or tallow fatty acids. As zwitterionic washing raw materials come alkyl betaines and especially alky sulfobetaines possible, e.g. 3- (N, N-dimethyl-N-alkylammonium) -propane-1-sulfonate and 3- (N, N-dimethyl-N-alkylammonium) -2-hydroxypropane-1-sulfonate.

109830/1959

aiÖwfc? OA *

Henkel & Cie GmbH Salt »4 tut Pat.ntanm.ldune D

401Ö

The anionic detergent raw materials can be in the form of sodium, ' Potassium and ammonium salts and as salts of organic bases, such as mono-, di- or triethanolamine, are present. If the anionic and zwitterionic compounds mentioned are an aliphatic hydrocarbon radical have, this should preferably be straight-chain and have 8 to 22 carbon atoms. In the connections with an araliphatic hydrocarbon radical contain the preferably unbranched alkyl chains on average 6 to 16 carbon atoms.

Polyglycol ether derivatives of alcohols, fatty acids and alkyl phenols which contain 5 to glycol ether groups and 8 to 20 carbon atoms in the hydrocarbon radical are primarily suitable as nonionic surface-active washing active substances. Polyglycol ether derivatives in which the number of ethylene glycol ether groups is 5 to 15 and the hydrocarbon radicals of which are derived from straight-chain, primary alcohols with 12 to 18 carbon atoms or from alkylphenolics with a straight-chain alkyl chain containing 6 to 14 carbon atoms are particularly suitable. By the addition of 3 to 15 mol

Propylene oxide to the latter polyethylene glycol ethers or by converting them into the acetals, detergents are obtained which are characterized by a particularly low foaming power distinguish.

Further suitable nonionic washing raw materials are the water-soluble, ο containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. Polyethylene oxide adducts with polypropylene glycol, A'thylendioo aminopolypropylene glycol and alkyl polypropylene glycol with _o 1 to 10 carbon atoms in the alleyl chain. The compounds mentioned usually contain 1 to 5 ethylene glycol units per propylene glycol unit. Non-ionic compounds of the amine oxide and sulfoxide type, which may also be ethoxylated, can also be used.

Henkel & Cie GmbH ropes 5 ^lur patent application D 408

Suitable detergent constituents are also inorganic cleaning salts, in particular condensed phosphates, such as pyrophosphates, phosphates, tetraphosphates, trimetaphosphates, tetrametaphosphates and more highly condensed phosphates in the form of the neutral or acidic sodium, potassium or ammonium salts. Alkali metal triphosphates and their mixtures with pyrophosphates are preferably used. Silicates can also be used, in particular sodium silicate in which the ratio of Na ₂ O: SiO _{3 is} 1: 3.5 to 1: 1.

The condensed phosphates can also be wholly or partly by organic, cleansing, nitrogen or be replaced phosphorus-containing complexing agents. For this count the alkali or ammonium salts of nitrilotriacetic acid, ethylenediaminotetraacetic acid, diethylutriaminopentaacetic acid and the higher homologues of the aminopolycarboxylic acid mentioned. Suitable homologs can, for example by polymerization of an ester, amide or nitrile of N-acetic acid aziridine and subsequent saponification carboxylic acid salts or by reacting polyamines with a molecular weight of 500 to 100,000 with chloroacetic acids or bromoacetic acid salts are produced in an alkaline medium. Further suitable aminopolycarboxylic acids are poly (N-ß-propionic acid) -ethylenimines with an average molecular weight of 500 to 200,000, which are analogous the N-acetic acid derivatives are available. Useful phosphorus-containing complexing agents are the alkali and Ammonium salts of aminopolyphosphonic acids, in particular aminotri-C methylene phosphonic acid), ethylenediaminotetra (methylenephosphonic acid), l-hydroxyethane-lA-diphosphonic acid, methylenediphosphonic acid, ethylenediphosphonic acid and the higher homologues of the polyphosphonic acids mentioned. Also mixtures of the aforementioned complexing agents are usable.

109830/1959

Henkel & Cie GmbH s · »·

Neutral salts, such as sodium sulfate and sodium chloride, and substances for regulating the pH value, such as bicarbonates, carbonates, borates and hydroxides of sodium or potassium _, and acids, such as lactic acid and citric acid, can also be used as components of the mixture. The amount of alkaline substances, including alkali silicates and phosphates, should be such that the pH value of a usable lye is 9 to 12 for coarse laundry and 6 to 9 for delicate laundry.

Through a suitable combination of different surface-active Detergent raw materials or synthesis salts with one another can in many cases increase the effectiveness, for example a improved detergency or reduced foaming power can be achieved. Such improvements are for example possible by combining anionic with nonionic and / or zwitterionic compounds with one another, by combining different nonionic compounds with one another or by mixtures of Washing raw materials of the same type, which differ in terms of the number of carbon atoms or the number and position of Distinguish double bonds or chain branches in the hydrocarbon. They can also act synergistically Mixtures of inorganic and organic synthesis salts used or combined with the mixtures mentioned above will.

Depending on their intended use, the agents can contain oxygen-releasing bleaches, such as hydrogen peroxide, alkali perborates, alkali percarbonates, alkali perphosphates, urea perhydrate and alkali persulfates or compounds containing active chlorine, such as alkali hypochlorites, chlorinated trisodium phosphate and chlorinated cyanuric acid or their alkali salts. The per connections can be mixed with bleach activators and stabilizers such as magnesium silicate.

109830/1959 ^ o ώλ «- 7 -

Henkel & CiG GmbH S · »· 7 ^Igf Palonlonm.ldvna 0 4018

Other suitable detergent ingredients are graying inhibitors, e.g. sodium cellulose glycolate, as well as the water-soluble alkali salts of synthetic polymers, which contain free carboxyl groups. These include the polyesters or polyamides made from tricarboxylic and tetracarboxylic acids and dihydric alcohols or diamines, also polymeric acrylic, methacrylic, maleic, fumaric, itaconic, citracon and aconitic acid and the copolymers of the unsaturated carboxylic acids mentioned or their copolymers with olefins.

Preparations intended for use in drum washing machines suitably contain known foam-absorbing agents Agents such as saturated fatty acids or their alkali soaps with 20 to 24 carbon atoms or triazine derivatives, by reacting 1 mole of cyanuric chloride with 2 to 3 moles of an aliphatic, straight-chain, branched or cyclic primary monoamine or by propoxylation or butoxylation of melamine.

To further improve the dirt-releasing properties of the agents according to the invention, these can also contain enzymes the class of proteases, lipases and amylases. The enzymes can be of animal and vegetable origin, e.g. obtained from digestive enzymes or yeasts, such as pepsin, Pancreatin, trypsin, papain, catalase and diastase. Preferably from bacterial strains or fungi, such as Bacillus subtilis and Streptomyces griseus, obtained enzymatic Active ingredients used that are relative to alkali, percompounds and anionic washing active substances are stable and also at temperatures between ^ 5 ° and 70 ° C cannot yet be inactivated to any significant extent.

Henkel & Cie GmbH page 8 ₂ ur patent application D 401Ö

Furthermore, bactericidal substances, in particular halogenated diphenyl ethers, halogenated diphenylurea derivatives and halogenated salicylic anilides may be present. To improve grip non-quaternary higher molecular ammonium compounds can be added, e.g. tallow fatty acid amide of aminoethylethanolamine. Mono- and diethanolamides or isopropanolamides of higher molecular weight are used as skin protection agents Fatty acids into consideration.

The detergents can be liquid, pasty or solid, for example powdery, in particular spray-dried, granulated or lumpy form. Liquid preparations can be used for the purpose of better Solubility with water-miscible solvents, in particular ethanol and i-propanol as well as solubilizers, such as the alkali salts of benzene, toluene, xylene or ethylbenzene sulfonic acid.

The composition of the various detergent ingredients, the proportion of which is a total of 99 to 99.99 percent by weight, based on the solids content, can be the heavy duty detergents of particular interest to the following Correspond to the scheme (data in percent by weight):

1953513

& Cie GmbH Since. 9 rur Pafonlonm.lduiie D

1 to 40 % of at least one compound from the class of anionic, nonionic and zwitterionic washing active substances,

10 to 80 % of at least one non-surface-active, cleaning enhancer or complexing building salt,

10 to 50 % of a per-compound, in particular sodium perborate containing water of crystallization or anhydrous, and mixtures thereof with stabilizers and activators, 0.1 to 20 % other auxiliaries and additives.

The washing-active substances can be up to $ 100, preferably 5 to 70 f "from compounds of sulphonate and or or Suifattyp, up to 100%, preferably 5 to 40% of non-ionic compounds from Polyglykoläthertyp and up to 100%, preferably 10 to 50 % of soap are made. the structure of salts can be up to 100%, preferably 25 to 95% of alkali metal triphosphates, and mixtures thereof with alkali metal pyrophosphates, up to 100%, preferably 5 to 50% of an alkali metal salt of a complexing agent from the class of polyphosphonic acids, nitrilotriacetic acid, Ä 'ethylenediaminetetraacetic acid and up to 100 %, preferably 5 to 75 %, of at least one compound from the class of alkali metal silicates> alkali metal carbonates and alkali metal borates.

To the other excipients and additives include in addition to the optical brighteners in particular the foam inhibitors that may be present in the inventive compositions in an amount up to 5 i>"preferably in an amount of 0.2 to 3%, and also the enzymes that in an amount up to 5 ° Ϋ * preferably 0.2 to 3 may be present ^ and the antiredeposition agents, the proportion can be up to 5% preferably from $ t $ to 5> 0.2.

109830/19

- 10 -

Henkel & Cie GmbH

Ropes -LO iur patent application D * fÜJ.Ö

The higher molecular weight ones preferably contained in the softeners Ammonium compounds can have the following formulas:

(D

Ri

(2)

fr

R ₁ -CO-NR ^ -NR ,,

Rr- R, -

O)

, N-CII ₂ N-CiU

(5)

(6)

^X N-CH ₂

R _c R ^ -NH-CO-R ₀ 56

109830/1959 - left -

OBlGlNAL

Henkel & Cie GmbH s · »» 11 «ι Pai» nfonmeUun _B ο 401θ

in which

R ₁ and R _2, identical or dissimilar, saturated or unsaturated aliphatic hydrocarbon radicals with 11 to 25, preferably 15 to 21 "carbon atoms, R, an alkyl or hydroxyl group with 1 to 2 carbon atoms,

Rj, = R., or a benzyl group, R ₁ . = R., or a hydrogen atom, Rg is an alkylene group with 1 to 5 carbon atoms

and A is an anion, for example a halide, acetate or Alkyl sulfate ion or an equivalent of a sulfate or Phosphate ions or the anion of a polyvalent carboxylic acid, e.g. oxalic or citric acid.

Mixtures of different surface-active ammonium compounds can also be used. The agents according to the invention preferably contain quaternary ammonium salts according to formula 1, in which the radicals R 1 and R _{2 represent} straight-chain, saturated hydrocarbon radicals having 16 to 18 carbon atoms and the radicals R ₇ and R _{2 represent} methyl or ethyl groups.

The quaternary ammonium compounds can also be wholly or partially be replaced by condensation products, "which are produced by reacting hardened tallow fatty acid triglyceride with aminoethylethanolamide obtained in a molar ratio of 1: 1 and with inorganic or organic acids, in particular glycolic acid, were neutralized.

The mixtures of higher molecular weight ammonium compounds and optical brightener can be in anhydrous form or else in the presence of water or water-miscible solvents be mixed. In the first case, mixtures of a firm to lard-like consistency are obtained. solidified by the addition of inert fillers or converted into granular, loose powder. Preferably however, the mixtures are in the form of water-containing, pourable dispersions or pastes. Contain such dispersions Generally from 5 to 15, preferably from 5 to 10% by weight surface-active ammonium compound.

19th

& Gie © mbH S · »· ^Λ tor Paientanmeldune D

The storage stability of the aqueous dispersions can, if necessary, be improved by adding small amounts of stabilizers. Suitable stabilizers are, for example, fatty acid alkylolamides, in particular fatty acid mono- or diethanolamide, fatty acid mono- or dipropanolamide and fatty acid mono- or diisopropanolamide, and also polyethylene glycols with a molecular weight of 200 to 10,000 and polyethylene glycol ether derivatives of higher molecular weight alcohols or alkyl phenolic acid esters, amines, fatty acid esters, and alkyl phenols polyhydric alcohols. In the aforementioned polyglycol ether derivatives, the hydrophobic hydrocarbon radical can have 10 to 24 carbon atoms and the polyglycol ether radical can have 2 to 50 ethylene glycol ether groups. The dispersions can contain the stabilizers in amounts of 0.05 to 5 %, preferably 0.1 to 1 % .

The customary additives and solvents can also be added to the aqueous dispersions. Neutral salts such as sodium chloride, sodium sulfate, sodium borate, sodium acetate, sodium citrate and the corresponding potassium and ammonium salts in amounts of up to 2 %, preferably 0.05 to 1 %, are suitable. Organic solvents such as low molecular weight alcohols, in particular ethanol and isopropanol, ether alcohols, glycols, di- and triglycols, glycerol, polyglycerol and glycerol ethers, ketones and alkyl oil ureas in amounts of up to 10 %, preferably 0.5 to 5 % , are also suitable. In addition, suitable preservatives, dyes and fragrances can be added to the agents.

As far as the washing and softening agents mentioned are also used for the simultaneous treatment of textiles made of synthetic fibers or If mixed fabrics made of cellulose and synthetic fibers are to be used, optical brighteners can also be added on synthetic fibers, but not on cellulose fibers. These include brighteners of the I, j5-diarylpyrazoline type, Coumarins, carbostyryls, benzoxazoles and benzimidazoles.

13 -

Henkel & Cie GmbH S.Ho I5 xur Pat.iUanmelduna D 4Ol8

Another area of application is the use of optical brighteners in textile stiffening and finishing agents in question. Such agents are usually contained in water soluble or dispersible polymers of natural or synthetic origin, such as starch, for example corn or Rice starch, alkoxylated starch, carboxymethyl cellulose, methyl or ethyl cellulose, oxyethyl cellulose, polyethylene oxide, in particular those with a molecular weight of 2000 to 20,000, polyvinyl alcohol, polyvinyl acetate, partially saponified Polyvinyl acetate, polyvinyl pyrrolidone, polyacrylonitrile, polyacrylic acid and copolymers of the above Viny! Polymers. Mixtures of different polymers are also possible common. To improve the properties of these agents, neutral salts such as sodium chloride, borax or Sodium acetate, solvents and softeners such as methanol, ethanol or isopropanol, ether alcohols, glycols, glycol ethers, Glycerine and other polyalcohols, also enionic and / or nonionic wetting agents, preservatives, fragrances and ironing aids, such as paraffins and kart waxes, are added will. The agents can be in the form of a powder, paste or aqueous dispersions. Your content of the invention Brightener combination is 0.01 to 1 percent by weight, based on solid substance.

Henkel & CIe GmbH s. *. 1 * «,, r _a H, *, n _m .u _uaa α ^ 018 Examples

Non-lightened cotton fabric was used 20 times each 10 minutes at a temperature of 60 ° C, a weight ratio washed from textile material to wash liquor of 1:20 and a detergent concentration of 5 g / l. The detergent had the following composition (data in percent by weight):

10 % n-dodecylbenzenesulfonate (Na salt)

3 % oleyl alcohol with 10 ethylene glycol ether groups

3 % Na soap from saturated C ^ -Cpp fatty acids

45 % pentasodium triphosphate

22 % sodium perborate

3.5 % sodium silicate (Na ₂ O: SiO ₂ «= 1: 3.5)

2.5 % magnesium silicate

0.5 % Na ethylenediaminetetraacetate

0.5 % sodium cellulose glycolate

The remaining 10 % was made up of optical brighteners, which were used in the form of the sodium salts, and sodium sulfate. The compound referred to below as A. is a brightener of the formula A in which the

Group "Cm ^ n ^ '^ n' ^ n + 1 ^{corresponds to the formula} -C ₂ H ^ -O-CH _5. In the case of the _{brightener designated with A 2} , this group corresponds to the formula -C ₅ Hg-O-CH ₅ . Brightener B consists of the sodium salt of 4,4'-bis- (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid according to formula B. The proportion the brightener and its total amount can be found in the following tables.

- 15 -

109830/1959

Henkel & Cie (3mbH

S.lle

15th

ivt patent application D

The brightness and the discoloration that occurred were determined photometrically using the "Elrepho" device (manufacturer Carl Zeiss, Oberkochen, Federal Republic of Germany) using a xenon lamp and the three color filters FMX / L, FMY / L and FMZ / L. The standardized color values were derived from the measured reflection values R _x , Κ _γ and R ₂ using the conversion factors specified by the device manufacturer

X = 0.785 R _x + 0.16? K ₂ Y = R _y

Z = 1.008 R ₂

calculated. From this, the coordinates χ and y, also called color value components, can be calculated in the CIE standard color table (CIE »Commission International de l'Eclairage) as follows:

X as

X + Y + Z

and y

X + Y +

A shift towards green that is clearly perceptible to the eye is with a greater increase in y and a simultaneous one small decrease of χ associated. In the following The table shows the color coordinates as a function of the amount of brightener, the brightness Y of the textile samples as well as the optically perceptible color shift indicated when the amount of brightener is increased «While when using the pure brightener types with increasing brightener concentration

- 16 -

109830/1959

8AO ORiGtNAL

Henkel & Cie GmbH s «it · Io mr Pat« ntanm «iduns d 40Io

a color shift to green occurs * which results in the following comparative experiments I and III in an increase in the y-coordinate by Γ3 to 14 units and in Comparative Experiment II by 20 units in the 3 · "and 4th digit after the comma, is in the inventive Examples no color shift to be seen. The change in the color value coordinate is y in these Cases no more than a maximum of 4 to 6 units. They differ in terms of brightness Tissue samples are not significantly different from each other.

- 17 -

109830/1959

8AD

Henkel & Cie GmbH

5 · ίι ·

xur patent application O

4018

example % Brightener 0.2 0.2 Color coordinates
dates y Bright
speed Color var
shift A ₁ B 0.4 0.4 X 0.3401 Y without 0.6 0.6 0.5220 0.5055 89.1 comparison 0.8 0.8 0.2975 0.5051 92.8 I. 1.0 1.0 0.2965 0.5057 93.1 reddish-white 0.155 0.067 0.2968 0.5059 93.5 after
greenish-white 0.267 0.155 0.2969 0.5065 95.5 0.4 0.2 0.2970 0.5045 95.1 0.555 0.267 0.2965 0.5047 95.2 comparison 0.677 0.555 0.2955 0.5054 95.7 bluish-white
Vl O Λ V * II 0.1 0.1 0.2956 0.5060 94.0 well cn
greenish-white 0.2 0.2 0.2959 0.5065 94.1 0.5 0.5 0.2961 0.5055 94.0 0.4 0.4 0.2967 0.5052 95.0 1 0.5 0.5 0.2965 0.3056 93.2 pure white 0.067 0.155 0.2965 0.5058 92.8 0.155 0.267 0.2964 0.5057 93.5 0.2 0.4 0.2965 0.3050 95.1 0.267 0.555 0.2965 0.3055 95.2 2 0.555 0.677 0.2965 0.5055 95.5 0.2965 0.5056 95.5 pure white 0.2962 0.5055 95.6 0.2960 0.5049 95.5 0.2962 0.3052 95.2 0.2959 0.5056 95.6 J 0.2961 0.5056 93.5 pure white 0.2959 0.5055 93.7 0.2958 93.8

Table I.

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109830/1959

ft v

Henkel & Cie GmbH Salt

example % Brightener 0.2 0.2 Color coordinates ι Bright Color var 0.4 0.4 dinater ι y speed shift A 2 B 0.6 0.6 χ 0.3401 Y without 0.8 0.8 0.3220 0.3052 89.1 - comparison 1.0 1.0 0.2974 0.3055 92.6 III 0.133 0.067 0.2968 0.3055 92.9 !
reddish white _; 0.267 0.133 0.2971 0.3063 93.1 after
greenish-white 0.4 0.2 0.2969 0.3065 93.1 0.533 0.267 0.2974 0.3043 92.9 0.677 0.333 0.2963 0.3047 93.2 comparison 0.1 0.1 0.2955 0.3054 93.7 bluish-white II 0.2 0.2 0.2956 0.3060 94.0 nacn
greenish-white 0.3 0.3 0.2959 0.3063 94.1 0.4 0.4 0.2961 0.3049 94.0 0.5 0.5 0.2970 0.3050 92.8 ι, 0.067 0.133 0.2968 0.3052 93.1 pure white 4th 0.133 0.267 0.2967 0.3050 92.9 0.2 0.4 0.29όδ 0.3053 93.3 0.267 0.533 0.2966 0.3048 93.1 0.333 0.677 0.2969 0.3050 92.9 5 0.2965 0.3052 93.3 0.2966 0.3050 93.4 pure white 0.2965 0.3053 93.6 0.2963 0.3049 93.5 0.2964 0.3048 93.2 6th 0.2962 0.30531 93.4 0.2963 0.3052 93.5 pure white 0.2961 0.3054 93.7 0.2961 93.8

Table II

- 19 -109830/1959

Henkel & CIe GmbH s »» · 19 ^tur * oi »" tanm.idun _e d ty8

Example 4

With a detergent of the composition (in percent by weight):

15 % Coeos fatty alcohol diglycol ether sulfate (Na-Salz)

15 % nonylphenol polyglycol ether (10 ethylene glycol ether groups)

2 % Coeos fatty acid diethanolamide 20 % disodium pyrophosphate 47 fo sodium sulfate

1 % optical brightener mixture in the ratio A. to B like 1: 2

cotton fabric 10 times were 15 minutes at 60 ⁰ C j a Wasehrr.ittelkonzentration of 5 g / l and a ratio of textile material to liquor of 1: washed 10th Despite the comparatively high concentration of brightener, there was no perceptible color shift. If the individual components A. and B were used in proportions of 1 to 6 each instead of the brightening mixture, a clearly visible greening compared to the initial color value occurred.

A comparison of Examples 1 to 3 and H shows that the color shift is independent of the composition of the remaining detergent components.

Example 5

Bauiflv / olltextilien were impregnated with an aqueous dispersion, the 10 g / l of a stiffening agent according to the following Composition contained (in percent by weight):

- 20 -

109830/1959 BAO ORIGINAL »

Henkel & Cie GmbH S * it.2O * gr Pal.rrtanm.rdvng D 401Ö

97.8 % rice starch

1.0 % polyethylene glycol (molecular weight 4000) 0.2 % wetting agent (sodium coconut fatty alcohol sulfate)

1.0 % optical brightener mixture in the ratio Ao ^{: B like} 2: 1.

The stiffened and ironed textiles were markedly lighter than those that had been treated with a brightener-free preparation of the same composition. ^O ne Färbverschiebung had not occurred.

Example 6

Cotton textiles that had previously been washed with a detergent according to Examples 1 to 3 were placed in a final rinse liquor which contained 1 g / l of the following.Avivagemittels:,. ~ _{V. r} >:

7.5 # di-tallow alkyl dimethyl ammonium chloride

2.7 % isopropanol

0.5 % polyethylene oxide (molecular weight 400)

0.3 % sodium acetate

0.08 % of the optical brightener mixture according to the invention in the ratio A ^: B such as 1: 2

Rest water

The weight ratio of textile material to treatment liquor was 1: 8. After spinning and drying, the samples were compared with non-finished comparison samples. Apart from a slight decrease in the degree of whiteness, which can be attributed to a slight quenching of the fluorescence by the quaternary ammonium salts, no color shift was perceptible.

SAD ORIGINAL

Henkel & CIO GmbH S «it« 21 for patent application D 4018

In the following table are about the invention Detergents, bleaches and softeners put together. Ingredients a to f and h to 1 were present as sodium salts, the pyrophosphate (ingredient m) came in the example 9 as the potassium salt, in all other examples as the sodium salt. As an enzyme (component s) used a preparation Maxatase obtained from Bacillus subtilis from the Koninklijke Nederlandsche Gist en Spiritusfabriek N.V. DeIft, with an activity of 100,000 LVU / g. The cosmetic agent (component w) consisted of example 10 and 11 from a reaction product of hardened Tallow fatty acid triglyceride with aminoethylethanolamine in a molar ratio of 1: 1, which is neutralized with glycolic acid had been, in Example 15 from a mixture of this reaction product with a di-tallow alkyl dimethyl ammonium chloride in a weight ratio of 3: 5 medium (component y) is a reaction product of 1 mol of cyanuric chloride with 2.7 mol of a primary η-Alky! amines of chain length Co-C-, g.

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109830/1959

(O ι co ro ω ο ι «Ν. (O (0

7th 8th 9 Examples (Declarations in weight . - *) 14th 15! ; - I. component 0.2 0.1 0.1 10 11 12th 13th 0.1 0.05 ' I. - I. 0.3 0.2 0.1 0, £> 5 0.1 0.2 0.2 0.1 0.05 ! - W. a) Type A optical brightener 6th - 5 0.05 0.1 0.3 0.2 10 - ' 0.7; 0.5 fr
O b) Type B optical brightener 3 - - 15th - - - - - φ c) n-dodecylbenzenesulfonate - 10 5 - 8.5 - 7.5 - - Ω
mm d) C ₁₂ -C ₁₈ olefin sulfonate - - 5 - - 0.5 - - - j 3
CT e) Ci4-Ci7 alkanesulfonate 3 4th - 10 - - - • m J f) Coconut fatty alcohol glycol ethersulfate (2 ÄO) 3 - - 5 1.5 - 2.5 - ; g) oleyl alcohol polyglycol ether (10 ÄO) - 2.2 - - 2 - 4th - 2.5 h) C i2 "C je" soap 25th . - - 2 - 0.5 - 6.5 i) C20-C22 soap - 0.5 1 - 10 - - - 0.1 j) nitrilotriacetate 10 20th - 0.4 - 0.5 0.5 - - - k) ethylenediaminetetraacetate - - 20th - 25th - 45 2 89.6 ro 1) tripolyphosphate - 20th - - - - 3 35 ro m) pyrophosphate 5 4.5 - - - 25th - 25th C. n) soda 4.4 - - - 5 20th 3.5 - a
2. ο) sodium silicate 25th 30th - 45 12th - 0.4 10 Q
3
3 p) sodium sulfate 3 - - - 20th 50 25th 4th K.
C. q) sodium perborate 1.5 - - - 2 - 3.0 - «3
O r) magnesium silicate 1.5 0.5 - - 0.5 - 0.5 - .pr s) enzyme - - 7th - - - 0.5 - O t) Na cellulose glycolate - - - - - - - - H
oo u) Na toluenesulfonate - - - 5 - - - - v) coconut fatty acid diethanolamide 0.1 0.1 0.2 5 3 - - 0.1 w) plasticizers 0.5 - - - - - o.i • x) dyes and fragrances 8.5 7.9 56.6 - - - 0.2 13.7 y) foam suppressants 14.5 8.3 3.5 3.4 z) water

CD cn co cn

co

Claims (1)

Claims Ij Texti! Treatment agents, characterized by; a Content of a mixture of optical brighteners of the formulas A) and B): C ₆ H ₅ NH HNC ^ -H, A) ^H 2n ₊ 1 ^C n ^OC m ^H 2m ^NH B) HNC ₆ H ₅ SO ^ M SO ₃ M wherein M is an alkali metal or an ammonium group, but preferably sodium, η and m are integers of 1 to 3 and where the weight ratio of the compound mentioned under A) to the compound mentioned under B) is 3: 1 to 1: 4, preferably 2: 1 to 1: 2. 109830/1959 8AO OBIGIHAU Henkel & Cie GmbH S.ite24 for patent application D 40l8 2. Agent according to claim 1, wherein η is 1 or 2 and η is 2 or 3. ^. Composition according to claim 1 and 2, characterized in that the related Peststoffe content of optical brighteners 0.01 to 1 wt -.% And of detergent ingredients 99-99 * 99 wt -% by.. 4. Composition according to claim J, wherein the detergent ingredients to 1 to 40 wt .- ^ of at least one compound from the Class of anionic, nonionic and zwitterionic surface-active detergent substances, 10 to 80 wt -.% Of at least one niehtoberfläehenaktiven, reinforcing cleaning or complexing action Building salt,. . 10 to 50 wt -.% Of per-compounds and mixtures thereof with stabilizers and activators and 0.1 to 20 wt -% consist of additives from the class of foam inhibitors, antiredeposition agents, enzymes, biocides, avivierend acting substances and neutral salts.. ■ 5. Means according to claim 4, wherein the washing active substances up to 100 %, preferably 25 to 70 % from those of the sulfonate and / or sulfate type, up to 100 %, preferably 5 to 40 % from nonionic compounds of the polyglycol ether type and up to 100 %, preferably 10 to 50 % consist of soap. 6. Composition according to claim 4, wherein the building salt up to 100 #, preferably 25 to 95 % of alkali metal triphosphates and mixtures thereof with alkali metal pyrophosphates, up to 100 %, preferably 5 to 50 % of one - 25 - Henkel & CIe GmbH Sail · 25 for patent application D 40l8 Alkali metal salt of a complexing agent from the class of polyphosphonic acids, nitrilotriacetic acid, ethylenediaminotetraacetic acid and up to 100 %, preferably 5 to 75 %, of at least one compound from the class of alkali metal silicates, alkali metal carbonates and alkali metal borates. 7. Composition according to claim 4, wherein the per compound is anhydrous and / or containing water of crystallization Sodium perborate. 8. A composition according to claim 4, characterized in that it contains up to 5% _$ preferably 0.2 to 3% of at least one Scharuminhibitor from the class of saturated, from 20 to 22 carbon atoms · containing fatty acids and their alkali metal soaps, and the substituted triazines, obtainable by reacting 1 mole of cyanuric chloride with 2 to 5 moles of a primary monoamine or by propoxylation and / or butoxylation of melamine. 9. Composition according to claim 4, characterized in that they contain up to 5%, preferably 0.2 to 3 % , of enzymes. 10 »Agents according to claim 4, characterized in that they contain up to 5%> preferably 0.2 to 3 % of graying inhibitors. 11. Composition according to claim 1 and 2, characterized in that the content of optical brighteners based on pesticides 0.01 to 1 wt .- ^ and 99 to 99.99 wt .- ^ of conditioning, higher molecular weight ammonium compounds and mixtures thereof with Contains emulsifiers, stabilizers, neutral salts and other additives. -26 .. 109830 / 19-59- Henkel & Cie GmbH s. ». 26 _IU r pateManm.uung d 12. Composition according to claim 11 in the form of an aqueous dispersion, characterized in that they 3 to 15, preferably 5 to 10 wt -.% To avivierend acting ammonium compounds, 0.05 to 5 », preferably 0.1 to 1 wt -.% Of dispersion stabilizers from the class of fatty acid alkylolamides, polyethylene glycols and Polyäthylenglykolderivate of higher molecular weight alcohols, amines, fatty acids and alkylphenols, 0 to 2, preferably 0.05 to 1 weight ^ of neutral salts, 0 to 10, preferably 0.5 to 5 % of organic solvents from the class of low molecular weight monohydric and polyhydric alcohols, ether alcohols, ketones and alkylolureas, and the optical brightener within the specified weight ratios, preferably in an amount of 0.001 to 0.2 wt -% by weight.. 13 · Agent according to claim 11 and 12, wherein the surface-active Ammonium compound of the formula R ₂ +
¹ A corresponds, in which R ₁ and R _{2 are} alkyl chains with 16 to 18 carbon atoms, R, and R ^ are alkyl chains with 1 to 2 carbon atoms and A "* is the anion of an acid. -27 - 109830/1959 Henkel & Cie GmbH Page 2 I to the patent application DT * UJLÖ 14. Textile stiffening and finishing agents with a content characterized water-soluble or water-dispersible polymer that, based on solids, from 0.01 to 1 wt -.% containing a mixture according to claim 1. 15. Means according to claim 14, characterized in that the polymer is made of starch. H e η k e 1 & ) C. i e. GmbH. i .V. ' / A. J / cot ^ y (Dr . Haas (Dr. TJagel) 109830/1959 8AO ORIGINAL