DE1792617A1 - Protein dissolving detergent, dish washing detergent and soaking agent - Google Patents

Description

Protein-containing soiling is known to be proportionate difficult to remove, which is why you can use the aur textile laundry or Detergents, dishwashing detergents and soaking agents intended for washing dishes often adds proteolytically active enzymes. Enzyme preparations are, however, due to their cumbersome extraction relatively expensive and, moreover, are high Temperatures, long storage times and chemical attack partially or completely inactivated. The applicant has now the Task set to produce detergents, dishwashing detergents and soaking agents with good protein-dissolving properties ^ in which the enzymes in whole or in part by more accessible, not inactivated bare connections are replaced.

The invention relates to washing, rinsing and protein-dissolving detergents Cleaning agent, characterized by a content of

a) at least one compound from the class of dialkyl disulfimides and their alkali and ammonium salts, in which the preferably straight-chain alkyl groups β to 10 Have carbon atoms,

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b) at least one compound from the class of the polymeric alkali metal phosphates, alkali metal silicates and the alkali metal salts of Aminopolycarboxylic acids and polyphosphonic acids,

where the weight ratio of the compounds mentioned under a) and b) is 0.5 * 99 * 5 to 1: J.

The dialkyl disulfimides, which react strongly acidic in the free state are expediently used in the form of their sodium, potassium or ammonium salts or mixtures thereof, with the Ammonium salts also include the salts of organic bases, such as mono-, di- or triethanolamine. Those in the dialkyl disulfimides alkyl radicals contained may be identical or different or branched. However, dialkyl disulfimides are preferred used with straight-chain alkyl radicals, under which the Di-n-oetyl disulfimide has been found to be particularly effective.

In addition to the dialkyl disulfimides, those according to the invention contain Detergents, dishwashing detergents and soaking agents, at least one inorganic or organic builder salt from the class of the polymeric alkali metal phosphates, alkali silicates and the alkali salts of aminopolycarboxylic acids and Polyphosphonslurep.

Suitable polymeric phosphates are PyropihoispJiafc®, T3? Iip! I © sphate, Tetraphosphate, fcrimetaphospliaig ,, TetvamBtaphospimt & and higher-; condensed phosphates in the form of the neutral © the acidic sodium,

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Potassium or ammonium salts. Alkali triphosphates and their equipment with pyrophosphates are preferably used. Furthermore, silicates are possible, in particular sodium silicate, in which the ratio of Na ₂ OtSiO _{2 is} 1: 3.5 to 1: 1. Suitable organic builder salts are the complexing alkali or ammonium salts of aminopolycarboxylic acids and / or aminopolyphosphonic acids, in particular the sodium or potassium salts of aminotriacetic acid, ethylene- ^ diaminotetraacetic acid, diethylenetriaminopentaacetic acid, triethylenetetramino-hexaacetic acid, triethylenetetraminohexaacetic acid, triethylenetetraminohexaessoacetic acid, triethylenetetraminohexaessoacetic acid, triethylenetetraminohexaessoacetic acid (methylenanthic acid, homoacetic acid, ethylenanthic acid, homohydroacetic acid) Ethylenediaminotetra- (methylenephosphonic acid), l-hydroxyethane-lil-diphosphonic acid, methylenediphosphonic acid, fithylenediphosphonic acid and the higher homologues of the polyphosphonic acids mentioned.

As Mschtingsbestandteile further Neutral salts such as sodium sulfate and sodium chloride, etc., and substances for regulating the pH value into consideration, such as bicarbonates, carbonates, borates, and hydroxides of sodium or potassium come, further acids, such as lactic acid and citric acid. The amount of alkaline substances, including alkali silicates and phosphates, should be such that the pH value of a usable lye for machine dishwashing is 10 to 14, for coarse washing 9 to 12 and for delicate washing 6 to 9.

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To further. Improvement of the paint dissolving properties the agents according to the invention can also contain enzymes the class of proteases, lipases and amylases. The enzymes can be of animal and vegetable origin, e.g. from ver. persistent ferments or yeasts such as pepsin, pancreatin, Trypsin, papaln, catalase and diastase. Preferably be off Bacterial strains or fungi such as Bacillus subtilis and Streptomyces griseus, extracted enzymatic active ingredients used that oppose alkali, per-compounds and anionic washing active substances are relatively stable and are not noticeably inactivated even at temperatures between ^ 5 and 70 C. Their relatively high resistance to oxidizing agents is possibly due to the low content of free sulfhydryl groups.

The enzymes are a valuable addition to the invention Means because they already become effective at temperatures at which the dialkyl disulfimides are not yet fully effective unfold. On the other hand, the sulfimides are also strongly alkaline at temperatures above 70 ° C. and with respect to them or active chlorine-containing compounds completely stable, while the majority of the known enzymes under the conditions mentioned are already inactivated to a considerable extent. A particular advantage can be seen in the fact that through the use the cheaper Dia Heyldisulfimide the necessary amount of enzymes can be reduced significantly.

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• According to their respective intended use, the invention Agents and other active washing substances, bleaching agents containing oxygen or chlorine and the usual additives contain.

Among the surface-active detergent raw materials that can be contained in the agents according to the invention, low-foaming compounds are primarily suitable for all areas of application in which a show development is to be completely or largely excluded, including in particular the nonionic polyglycol ether derivatives of alcohols, fatty acids and alkylphenols ^ which contain 3 to J5Q glycol ether groups and 8 to 20 carbon atoms in the hydrocarbon radical. 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 alkylphenols with a straight-chain alkyl chain containing 6 to 1.4 carbon atoms are particularly suitable. The addition of 2 to 1.5 moles of propylene oxide to the last-mentioned polyethylene glycol ethers or conversion into the acetals gives detergents which are distinguished by a particularly low foaming power.

Other suitable non-ionic washing raw materials are the water-soluble, 20 to 250 ethylene glycol ether groups and 10 to 100 Polyethylene oxide adducts containing propylene glycol ether groups

i-a e, 109847/1771 - 6 -

* on polypropylene glycol, ethylene diamino polypropylene glycol and Alkyl polypropylene glycol having 1 to 10 carbon atoms in the alkyl chain. The compounds mentioned usually contain 1 to 5 ethylene glycol units per propylene glycol unit.

Detergents and cleaning agents in which foam development does not interfere or is desirable can use anionic washing raw materials of the sulfonate or sulfate type. Examples of such Detergent raw materials are olefin sulfonates, such as those produced by sulfonation of primary or secondary aliphatic monoolefins obtained with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis, also alkyl sulfonates, as they are made from n-alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins. Are also suitable Alkylbenzenesulfonates, o ^ -Sulf © fatty acid esters, primary and secondary Alkyl sulfates and the sulfates of ethoxylated or propoxylated Alcohols. More compounds of this class, the may possibly be present in the detergents ^ are the higher molecular weight sulfated partial ethers and partial esters of polyvalent ones Alcohols, such as the alkali salts of the monoalkyl ethers or the Monofenic acid esters of Glyeerinmpnosulphuric acid ester or the

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1,2-dioxypropanesulfonic acid. Furthermore, sulfates come from ethoxylated or propoxylated fatty acid amides and alky! phenols as well as fatty acid taurides and fatty acid isethionates.

Except for the mentioned VJah raw materials of the sulfonate and sulfate type The agents can also contain alkali soaps of fatty acids, ampholytes, such as alkylbetaines and alkylsulfobetaines and non-ionic substances Contain surfactants of the type of amine oxides and sulfoxides.

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

By a suitable combination of various surfactants g detergent raw materials or construction salts with one another can What cn force or a reduced foaming capacity are achieved in many cases V7irkungssteigerungen, for example, improved "" Such improvements are possible, for example by combining anionisehen with nonionic and / or zwitterionisehen compounds ,, by combining different anionic compounds with one another, by combining different non-ionic compounds with one another or also by mixtures of VJash raw materials of the same type, which differ with regard to the number of

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Carbon atoms or the number and position of double bonds or differentiate chain branches in the hydrocarbon radical. Synergistic / inorganic mixtures can also be used and organic salts can be used or combined with the above-mentioned mixtures.

The agents can also release oxygen or contain active chlorine Bleaching agents, such as alkali perborates, alkali percarbonates, Alkali perphosphates, urea perhydrate, alkali hypochlorites, chlorinated trisodium phosphate and chlorinated cyanuric acid or their alkali salts, lead activators and stabilizers, such as Contain magnesium silicate.

Other suitable ingredients in the mixture are graying inhibitors, such as sodium cellulose glycolate, disinfecting and finishing agents, fillers such as urea, abrasive agents. Dyes and fragrances and optical brighteners, for example those of the diaminestibendisulfonic acid type according to Formula;

in which X and Y have the following meanings: NH, NH-CH ,,

OH, N (CH ₂ -CH ₂ OH) ₂ , morpholino, dimethylmorpholino, NH-CgH / NH-C ₆ H ₄ -SO ^ HZOCH ₃ , Cl, 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 diarylpyrazole type can also be used be present according to the formula below:

Ar'-C CH ₉

Il I

N v.

^N. ■ '■■■■. ■ '*

. '■' · ' Ar

In this formula mean

R is a V / assers t off atom, an alkyl radical or aryl radical,

which may be substituted,

Ar + Ar ¹ aryl radicals, such as phenyl, diphenyl or naphthyl, which can carry further substituents, such as hydroxy, alkoxy, hydroxyalkyl, amino, alkylamino, acylamino, carboxyl, sulfonic acid and sulfonamide groups

or halogen atoms.

10.98477177.1 " ¹⁰ "

1,3-Diarylpyrazolines in which R represents a hydrogen atom.

Preparations for use in drum washing machines or automatic dishwashers can also contain known anti-foaming agents, such as saturated fatty acids or their alkali soaps with 20 to 24 carbon atoms or Triazine derivatives obtained by reacting 1 mole of cyanuric chloride with 2 to 5 moles of an aliphatic, straight-chain, branched one or cyclic primary monoamine or by propoxylation or butoxylation of melamine are available.

The detergents and cleaning agents can be liquid or pasty or solid, for example powder, granulated or lumpy form. Liquid preparations can be mixed with water Miscible solvents, especially ethanol and i-propanol as well Solubilizers, such as the alkali salts of benzene, toluene, xylene or contain ethylbenzenesulfonic acid. To increase the foaming power and to improve skin tolerance, alkylolamides, such as fatty acid mono- and dietholamides, can be added will.

The preparation of the agents according to the invention can be carried out in a conventional manner Way by mixing, granulating or spray drying. If enzymes have been used, recommends! it yourself, this with To mix non-ionic chemical raw materials and, if necessary, 2 fragrances or in the melt of a water-containing crystal

-Xl-

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To disperse salt, e.g. Glauber's salt, and then combine these premixes with the other powder components. As a result, the enzymes are cemented to the remaining powder particles so that the mixtures do not form dust or do not tend to separate.

The mixtures can thus have the following composition, the following data in percent by weight related to anhydrous substance:

0.5-25%, preferably 1-15% dialkyl disulfimide

or its salts,

- 90 %, preferably 20 to 60 % inorganic and / or

organic building salts,

- 40 %, preferably 1 to 20 % of at least one compound from the class of anionic, nonionic and zwitterionic surfactants,

- 50 % _ß preferably 1 to 30 % bleaching agents, in particular per compounds and their mixtures with bleach activators or stabilizers and active chlorine compounds,

0 - 5 % r preferably 0.1 to 2.5 % enzymes,

- 20 #, preferably 1 to 12 %, other detergent ingredients * such as graying inhibitors, foam-suppressing agents, skin protection agents, organic silk, optical brighteners, solubilizers as well as dyes and fragrances.

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Some compositions are listed below which have proven particularly useful in practice. However, the invention is not limited to the following mixtures, but these can be modified in many respects or replaced by the in The additives listed in the description may be added. The sulfate and sulfonate detergents and soaps generally come as sodium salts for use. As far as liquid preparations are concerned acts, the anionic washing active substances can advantageously be in the form of the mono-, di- or triethano-ammonium salts can be used.

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. '' Powdery, low-foaming detergent: 1 - 15 % sodium salt of di-n-octyl disulfimide

Γ - $ 15 sulfonate detergent raw material from the class of alkylbenzenesulfonates, Olefin sulfonates and n-alkanesulfonates,

'- 5 % alkyl polyglycol ether (C ₁₂ -C ^ -alkyl) or alkylphenol polyglycol ether (Cg-C - ^ - alkyl) with 5 to 10 ethylene glycol ether groups,

- 5 % soap C ₁₃ -C ₁₈ , ", m

- 50 % of a condensed alkali phosphate from the class of pyro- or triphosphates,

0.1-20 %. Complexing agents from the class of alkali salts of aminopolycarboxylic acids, aminoalkylenepolyphosphonic acids and hydroxyalkanephosphonic acids,

1. - 5 % sodium silicate,

0.1 - 50 % of an inorganic salt from the class of

Carbonates, bicarbonates, borates, sulfates and. Alkali metal chlorides,

0.5 - ■ 4 % magnesium silicate, equivalent

10-35 % sodium perborate tetrahydrate

0 - 5 ^ enzyme,

0.2 - 5 % foam suppressant,

0.05-1 % of an optical brightening agent

0.5-3 # sodium cellulose glycolate.

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2. Machine dishwashing detergent:

0.5 - 3 % sodium salt of di-n-octyl disulfimide,

0-3 # alkyl polyglycol ether (C ₁₂ -C ₁ g-alkyl) or

Alkylphenol polyglycol ether (Cg-C ^ -alkyl) with 5 - 30 ethylene and 5 - 30 propylene glycol ether groups,
50 -95/6 pentasodium triphosphate,

1 - 40 # sodium silicate (Na ₀ O: SiO ₀ = 1: 1 to 1: 3) * A 0.5 - 5 # foam suppressant,

0 - 5 # potassium dichloroisocyanurate

3 Liquid detergents, dishwashing detergents and cleaning agents:

1 - 15 i> sodium salt of di-n-octyl sulfimide, 0.5 - 10 % sulfonate detergent raw material, 0 - 10 % alkyl polyglycol ether sulfate (Cg-Cg-alkyl,

1-5 ethylene glycol ether groups), - 30 ^ neutral or acidic potassium pyrophosphate, 0 - 5% foam suppressant, W 0.1 - 5 % fatty acid amide-ethylene glycol ether condensate

(C ^ jQ-Cig-alkyl, 1-10 ethylene glycol ether groups), 0-10 Jß solubilizer from the class of the alkali salts benzene, toluene or xylene sulfonic acid,

0 - 10 % organic solvents from the class of C ₀ -C, alcohols and ether alcohols,

0 1 % optical brightener

Remainder water, fragrances, dyes, preservatives, < middle.

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. Soaking and pre-wash detergent:

1 - 5 % sodium salt of di-n-octyl disulfimide, 0 - 5 lbs sulfonate detergent raw material ,

0 - 1>% alkyl polyglycol ether (C ^ g-Cj ^ g-alkyl) or alkyl

phenol polyglycol ether (Co-G ^ g-alkyl) with 5-12 ethylene glycol ether groups, 10 - 50 % soda,
5 ■ - $ 50 sodium triphosphate and its mixtures

with sodium pyrophosphate, ^

1 - 5 # ■ water glass,

0 - 5 $ magnesium silicate, 0 - 5 % enzyme.

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- l6 -

Examples

Soiled with a standardized, protein-containing soiling (EMPA-Fermentanschmutzung) cotton fabric was washed in a stirring vane-machine, wherein the wash liquor within 20 minutes from 20 to 50 C heated up and was kept for another 10 minutes at 5O ⁰ C. The weight ratio of textile to washing liquor was 1:10, the hardness of the tap water was 16 ° dH and the concentration of the detergent mixtures listed in the table below was 5 g / l. The percentage of lightening was determined photometrically.

The table shows the comparative tests with A, B and C, the examples according to the invention are marked with numbers. The numerical values show that the agents according to the invention, in particular in combination with enzymes cause improved dirt removal. ·

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component

.Na-Di-n-octyl disulfimide

Oleyl alcohol polyglycol ether (ίθ ethylene glycol ether groups)

Pentasodium triphosphate sodium sulfate enzyme

Lightening examples
3 4

10

10

0.5

0.5

15th

- . 45 , 5 .5 . 5 5 45 44 45 45 45 45 45 40 40

47.6 48.8 48.7 51

49

Comparison/

45 45 " 55 54.5

0.5

58.1 47.1 43.9

OD I CO CJ) -J

Claims (1)

Claims a) at least one compound from the class of the dialkyl disulfide imides as well as their alkali and ammonium salts, in which the preferably straight-chain alkyl groups have 6 to 10 carbon atoms exhibit, b) at least one compound from the class of the polymeric alkali metal phosphates, alkali metal silicates and the alkali metal salts of Aminopolycarboxylic acids and polyphosphonic acids, the weight ratio of those mentioned under a) and b) Connections 0.5 J 99 * 5 to 1: J5. , 2. Means according to claim 1, characterized by a content of alkali or ammonium salts of di-n-octyl disulfimide. 3 · Means according to claim 1 or 2, characterized by a Content of enzymes. 4. Means according to one or more of the preceding claims, characterized by the following, aiff anhydrous substances related composition in percent by weight? - 19 - 108847/1771 0.5 - 25 %, preferably 1 to 15 % dialkyl disulfimide or its salts, - 90 %, preferably 20 to 60 -Jo inorganic and / or organic building salts, - 40 #., Preferably 1 to 20 % of at least one compound from the class of anionic, nonionic and zwitterionic surfactants, - 50 #, preferably 1 to 50 % bleaching agents, in particular per compounds and their mixtures with bleach activators or stabilizers and active chlorine compounds, 0 - 5 % * preferably 0.1 to 2.5 % enzymes, O - 20 %, preferably 1 to 12 % other detergent components such as graying inhibitors, foam Depressants, skin protection substances, organic silk, optical brighteners, solubilizers, as well Dyes and fragrances. H e η k e 1 ft C i e. GmbH. Hail) i.V. * A. (Dr. Haas) (Dr. 1098-47 / 1771