DE1964024A1 - Detergents and cleaning agents - Google Patents

Description

Henkel & Cie GmbH Düsseldorf, December 8th, 1969

• toe λ η? L Henkelstrasse 67 Patent Department | 3O * "U /," t

Dr. Wa / Ml

Patent application

D 3676
"Detergents and cleaning agents"

It is well known that detergents and cleaning agents often contain larger amounts of condensed alkali metal phosphates, especially pentasodium triphosphate. The phosphates are supposed to bind the hardness components of the tap water in a complex way Increase the cleaning power of the capillary-active washing active substances. However, one is for various reasons strives not to have the phosphate content of the funds to increase a certain percentage or to lower it compared to the previously usual proportions. The task was therefore the polymer phosphates contained in detergents and cleaning agents are partly replaced by other phosphate-free substances to replace and at the same time improve the cleaning power and biodegradability of the mixtures.

Subject of the invention with which this object is achieved, are detergents and cleaning agents containing structural salts, characterized by a content of

a) I part by weight of at least one kapi'llar-active compound from the class of anionic, nonionic and zwitterionic washing active substances and

b) 0.5 to 20 parts by weight of a mixture of building salts, which consists of 20 to 75% by weight, preferably 30 to 65% by weight, of pentasodium triphosphate, 10 to 60, preferably 15 to 50% by weight , of sodium citrate and 3 to 50% by weight , preferably

5 to 40 wt .- ^ consists of sodium _{metasilicate (Na 2} 0: Si0 ₂ »l! 1).

109826/1741

“AD ORIGINAL

Henkel & CIe GmbH «ι« 2 _w rat.Monm.Mii «! ο 5o7o

Of particular interest are detergents with a low foaming power that are suitable for use in drum washing machines. If the capillary-active washing active substances used promote strong foam development, the agents contain 0.01 to 1 part by weight of at least one foam inhibitor. Suitable foam inhibitors are saturated fatty acids or their alkali metal salts with 18 to 24 carbon atoms, which in particular contain higher proportions of araehic acid, behenic acid and lignoceric acid and can be obtained, for example, from hardened peanut, beet or fish oil. Triazine derivatives are also suitable, for example N, N ¹ , N "-trialkylmelamines or 2,4-diaminoalkyl-6-chloro-1,3 * 5-triazines in which the alkyl radicals have 6 to 24 carbon atoms, and also propoxylated and / or butoxylated melamines with 6 to 100 polyglycol ether groups, for example one with 10 to 100 moles of propylene oxide or one with 6 to 30 moles of butylene oxide or a melamine first reacted with 3 to 30 moles of propylene oxide and then with 3 to 30 moles of butylene oxide . be advantageously used preferably is sized, the amount of foam inhibitors such that it contains 1 to 30 wt -% of the foaming is washing-active substance..

If necessary, paraffin hydrocarbons, haloparaffins, higher molecular fatty acid esters or triglycerides or dicarboxylic acid esters of higher molecular fatty alcohols used as foam suppressants or used in a mixture with the aforementioned foam inhibitors. However, the foam-suppressing effect of these substances is less than that of the foam inhibitors mentioned above, in particular if the detergents are soap-free. It is therefore advisable to use them only in soap-based products «

1Ö & Ö26 / 1741

BAD ORSGiNAL

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Henkel & CIo GmbH μ » 3» «r ·» «*» «»! * «· T> 36f6

The detergents and cleaning agents can be customary anionic Contain sulphonate or sulphate-type washing raw materials. 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 subsequent alkaline or acidic hydrolysis are obtained, as well as alkyl sulfonates, as they are made from n-alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins. Also suitable are <x / -Sulfof enoic 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 sulfated ones Partial ethers and partial esters of polyhydric alcohols, such as the alkali metal 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 as well as fatty acid taurides and fatty acid isethionates infr-age. .

Alkali soaps are further suitable anionic detergent raw materials of fatty acids of natural or synthetic origin, e.g. the sodium soaps from coconut, palm kernel or Tallow fatty acids. The zwitterionic detergent raw materials are alkyl betaines and in particular AHey! Sulfobetaines possible, e.g. 5- (N, N ~ dimethyl-N-alkylammonium) -propane-1-sulfonate and 3- (N, N-dimethyl-N-alkylammonium) -2-hydroxypropane-1-sulfonate.

109826/1741

Henkel & CIo GmbH * · »·" ι «fei« Me »m» u »ni o ~ *>& J

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 have an aliphatic hydrocarbon radical, this should preferably be straight-chain and have 8 to 22 carbon atoms. In the compounds with an araliphatic hydrocarbon radical, the preferably unbranched alkyl chains contain on average 6 to 16 carbon atoms.

Polyglycol ether derivatives of alcohols, fatty acids and alkylphenols which contain 3 to 50 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 whose hydrocarbon radicals are straight-chain are particularly suitable. primary alcohols with 12 to 18 carbon atoms or from alkylphenoien with a straight chain, 6 to 14 carbon atoms having alkyl chain. By adding 5 to 15 moles of propylene oxide to the last-mentioned polyethylene glycol ethers or by converting them into the acetals, detergents are obtained which are characterized by a particularly low foaming power.

Other suitable nonionic washing raw materials are the water-soluble 20 to 250 ethylene glycol ether groups and from 10 to 100 polyethylene oxide adducts containing propylene glycol ether groups with polypropylene glycol, ethylene diamino polypropylene glycol and alkyl polypropylene glycol having 1 to 10 carbon atoms in the alkyl chain. The mentioned Compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit, including nonionic ones Compounds of the amine oxide and sulfoxide type, the ßgf. can also be ethoxylated can be used.

109826/1741 -5-

BATH ORIGINAL Henkel & CIe GmbH μη 5 _{w ίθ} ι.Μ _Ο π «.. Μ« π _β t »5θ7θ

In many cases, through a suitable combination of different surface-active detergent raw materials with one another Increases in effectiveness, for example improved washing power or reduced foaming power, can be achieved. Such improvements are possible, for example, 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 double bonds or chain branches in the hydrocarbon.

Depending on their intended use, the agents can contain oxygen-releasing bleaching agents, such as hydrogen peroxide, Alkali perborates, in particular sodium perborate, alkali percarbonates, alkali perphosphates, urea perhydrate and alkali persulfates or active chlorine-containing compounds such as alkali hypochlorites, chlorinated trisodium phosphate and chlorinated cyanuric acid or its alkali salts. The per compounds can also be mixed with bleach activators are present.

In addition to the capillary-active washing active substances, build-up salts, foam inhibitors and bleaching agents, the agents can also contain other customary detergent ingredients. These include neutral salts, in particular sodium sulfate, silicates, such as magnesium silicate, which is suitable as a perborate stabilizer, _{and water glass, which acts as a corrosion inhibitor and has a Na 3 OsSiO 2} ratio of 10 to 1ί3 * 5 the hot spray drying of liquid detergent concentrates by partial hydrolysis of the sodium triphosphate.

109826/174 T - 6 -

Henkel & CIe GmbH $ # »· 6 _zvt rai.ni _O nm.idun _e d & S

Other suitable detergent ingredients are gray scale 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 and polyamides made from TrI «and tetracarboxylic acids and dihydric alcohols or diamines, also polymeric acrylic, methacrylic, maleic, Pumar, Itaeon, Citracon and aconitic acid and the copolymers of the unsaturated carboxylic acids mentioned or their copolymers with olefins.

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. from digestive ferment en or yeast, such as pepsin, pancreatin, trypsin, papain, catalase and Diastasis. Preferably from bacterial strains or fungi, such as Bacillus subtilis and Streptomyces griseus, recovered enzymatic active ingredients used, the opposite Alkali, per-compounds and anionic washing active substances are relatively stable and also at temperatures not yet significantly inactivated between 45 ° and 70 ° C will.

109326/1741

Henkel & CIe GmbH «·« · 7 «« ■ TaH * anm »\ tunt ο 367"

Suitable optical brighteners are those of the bis (triazinyl) -4, ² i- ^l -diaminostirDendisulfonsäuretyp of the formula; X

: N Vn- # Vc = c

^{r ===} T

in which X and Y have the following meanings: NH ₂ , NH-CH ₅ , NH-CH ₂ -CH ₂ OH, CH ₅ -N-CH ₂ -CH ₂ OH, N (CH ₂ -CH ₂ OH) ₂ , Morpholino, dimethylmorpholino, NH-C ₆ H ₅ , NH-C ₆ H ^ -SO ₅ H, OCH ,, Ci; 'where X and Y can be the same or different. Those compounds in which X is an anilino and Y is a diethanolamino or morpholino group are particularly suitable.

Optical brighteners of the Diarylpyra- ' zoline in question according to the formula below. ·

Ar-C- ₀ * Sj I ²

CH. / 2

I- · ■

In this formula, Ar and Ar ^{f are} aryl radicals such as phenyl. Diphenyl or naphthyl, which can carry further substituents, such as hydroxyl, alkoxy, hydroxyalkyl, amino, alkylamino, acylamino, carboxyl, sulfonic acid and sulfonamide groups or halogen atoms. A 1,2-diarylpyrazoline derivative is preferably used in which the radical Ar is a p-sulfonamidophenyl group and the radical Ar ^{1 is} a p-chlorophenyl group. In addition, whiteners suitable for lightening other types of fibers can also be present, for example those of the naphthotriazole stilbene sulfonate, ethylene-bis-benzimidazole, ethylene-bis-benzoxazole, thiophene-bis-benzoxazole, dialkylaminocoumarins and cyanoanthracene type. These brighteners or their mixtures can be contained in the agents in sizes from 0.01 to 1.5 wt .-%, preferably 0.1 to 1 wt .-%. .

109826/1741 bad o _{R) S (NAL} \

- 8 -

Henkel & Cie GmbH u \ i * Ö «

The agents can also contain complexing agents to stabilize the optical brighteners. These include the alkali salts of Sthylenediamino-tetraacetic acid, which are preferably used, and also the alkali salts of diethylenetriaminopentaacetic acid and the higher homologues of the aminopolycarboxylic acid mentioned. Suitable homologs can be prepared, for example, by polymerizing an ester, amide or nitrile of N-acetic acid aziridine and subsequent saponification to carboxylic acid salts or by reacting polyamines with a molecular weight of 500 to 100,000 with chloroacetic acid or bromoacetic acid salts in an alkaline medium. Further suitable complexing agents are the alkali salts of aminopolyphosphonic acids, in particular aminotri (methylenephosphonic acid), ethylenediaminotetra (methylenephosphonic acid), 1-hydroxyethane-1il-diphosphonic acid, methylenediphosphonic acid, ethylenediphosphonic acid and the higher homologues of the polyphosphonic acids mentioned. Mixtures of the abovementioned complexing agents can also be used.

Bactericidal substances, in particular halogenated substances, can also be used Diphenyl ethers, halogenated diphenyl urea derivatives and halogenated Salicylic anilides may be present. Non-quaternary higher molecular ammonium compounds can be used to improve the grip be added, e.g. the tallow fatty acid amide of aminoethylethanolamine.

The detergents can be liquid or pasty, preferably however, in solid, for example powdery, granulated or lumpy, in particular spray-dried, form. For the purpose of better solubility, liquid preparations can use solvents which are miscible with water, in particular ethanol and i-Propanol and solubilizers such as the alkali salts of benzene, toluene, xylene or ethylbenzenesulfonic acid.

- 9 - ^ 10 98 26/174 1 _{BAD 0RI} ginal

196424

Henkel & Cie GmbH s "it · 9 wratMtaitm" idunf ο] 5 ° 7o

In the preparation of the detergent one can proceed in such a way that the sodium citrate is used immediately as such mixed with the other detergent ingredients or the aqueous, pasty detergent formulation, or that you add free citric acid to these mixtures and ensure that the mixtures for the excess of alkaline compounds required for neutralization, for example sodium hydroxide or soda. In this case the salt is formed during the manufacture or use of the agent

If the agents are foam inhibitors from the class of substituted ones Containing triazines and melamines, these are advantageously those already available as powders or granules Detergent constituents or a part thereof admixed, granulated on or in molten form or sprayed onto it after dissolving in a volatile solvent.

The quantitative composition of the funds corresponds to preferably according to the following scheme:

1 part by weight of capillary washing-active substance, up to 100%, preferably 5 to 70 $ of compounds from Sui fonat- and or or sulfate type, up to 100% _t preferably from 5 to ^l \ 0% of non-ionic compounds from Polyglykoläthertyp and up to 100 %, preferably 10 to 50 % consist of soap,

0.5 to 20, preferably 1 to 10 parts by weight of that of pentasodium triphosphate, sodium citrate and sodium metasilicate existing salt mixture,

0.01 to 1 part by weight, preferably an amount which is 1 to 1 part by weight of the capillary-active washing activity, of foam inhibitors, preferably from the class of the saturated, 18 to 2 ^{liters of} carbon atoms

109826/1741, _A.

BATH

196424

Henkel & Cfe GmbH $ «ιι · 10 zur foi« nhinrn.i <! Img D 3676

containing fatty acids and their alkali metal soaps and the substituted triazines, obtainable by Reaction of 1 mole of cyanuric chloride with 2 to 3 moles of a primary monoamine or by propoxylation and or or butoxylation of melamine,

0 to 5 *, preferably 0.5 to 3 parts by weight of anhydrous or sodium perborate containing water of crystallization,

0 to 3 *, preferably 0.1 to 2 parts by weight of others Detergent ingredients, which preferably have the following composition

0.1 - 80 # neutral salts, especially sodium sulfate, 0 - 40 % tetrasodium pyrophosphate, 0 - 10 % sodium ethylenediaminetetraacetate, 0.5 - 40 # magnesium silicate,

0.1 - 20 % graying inhibitors, especially sodium carboxymethyl eluxose,

0 - 20 % enzyme,

0 - 10 # of at least one optical brightener.

The agents of the invention exhibit a high detergency and an improved soil-carrying capacity, where the effects are greater than when _t 1eder of the three components mentioned under b) Salsgemisehes alone would present itself. Because of the reduced phosphate content, the detergents are characterized by a good biodegradability and not promote polluted with sewage rivers and lakes in an undesired V / else, the algae and plant growth. Compared with mixtures that contain exclusively or predominantly nafcrium triphesphate as a scaffold, they lead to reduced damage to the textile fiber when used.

109826/1741

BATH

& CIO GmbH S «l!« Ll we PaUntonmtMwni 6

Examples 1 to 16

The detergents used had the following composition (data in

Components A. 0 B. C. D. n-dodecylbenzenesulfo "
nat (Na-SaIz) 14, - 9 * 5 oJ-01efinsulfonat
(Na-SaIz) - 14.0 - . -. • n-Alkanesulfonate (Na-Salz) - 5 - 14.0 - Ethoxylated oleyl alcohol
(9 EtO) 2, 0 2.5 2.5 3.5 Fatty acid from hydrogenated
Rapeseed oil 1, 5 1.0 1.0 1.0 Coconut sebum soap IiI
(Na-SaIz) 2, 3.5 3.5 4.5 Ethylene oil ^ n & notetra-
acetate - 0 - - 0.2 Tetrasodium pyrophosphate " 9, 0 8.0 8.0 5.0 Sodium water glass 4th 4.0 4.0 4.0

Sodium perborate tetrahy- 16.0 20.0 20.0 20.0 drat

Sodium sulfate 8.0 3.0 3.0 3.0 Carboxymethyl cellu 1.7 1.5 1.5 1.7 loose (Na-SaIz) optical brighteners - - 0.5 water 7.3 7.5 7.5 7.1 Building salts 34.0 35.0 35.0 40.0

Tab. 1

- 12 -

109826/1741

BATH ORIGINAL Henkel & CIe GmbH Stn »12»

The olefin sulfonate was derived from straight-chain Cje-C-ig-olefins (mean chain length C, g, -) ^al > Product containing secondary sulphonate groups. The abbreviation EtO stands for ethylene oxide groups. In the case of agents A, B and C, no brightener was added in order not to partially obscure the results of the white value determination by fluorescence phenomena.

The composition of the so-called "building salts" Mixture is shown in Table 2. The compounds were used as sodium salts.

To test the washing power, cotton swatches that had been soiled evenly with a mixture of dust and sebum were washed in a laboratory washing machine (launderometer). The detergent concentration was 4 g / l, the weight ratio of wash liquor to textile 1:12, temperature 90 ⁰ C and the washing time 15 minutes. The tap water had a hardness of 16 ° dH (corresponding to 160 mg CaO in _: liter). The whiteness of the fabrics, rinsed three times and then dried, was determined photometrically. The results are shown in Table 2. Each test series was preceded by comparative tests in which the building salt consisted of only one component? ^ ·· ^. The results show the superiority of the mixtures according to the invention.

1 / KD ORIGINAL 109826/1741

196424

Henkel & Cie GmbH Sa »· 15 * ^ur PaMMannuIdung D

Example- Washing Triphos Citrate Metasili White middle phat
% cat
% value _ A. 100 - - 76 - - 100 -. 76 - - - 100 75 1 50 35 15th 78 2 60 30th 10 79 3 45 25th 30th 78 4th 40 50 10 78 5 43 17th 40 77 6th 65 30th 5 78 B. 100 - - 75 - 100 - 76 - mm 100 75 6th 50 35 15th 77 7th 60 30th 10 79 8th 45 25th 30th 78 9 40 50 10 77 10 65 30th 5 78 C. 100 75 - mm 100 - 76 - - - 100 74 11 50 35. 15th 78 12th 60 30th 10 78 13th 45 25 · 30th 77 14th 40 50 10 78 15th 65 30th 5 78 D. 100 - 79 - - 100 79 M * - - 100 78 ■ 16 60 30th 10 80 17th 40 50 10 80

Tab,

iAD

- 14 -

Claims (1)

Henkel & GIe GmbH s "ii" 14 'wr _O i "nion" tWHB9 d Claims Washing and cleaning agents containing structural salts, characterized by a content of a) 1 part by weight of at least one capillary-active compound from the class of anionic, nonionic and zwitterionic washing active substances and b) 0.5 to 20 parts by weight of a mixture of structure of salts, the 20 to 75, preferably 50 to 65 wt -.% of pentasodium triphosphate, 10 to 60, preferably 15 to 50 wt -.% of sodium citrate and 3 to 50 , preferably 5 to 40 wt .- ^ of sodium metesilicate (Na ₃ O: SiO ₂ «1: 1). Agent according to claim 1, characterized by a content of 0.01 to 1 part by weight of a foam inhibitor, preferably from the class of saturated fatty acids containing 18 to 24 carbon atoms and their alkali metal soaps and substituted triazines, obtainable by reacting 1 mol of cyanuric chloride with 2 to 3 mol of a primary monoamine or by propoxylation and / or butoxylation of melamine. Agent according to claims 1 and 2, characterized in that the active washing substances mentioned under a) are up to 100%, preferably 25 to 70 % of those of the sulfonate and / or sulfate type, up to 100 56, preferably 5 to 40 % of nonionic Compounds of the polyglycol ether type and up to 100 %, preferably 10 to 50 $ consist of soap. - I ₅ - 109826/1741 Henkel & Cie GmbH «· η · 15«> r »« i «> ie« «« H <iinD 5676 4. Means according to claim 1 to j3, characterized in that that they contain up to 5 parts by weight, preferably 0.5 to 5 parts by weight, of anhydrous or crystalline water Contain sodium perborate. 5. Means according to claim 1 to 4, characterized in that that they contain up to 3 parts by weight, preferably 0.1 to 2 parts by weight, of other detergent ingredients preferably contain the following composition: 0.1 - 80 # neutral salts, especially sodium sulfate, 0 - kO $ tetrasodium pyrophosphate, 0 - 10 # sodium ethylenediarainotetraacetate, 0.5 - 40 % magnesium silicate, 0.1-20% graying inhibitors, in particular Sodium carboxymethyl cellulose, 0 - 20 % enzyme, 0 - 10 % of at least one optical brightener. Henkel & C i e. GmbH. i.V. (Dr. Haas) (Dr./Nagel) BAD OWGLAL 109826/1741