DE2136672B2 - Detergents and cleaning agents - Google Patents

Description

COOM

As is known, the washing and cleaning power of soaps and synthetic surfactants can be determined Addition of certain water-soluble inorganic or organic salts, which are generally capable of binding complexes for alkaline earth and heavy metal ions, increase considerably. Such so-called Builder substances are present in the commercially available detergents and cleaning agents, whereby in the commercially available Preparations preferably tripolyphosphates are used as builder substances. These tripolyphosphates the detergents and cleaning agents are in the public increasingly for the blamed the undesirably high phosphate content of the waters. So far, however the still highly controversial view that the observed watercourses are due to excessive water consumption Algae growth largely due to the

built up, where η is a number from 5-500, preferably 10-100, M is a cationically dissociable group, preferably an alkali metal and especially sodium, and X is preferably the OH group or an optionally substituted amino group.

In the polycarboxylates according to the invention, some of the carboxyl groups can be present as free acid or

bo with a group X = OH intramolecularly or intermolecularly be esterified. With those from 5-dichloropropionic acid The radical X can also be a chlorine atom in minor proportions mean. Used in the manufacture of a S-dihalopropionic acid ester of a lower alcohol assumed, the carboxyl function can in minor proportions in the polycarboxylates -COOM present as an ester group.

The invention is based on the knowledge that the process products according to the above-mentioned German Patent application suitable as structural substances for detergents and cleaning agents.

The washing and cleaning agents according to the invention contain at least one surfactant from the group of anionic, zwitterionic and nonionic surfactants as well as builder substances and are characterized by that the builder substances at least partially from water-soluble salts of polymeric α-hydroxy and «-aminoacrylic acids, the reaction products of ocjS-dihalopropionic acids or their esters, in particular «, Ö-dibromopropionic acid or its Esters, in an aqueous medium with basic agents from the group of hydroxides, carbonates, Acetates, alkalis, especially sodium, ammonia, primary, secondary and tertiary amines or quaternary ammonium hydroxides. Optionally, the invention Agents also contain other common ingredients of detergents and cleaning agents.

The polymeric -hydroxy- and Λ-aminoacrylates which can be used according to the invention have typical Properties of structural substances, in particular they are characterized by good complex binding capacity against alkaline earth and heavy metal ions as well as good washing and dirt carrying capacity. They are therefore suitable as a phosphorus-free substitute for tripolyphosphate in detergents and cleaning agents. The alkali salts, in particular the sodium salts of the polymeric -hydroxyacrylates, are particularly preferred.

According to the German patent application, the polycarboxylic acids which can be used according to the invention are prepared P 20 61 584.3 for example «, / I-dibromopropionic acid together with water and 1 to 1.5 mol of a water-soluble base, such as. B. Sodium Acetate for so long heated to boiling until no further precipitate forms. The insoluble intermediate product thus obtained, that can be isolated is made by dissolving in hot sodium hydroxide solution in the sodium salt of poly- «- hydroxyacrylic acid convicted. The solid product can be reduced by concentration of this solution or by precipitation received a lower alcohol. The above intermediate is used instead of using caustic soda for example with a 50% solution of a primary or secondary amine, the polycarboxylic acid is converted into the corresponding amine salt, where to a greater or lesser extent in -position to the carboxyl group the corresponding Amino group is introduced.

The polycarboxylic acids according to the invention can, however, also be prepared in a single process step if the α, γ-dihalopropionic acids are used or their esters of lower alcohols with at least such amounts of an aqueous base treated, which are necessary for dehalogenation and salt formation. To speed up the manufacturing process can catalysts of the type of organic and inorganic per-compounds such as z. B. dibenzoyl peroxide, cumene hydroperoxide, sodium bo perborate, potassium peroxydisulfate, etc. can be used.

The detergents and cleaning agents with a content of alkali salts of the poly - «- have hydroxyacrylic acids For example, the following composition, based on the anhydrous substances, on:

1 - 80, preferably 5 40% by weight of a surfactant grain donor, consisting of anionic and / or zwitterionic and optionally nonionic Surfactants,

99-20% by weight, preferably 95-60% by weight of structural substances, those wholly or partly composed of water-soluble salts of the polycarboxylic acids defined above exist, and

0-30, preferably 1-25% by weight of other common ingredients of detergents and cleaning agents.

To the other usual detergent and cleaning agent ingredients belong e.g. B. foam stabilizers, non-surfactant foam inhibitors, bleaching components, Dirt carriers, fabric softeners, brighteners, antimicrobials, Enzymes, dyes and fragrances.

The content of the above-defined polycarboxylic acids in the detergents and cleaning agents according to the invention can vary within wide limits. Thus, the agents consist of at least 1% by weight, preferably at least 3% by weight, based on the total amount of the preparation, of the polycarboxylates defined above.

For example, quantities of complexing agents are sufficient to bind heavy metal ions during washing, which are in the order of 2 percent by weight, based on the total detergent. Exist the structural substances in the above formulation only partly consist of the polycarboxylates defined above, see above 10-95, preferably 10-60 percent by weight of the builder substances from such inorganic substances and / or organic water-soluble substances exist that were previously used in detergents and cleaning agents Builder substances were used, and which are described in detail below. Preferred those customary builder substances are used which do not contain phosphorus and / or nitrogen.

The surfactant component of the above formulation preferably consists of at least 50 percent by weight of anionic surfactants, among which anionic surfactants are essentially capillary-active sulfates and / or sulfonates and / or soaps.

In the agents according to the invention, the amount of builder substances is preferably 0.5 to 7 times and especially 1 to 5 times the total surfactants.

If the preparations according to the invention contain more than 40 percent by weight of the above-mentioned surfactant component, then they are mostly used for commercial purposes e.g. B. used in laundries and in the textile industry, where they are used less alone, more often in combination with common additives.

The agents according to the invention can be in the form of powders, pastes, solutions or suspensions, with the liquid preparations contain 50 percent solid matter by weight and, in addition to water, also water-soluble organic ones May contain solvents and hydrotropes.

The composition of powdered preparations according to the invention, especially as detergents are generally in the range of the following recipe:

5-80, preferably 8-40% by weight of a surfactant component containing at least one surfactant the group of sulfonates, sulfates, soaps and zwitterionic surfactants, optionally nonionic Surfactants and optionally one

or more of the following substances:
0-10, preferably 0.5-8% by weight of foam stabilizers,
0-10, preferably 0.5-8% by weight non-tensile

dic foam inhibitors,

20-95, preferably 60-92% by weight of structural substances which consist entirely or in part of the polycarbonates defined above, and
0-30% by weight, preferably 1-15% by weight of other detergent ingredients such as B. bleach components, dirt carriers, fabric softeners, antimicrobials, enzymes, brighteners, dyes and fragrances, water.

If the detergents are to have bleaching properties, they can also have a bleaching component contain, including any stabilizers and / or activators for per compounds 2—40, preferably 7-35 percent by weight of the total detergent, in such detergents the amount of builder substances is reduced, but not more than 20 percent by weight, or the Quantity of all components is proportionally reduced

Low-foam detergents suitable for use in drum washing machines according to the above Recipes contain either a combination of sulfonate and / or sulfate type surfactants and soap in the Quantity ratio from 30: 1 to 1: 5, preferably from 20: 1 to 1: 2, and / or a non-surfactant foam inhibitor. Contained in such low-foam detergents the soaps derived from saturated fatty acids having 20-24, preferably 20-22 carbon atoms Proportions, the amount of which is at least 5 percent by weight, preferably at least 10 percent by weight of the total amount of soap.

The production of powder detergents and cleaning agents according to the invention can be carried out according to various methods known per se take place. For example, the powder can be more or less fine or individual components present as granules by mixing to powder detergents and Bring detergents together. According to the technically preferred production method for Washing and cleaning agents, the aqueous batch is hot-dried in a manner known per se, resulting in hot surfaces or in a stream of hot air. If you put the invention Preparations on the way via an aqueous approach of the constituents by hot drying are so certain components such as B. foam inhibitors, bleaches, enzymes, etc. not in the aqueous approach incorporated, but subsequently added to the powder detergent. It is where appropriate It is advantageous to mix such substances with some of the structural substances first in a dry one To transfer powdery intermediate product, which is then added to the washing powder or cleaning agent powder in the usual way is added.

The following are the ingredients contained in the detergents and cleaning agents according to the invention Described in more detail sorted by substance class.

As builder substances, optionally used together with the polycarboxylates defined above weakly acidic, neutral and alkaline reacting inorganic and organic are suitable Salts, especially inorganic or organic complexing agents.

Useful inorganic and organic builders are for example the bicarbonates, carbonates, sulfates, borates, silicates or hydroxides of alkalis as well as the alkali salts of organic, non-capillary active, Sulfonic acids, carboxylic acids and sulfocarboxylic acids containing 1 to 8 carbon atoms. These include for example water-soluble salts of benzene, toluene or xylene sulfonic acid, water-soluble salts of sulfoacetic acid, Sulfobenzoic acid or salts of sulfodicarboxylic acids and the salts of acetic acid, lactic acid,

ίο citric acid and tartaric acid.

The water-soluble salts of higher molecular weight polycarboxylic acids from the Group of polymers of maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, methylenemalonic acid and citraconic acid are also suitable copolymers of these acids with one another or with other polymerizable substances, such as. B. with ethylene, propylene, acrylic acid, methacrylic acid, crotonic acid, 3-butene carboxylic acid, 3-methyl-3-bulene carboxylic acid and with vinyl methyl ether, vinyl acetate, isobutylene, Acrylamide and styrene are useful.

As complexing agents containing phosphorus and / or nitrogen The alkali metal salts of amino and polyamino-polycarboic acids can optionally be used in minor amounts such as B. the

Nitrilotriacetic acid,

Ethylenediaminetetraacetic acid,

N-hydroxyethyl-ethylenediamine triacetic acid

and of di-, tri- and tetraphosphonic acids such as. B. the

Methylenediphosphonic acid,
j -) 1-hydroxyethane-1,1-diphosphonic acid,

l-aminoethane-l, l-diphosphonic acid,

Amino-tri-methylenephosphonic acid,

Methylamino or

Ethylamino-dimethylenephosphonic acid and
Ethylenediamine-tetra-methylenephosphonic acid

can be used.

In the detergents according to the invention, additional dirt carriers can be contained, which of Keep the dirt detached from the fibers suspended in the liquor and thus prevent graying. These are water-soluble colloids mostly of organic nature, such as glue, gelatin, salts of Ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acid sulfuric acid esters cellulose or starch. Water-soluble polyamides containing acidic groups are also useful suitable for this purpose. Soluble starch preparations and other than those mentioned above can also be used Use starch products such as B. degraded starch, aldehyde starches, etc. Also polyvinylpyrrolidone is useful.

The surfactants contain at least one hydrophobic radical of mostly 8-26, preferably in the molecule 10-22 and especially 12-18 carbon atoms and at least one anionic, nonionic or zwitterionic water-solubilizing group. The preferably saturated hydrophobic residue is usually more aliphatic, possibly also of an alicyclic nature; he can with the

b5 water-solubilizing groups be connected directly or via intermediate links, such as. B. via benzene rings, Carboxylic acid ester or carbonamide groups, ether- or ester-like bound resie polyvalent

Alcohols.

Soaps made from natural or synthetic fatty acids, possibly also made from, are used as anionic detergent substances Resin or naphthenic acids can be used, especially if these acids have iodine numbers of at most 30 and> preferably less than 10.

Of the synthetic anionic surfactants, the sulfonates and sulfates have particular practical ones Meaning.

The snlfonaten include, for example, the i <> Alkylbenzenesulfonates with preferably straight-chain Cq_15-, in particular Cm_n-alkyl radicals, the alkanesulfonates, obtainable from preferably saturated aliphatic Cs- is, in particular C12- ^ hydrocarbons on sulfochlorination or sulfoxidation, the mixtures known under the name "Oiefinsulfonate" Alkene sulfonates, Hydroxialkansulfonaten and Disulfonaten, which with acid or alkaline hydrolysis of the terminal or intermediate Cs-ie- and preferably Ci2-i8-olefins by sulfonation with sulfur trioxide 2 (1 sulfonation products initially formed arise. The sulfonates which can be used according to the invention also include salts, preferably alkali salts, of Λ-sulfofatty acids and salts of esters of these acids with mono- or polyvalent, 1 - 4 and preferably> ■> 1 - 2 carbon atoms containing alcohols.

Further useful sulfonates are salts of fatty acid esters of oxethanesulfonic acid or Dioxypropanesulfonic acid, the salts of the fatty alcohol esters of lower, 1-8 carbon atoms containing aliphatic jo or aromatic sulfomono- or dicarboxylic acids, the alkyl glyceryl ether sulfonates and the salts of amide-like condensation products of fatty acids or sulfonic acids with aminoethanesulfonic acid.

If surfactants of the sulfate type are fatty alcohol sulfates to r> name, in particular made from coconut fatty alcohols, tallow fatty alcohols or from oleyl alcohol sulfated fatty acid alkylolamides or fatty acid monoglycerides and sulfated alkoxylation products of Alkyl phenols (Cs-15 alkyl). Fatty alcohols, fatty acid - »n amides or fatty acid alkylolamides with 0.5 - 20, preferably 1-8 and especially 2-4 ethylene and / or propylene glycol residues in the molecule.

Suitable anionic surfactants of the carboxylate type are, for. B. the fatty acid esters or fatty alcohol r> ethers of hydroxycarboxylic acids and the amide-like condensation products of fatty acids or sulfonic acids with aminocarboxylic acids, e.g. B. with glycocolla, sarcosine or with protein hydrolysates.

The anionic surfactants are mostly in the form of salts of -m Alkali metals, especially sodium, ammonium, lower aliphatic amines or alkylolamines before.

The nonionic surfactants, here called "nonionics" for the sake of simplicity, include the through Addition of 4-100, preferably 6-40 and especially 8-20 mol of ethylene oxide to fatty alcohols, Alkylphenols, fatty acids, fatty amines, fatty acid or sulfonic acid amides available polyethylene glycol ethers, in addition, the still water-soluble accumulation prob products of propylene or butylene oxide to this. The nonionics also include those which are inherently water-insoluble Polypropylene glycols or from water-insoluble propoxylated lower, 1-8, preferably 3-6 Aliphatic alcohols containing carbon atoms or b5 obtained from water-insoluble propoxylated alkylenediamines by ethoxylation to water solubility Products. Finally, as nonionics, the partly

still water-soluble reaction products of the abovementioned aliphatic alcohols with propylene oxide use.

As nonionics are also mono- or diethanolamine, dihydroxypropylamine or other polyhydroxyalkylamines, z. B. the glycamines derived fatty acid or sulfonic acid alkylolamides, useful. Furthermore, the oxides of higher tertiary amines with a hydrophobic alkyl radical and can be used as nonionics two shorter, up to 4 carbon atoms each containing alkyl and / or alkylol residues are considered.

Zwitterionic surfactants contain both acidic groups in the molecule, such as. B. carboxylic, sulfonic acids Sulfuric acid half ester, phosphonic acid and phosphoric acid partial ester groups, as well as basic groups, such as. B. primary, secondary, tertiary and quaternary Ammonium groupings. Zwitterionic compounds with quaternary ammonium groups belong to the Type of betaine. Carboxy, sulfate, and sulfonate betaines have good compatibility with others Surfactants of particular practical interest.

The foaming power of the surfactants can be increased or increased by combining suitable surfactant types as it can be changed by adding non-surfactant organic substances can.

Suitable foam stabilizers, especially in the case of surfactants of the sulfonate or sulfate type, are capillary-active Carboxy- or sulfobetaines as well as the above-mentioned nonionics of the alkylolamide type; also are for Fatty alcohols or higher terminal diols have been proposed for this purpose.

A reduced foaming capacity, which is desirable when working in machines, is achieved in many cases by combining different types of surfactants. z. B. of sulfates and / or sulfonates and / or of Nonionics on the one hand with soaps on the other hand. With soaps, the foam attenuation increases with the degree of saturation and the C-number! of the fatty acid residue; Soaps of saturated C? <i-24 fatty acids have proven to be a foam suppressor proven.

Non-surfactant-like foam inhibitors may include N-alkylated aminotriazines containing chlorine, by reacting 1 mole of cyanuric acid chloride with 2-3 moles of a mono- and / or dialkylamine 6-20, preferably 8-18 carbon atoms in the alkyl radical. Propoxylated and / or butoxylated act similarly Aminotriazines, e.g. B. Products obtained by adding 5-10 moles of propylene oxide to 1 mole Melamine and further addition of 10-50 mol of butylene oxide to this propylene oxide derivative.

Other non-surfactant-like foam inhibitors are water-insoluble organic compounds such as paraffins or haloparaffins having melting points below 100 ⁰ C, aliphatic C ₈ - to C ₄₀ ketones and aliphatic Carbonsäureester, in the acid or in the alcohol radical, optionally also in each of these two radicals, contain at least 18 carbon atoms (e.g. triglycerides or fatty acid fatty alcohol esters); they can be used in particular with combinations of surfactants of the sulfate and / or sulfonate type with soaps to dampen the foam.

As particularly low-foaming nonionics, optionally in combination with anionic and Zwitterionic surfactants can be used and the foaming power of better foaming surfactants Addition products of propylene oxide to the capillary-active ones described above are suitable

Polyethylene glycol ether and the Pluronic, Tetronic and Ucon fluid types also described above.

Among the preferably inorganic per compounds used as bleaching agents, sodium perbo-> rat tetrahydrate

(NaBO ₂ · H ₂ O ₂ · 3 H ₂ O)

particular practical importance. In its place, partially or completely dehydrated perborates, ie up to i <> NaBO ₂ · H ₂ O ₂ , can be used. _{The borates NaBO 2} · H ₂ O ₂ described in DE-PS 9 Ol 287 or in US-PS 24 91 789, in which the ratio of Ma ₂ O to B ₂ O _{3 is} less than 0, can also be used, 5: 1 and preferably in the range of ι> 0.4-0.15: 1, while the ratio of H ₂ O _{2 to} NaIn falls in the range of 0.5-4: 1. All of these perborates can be wholly or partially replaced by other inorganic per compounds, in particular peroxohydrates, e.g. B. the peroxohydrates of ortho-, _'o pyro- or polyphosphates, especially tripolyphosphates and carbonates.

It is recommended that conventional water-soluble in the products for stabilization of the compounds and to incorporate water-insoluble or stabilizers or in amounts of 2 ^r> 0.25-10 wt .-%. As water-insoluble perstabilizers, which make up, for example, 1-8, preferably 2-7%, of the weight of the total preparation, the magnesium silicates MgO obtained by precipitation from aqueous solutions with w SiO ₂ = 4: 1 to 1: 4, preferably 2: 1 to 1: 2 and especially 1: 1. Other alkaline earth metal, cadmium or tin silicates of the appropriate composition can be used instead. Hydrous oxides of tin are also suitable as stabilizers. Water-soluble stabilizers, which may be present together with water-insoluble ones, are the organic complexing agents, the amount of which is 0.25-5, preferably 0.5-2.5%, of the weight of the total preparation can make out.

The active chlorine compounds used as bleaching agents can be of an inorganic or organic nature.

The inorganic active chlorine compounds include alkali hypochlorites, especially in the form of their Mixed salts or addition compounds to orthophosphates or to condensed phosphates such as for example, pyro- and polyphosphates or alkali silicates can be used. Contain the Detergents according to the invention monopersulphates and chlorides, active chlorine is formed in aqueous solution. so

Particularly suitable organic active chlorine compounds are the N-chlorine compounds in which one or two chlorine atoms are bonded to a nitrogen atom, the third valence of the nitrogen atoms preferably leading to an electron-withdrawing group, in particular to a CO or S0 ₂ group. These compounds include dichloro and trichlorocyanuric acid or their salts, chlorinated alkylguanides or alkyl biguanides, chlorinated hydantoins and chlorinated melamines. *O

Certain N-acyl, Ο-acyl compounds and carbonic or pyrocarbonic acid esters, whose activation value for the percompounds (= titer) is at least 3, preferably, serve as activators for _{per-compounds which produce H 2} O _{2 in water} is at least 44 This activation value is determined in the following way:

Solutions that

0.615 g / L NaBO ₂ · H ₂ O ₂ · 3 HO

(4mmol / l) and
2.5 g / L Na ₄ P ₂ O ₇ · 10H ₂ O

are, after heating to 6O ⁰ C with mmol / 1 activator and kept for 5 minutes with stirring at the specified temperature. 100 ml of this liquid are then added to a mixture of 250 g of ice and 15 ml of glacial acetic acid and, immediately after the addition of 0.35 g of potassium iodide, titration is carried out with 0.1 N sodium thiosulphate solution and starch as an indicator. Under the given experimental conditions, for a 100 ⁰ / o activation of the peroxide used is consumed 8.0 ml of thiosulfate solution, ie, the titre is 8.0. However, this maximum value is almost never reached; good activators have a titer of at least 4.5. Usable activations can often be achieved with activators with a titer of at least 3.0.

From the bottom to be described types of activators are especially compounds having a melting point "on at least 70 ⁰ C, preferably at least 100 ° C and in particular of at least 150 ° C. Furthermore, the equivalent weight of these compounds (equivalent weight is understood here as the quotient of the molecular weight and the number of acyl radicals present in the molecule) should be at most 170, preferably at most 130 and in particular at most 110.

The activators which can be used according to the invention include

_{a) the N-diacylated and N 1} N'-tetraacylated amines known from German patents 11 62 967 and 12 91 317 such. B. Ν, Ν, Ν ', Ν'-tetraacetyl-methylenediamine or -ethylenediamine, Ν, Ν-diacetylaniline and N, N-diacetyl-p-toluidine or 1,3-diacylated hydantoins, such as the compounds 1, 3-diacetyl-5,5-dimethylhydantoin and 1,3-dipropionylhydantoin;

b) the N-alkyl-N-sulfonyl-carbonamides known from British patent specification 10 03310, for example the compounds
N-methyl-N-mesyl-acetamide,
N-methyl-N-mesyl-benzamide,
N-methyl-N-mesyl-p-nitrobenzamide and
N-methyl-N-mesyl-p-methoxybenzamide;

c) the N-acylated cyclic activators described in Swiss Patent 4,07,387 Hydrazides, acylated triazoles or urazoles such as, for example, monoacetyl maleic acid hydra ^ id;

d) the Ο, Ν, Ν-trisubstituted hydroxylamines described in German patent application P 17 19 5743-43 such. B.
O-Benzoyl-NN-succinyl-hydroxylamine,
O-acetyl-NN-sucdnyl-hydroxylamine,
Op-methoxybenzoyl-NN-succinyl-

hydroxylamine,

Op-nitrobenzoyl-NN-succinyl-hydroxylamine
and
Ο, Ν, Ν-triacetyl-hydroxylamine;

e) the Ν, Ν'-diacyl-sulfurylamides known from German Offenlegungsschrift 18 01 713, for example
N.N'-dimethyl-N.N'-diacetyl-sulfurylamide

and
N, N'-diethyl-N, N'-dipropionyl-sulfurylamide;

f) the triacyl cyanurates, for example triacetyl cyanurate and tribenzoyl cyanurate of the German

Auslegeschrift 12 94 919;
g) the carboxylic acid anhydrides known from Swiss Patent 3 4/930 or German Patent 8 93 049 or German Offenlegungsschrift 14 44 001, such as. B.

Benzoic anhydride,

m-chlorobenzoic anhydride,

Phthalic anhydride,

4-chlorophthalic anhydride;
h) the sugar esters known from Swiss patent specification 3 48 682, for example glucoscpentaacetate;

i) the 1,3-diacyl-4,5-diacyloxy-imidazolidines of German Offenlegungsschrift 18 01 141, for example the connections

!, S-Diformyl- ^ S-diacetoxy-imidazolidine,
1,3-diacetyl-4,5-diacetoxy-imidazo) idin,
lS-diacetyl ^ .S-dipropionyloxy-

imidazolidine;

j) the compounds tetraacetylglycoluril and tetrapropionylglycoluril known as activators from German Offenlegungsschrift 15 94 865;
k) proposed as activators for per compounds diaeylated 2,5-diketopiperazines such as

1,4-diacetyl-2,5-diketopiperazine,
! , 4- dipropionyl-2,5-diketopiperazine,
1,4-dipropionyl-3,6-dimethyl-

2,5-diketopiperazine;

1) the carbonic acid esters of German Offenlegungsschrift 14 44 024, for example the sodium salts of p- (ethoxycarbonyloxy) -benzoic acid and p- (propoxycarbonyloxy) -benzenesulfonic acid.

Often it is sufficient to activate only part of the available active oxygen; this is enough Activator additives of at least 0.05 mol of activator per g-atom of active oxygen. If you put on one

ίο Activation of the active oxygen as far as possible Value, the addition of activator can be increased by up to 2 mol, preferably up to 1 mol. Preferred works one with 0.1-1 mole of activator per g-atom of active oxygen. However, these amounts can be changed according to the

ι ^r > Change the activity of the activator used.

When the per compounds are activated by the N-acyl and O-acyl compounds mentioned, a Part of the alkali in the washing and bleaching liquors due to the organic peracids or the resulting organic peracids resulting organic carboxylic acids such as. B. acetic acid, propionic acid, benzoic acid and consumed advantageously replaced by adding appropriate amounts of alkalizing agent.

The brighteners that can be used are mostly, albeit

2) not exclusively, derivatives of aminostilbene sulfonic acid or diaminostilbene disulfonic acid, diarylpyrazolines, carbostyril, l, 2-di- (2-benzoxazo-IyI) - or 1,2-di- (2-benzimidazo! yl) ethene, benzoxazolyl thiophene and coumarin.

jo examples of brighteners from the class of the diaminostilbene disulfonic acid derivatives are compounds according to formula I:

In the formula, R | and R ₂ denotes alkoxy groups, the amino group or radicals of aliphatic aromatic or heterocyclic, primary or secondary amines and radicals of aminosulfonic acids, aliphatic radicals present in the above groups preferably containing 1-4 and in particular 2-4 carbon atoms, while the heterocyclic ring systems are mostly 5- or 6-membered rings. The aromatic amines are preferably the radicals of aniline, anthranilic acid or anilinesulfonic acid. Brighteners derived from diaminostilbene disulfonic acid are mostly used as cotton whiteners. The following products derived from formula I are commercially available, with R] being the remainder

-NHC ₆ H ₅

represents and R _{2 can represent the} following radicals:
-NH ₂ , -NHCH ₃ , -NHCH ₂ CH ₂ OH,
-NHCH ₂ CH ₂ OCH ₃ , -NHCH ₂ CH ₂ CH ₂ OCH ₃ ,
-N (CH ₃ ) CH ₂ CH ₂ OH, -N (CH ₂ CH ₂ OH) ₂ ,
Morpholino, -NHC ₆ H ₅ ,
-NHC ₆ H ₄ SO ₃ H, -OCH ₃ .

Some of these brighteners are transition types to the polyamide brighteners in terms of fiber affinity to look at, e.g. B. the brightener with

R ₂ = -NHC ₆ H ₅ .

4j To the building wool brighteners of the diaminostilbene disulfonic acid type also includes the compound 4,4'-bis (4-phenyl-1,2,3-triazol-2-yl) -2,2'-stilbene disulfonic acid.

The polyamide brighteners include diarylpyrazolines of the formulas II and III:

R, R ₅

C-

Ar ₁ -N
CH ₁ -

r, \

c \
R ₆

C-Ar ₂

-CH, C.

(IH)

In formula II, R ₃ and R ₅ denote hydrogen atoms, optionally through carboxyl, carbonamide or ester groups

pen substituted alkyl or aryl radicals, R4 and R _h hydrogen or short-chain alkyl radicals, An and Ar> aryl radicals, such as phenyl, diphenyl or naphthyl, which can carry further substituents, such as hydroxy, alkoxy, hydroxyalkyl, amino, alkylamino , Acylamino, carboxyl, carboxylic acid ester, Si: lfonic acid, sulfonamide and sulfone groups or halogen atoms. Commercially available brighteners of this type are derived from the formula III, with the radical R7 representing the groups

Cl, -SO ₂ NH ₂ , -SO ₂ CH = CH ₂ and
-COOCH ₂ CH ₂ OCH,

can represent, while the radical R ₈ usually means a chlorine atom. 9-cyanoanthracene is also one of the polyamide brighteners.

The polyamide brighteners also include aliphatic hairs or aromatic substituted aminocoumarins, e.g. B. 4-methyl-7-dimethylamino or 4-methyl-7-diethylaminocoumarin. The compounds are also used as polyamide brighteners

1- (2-Benzimidazolyl) -2- (l-hydroxyethyl-2-benzimidazoly!) - ethylene and

l-ethyl-S-phenyl ^ -diethylamino-carbostyril
useful. As brighteners for polyester and polyamide fibers, the compounds are

2,5-di- (2-benzoxazolyl) thiophene,

2- (2-BenzoxazolyI) naphtho [2,3-b] thiophene

and

1,2-di (5-methyl-2-benzoxazolyl) ethylene
suitable.

If the brighteners are used together with other components of the products according to the invention as aqueous Solution or paste are present and converted into a solid state by hot drying, it is recommended to use The brighteners stabilize organic complexing agents in amounts of at least 0.1, preferably 0.2-1 Incorporate wt .-% of the solid products.

The enzyme preparations to be used are usually a mixture of enzymes with different effects, e.g. B. of proteases, carbohydrases, esterases, lipases. Oxidoreductases, catalases, peroxidases, ureases, Isomerases, lyases, Ti ansferases, desmolases or nucleases. Of particular interest are the ones from Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis or Streptomyces griseus, in particular Proteases or amylases, which are relative to alkali, percompounds and anionic surfactants are stable and are still effective at temperatures of up to 70 ° C.

Manufacturers usually supply enzyme preparations as aqueous solutions of the active ingredients or as a powder. Granules or brought onto the market as cold-atomized products. They contain as blending agents often sodium sulfate, sodium chloride, alkali ortho-, Pyro- or polyphosphates, especially tripolyphosphate Particular importance is attached to dust-free Preparations; they are obtained in a manner known per se by incorporating oily or pasty products Nonionics or by granulating with the help of melts of salts containing water of crystallization in their own Crystal water.

Enzymes can be incorporated which are specific for a certain type of soil, for example Proteases or amylases or lipases; preference is given to using combinations of different enzymes Effect, especially combinations of proteases and amylases.

The constituents of the washing and cleaning agents according to the invention, in particular the builder substances are usually selected so that the preparations react neutrally to clearly alkaline, so that the pH value

■■> a 10% solution of the preparation mostly in the area from 7 to 12. Detergents for mild detergents and cleaning agents for hard surfaces are mostly neutral to weakly alkaline reaction (pH = 7-9.5), while in general cooking detergents stronger

κι alkaline (pH value = 9.5-12, preferably 10-11.5) are set.

Examples

The following examples describe compositions of some preparations according to the invention. The one in it The salt-like constituents contained therein are present as sodium salts, unless expressly stated otherwise is detected. The related terms and abbreviations mean:

2 (i "ABS" is the salt of a product obtained by condensing straight-chain olefins with benzene and sulfonating the alkylbenzenesulfonic acid with 10-15, essentially 11-13, obtained in this way Carbon atoms in the alkyl chain;

2't "alkanesulfonate" a sulfonate obtained from paraffins with 12-16 carbon atoms by sulfoxidation;

"Fs-ester sulfonate" is made from the methyl ester of a hardened tallow fatty acid by sulfonating with SOj

χι obtained sulfonate;

"Olefin sulfonate" is a mixture of olefins containing 13-18 Carbon atoms by sulfonating with SO3 and hydrolyzing the sulfonation product with alkali obtained sulfonate, which essentially consists of alkene sulfonate

sj fonat and oxyalkanesulfonate, but also still contains small amounts of disulfonates, every preparation containing olefin sulfonate has been used made two different types of olefin sulfonate; one was straight-chain from a mixture

4 (i terminal olefins, the other was made from a mixture of internal olefins;
"KA-ÄO-sulfate" is the sulfated adduct of 2 moles of ethylene oxide with 1 mole of coconut fatty alcohol (C ₁₂ -C ₁₄ );

“Soap A or B” is a mixture of fatty acids of 9% by weight 0/0 Cb. 14% by weight of C ₂₀ and 77% by weight of C _:: (iodine number 3) (A); or 8% by weight of C ₁₆ , 32% by weight of C ₁₈ , 12% by weight of C ₂₀ and 48 _{% by weight of C 22} (iodine number 4) (B) manufactured soap: "KA + 7ÄO" and »ΝΡ + 9ΛΟ« the addition

-, (i products of ethylene oxide on coconut alcohol (C ₁₂ -Ci _s ) or on nonylphenol;

“Perborate” is a product containing about 10% active oxygen with the approximate composition NaBO ₂ · H ₂ O ₂ · 3 H ₂ O;

"CMC" the salt of carboxymethyl cellulose.

A mixture of about 45% of an N, N'-di (aI-kylamino) chlorotriazine was used as a non-surfactant foam inhibitor in the examples and about 55% of an N, N ', N "-tri (alkylamino) triazine used in this triazine

The alkyl radicals are found as a mixture of homologues with 8-18 carbon atoms. The monochlorotriazine derivative or the Use trialkylaminotriazine. If the products described are synthetic sulfates or sulfonates together with soap can contain the other non-surfactant foam inhibitors mentioned in the description can be used, such as, for example, paraffin oil or paraffin.

During the preparation of the preparations, the non-surfactant foam inhibitor was used in a suitable organic solvent dissolved or in a molten state by means of a nozzle on the moving powdery preparation sprayed on.

In all of the examples, the quantitative data relate to on the pure substances. These substances can production-related accompanying substances such as Contain water, sodium sulfate, sodium chloride, sodium carbonate, etc. Since such accompanying substances In no way affect the effectiveness of the individual substances if they are not in the Mentioned recipes. The term “remainder” therefore essentially stands for water and the aforementioned salts as well as for> "dyes and fragrances.

The preparations according to the invention described in the examples in Table I contain builder substances ΡοΙν-Λ-hydroxyacryiate, which according to the following Regulation or in analogy to it can be produced.

Sodium poly-A-hydroxy acrylate

4000 3000

2000

A mixture of 464 g (2 moles) λ-j3-dibromopropionic acid. 274 g (2 mol) of sodium acetate, containing water of crystallization, and 500 ml of water were heated to the boil with stirring. After a short time, a precipitate formed which was complete after 2 hours. The precipitate was filtered off with suction, first with water, then with it Acetone washed, sucked dry and dissolved in about 1.21 hot 2 η sodium hydroxide solution. The cooled solution was poured κι into about 2.5 l of methanol, the sodium salt of the polymeric α-hydroxy acrylic acid precipitated as a white powder % solution of the product in 2N Nairon lye had the specific viscosity η-U = 0.2.

A product with the same specific viscosity was obtained when the reaction with 2 mol Λ-ß-dibromopropionic acid methyl ester (492 g) carried out.

The sodium poly-A-hydroxyacrylate (η ■ :, = 0.2) prepared according to the above procedure is characterized by the following infrared spectrum.

1500

! ! II ■ »I ! I 'I LJ I

Sodium poly- CL -hydroxyacrvlate
20th

7 8 9

WAVELENGTH (MICRONS)

example 1

A heavy duty detergent of the following composition was made by mixing the individual components manufactured:

(1) 5% by weight SECTION; (2) 4% by weight NP + 9ÄO; (3) 5% by weight Soap A; (4) 30% by weight Perborate; (5) 5% by weight Na ₂ O.3.3 SiO ₂ ; (6) 2% by weight Magnesium silicate;

(7) 0.5% by weight of brighteners of formula I on column II. 12.in

the Ri denotes the anilino and R _{2 denotes}

2,2'-dihydroxy diethylamino residue
represent;

(8) 40% by weight sodium poly-α-hydroxyacrylate with

the specific viscosity η;, = 0.2;

(9) 0.5% by weight of an alkaline protease;
(10) balance sodium sulfate and water.

Washing, dirt-carrying and Kompiex-binding properties of the above detergent are comparable to the

909 542/79

corresponding properties of a comparative detergent of similar composition, but which instead of 40% by weight of sodium poly-α-hydroxyacrylate contains 40% by weight of sodium tripolyphosphate. 18th

Examples 2-7

In the other examples in the table, no. 2–4 heavy duty detergents, no. 5 and 6 mild detergents and no. 7 a pre-wash detergent.

Tabtlle

Part of the preparation Wt% 9 Part of the 2 Preparation after 2 5 7th 6th 8th 7th 2 example 7th 4th 2 3 5 4th SECTION 20th Alkanesulfonate 2.5 4th 35 Fs-ester sulfonate 4th 4th Olefin sulfonate 3 3 3 3 15th KA-ÄO-sulfate 0.5 10 Soap A 2 15th Soap B 35 22nd NP + 9ÄO 20th 12th 8th 2 10 KA + 7AO 15th 10 45 50 0.3 Non-surfactant foam inhibitor 10 4th 5 Poly-ff-hydroxyacrylate 12th 25th 10 Na ₂ SO ₄ 20th 10 5 Na ₂ O • 3.3SiO ₂ 25th 1 1 Na ₅ P ₃ O ₁₀ 0.3 Na ₂ CO ₃ 1.5 0.2 1 1 Perborate 0.3 0.3 MgSiO ₃ CMC Brightener

Example 8

A surface cleaner for cleaning hard surfaces such as B. wall tiles, tiles, sink and Wash basins, lacquered doors, walls, smooth floor coverings, household appliances such as crockery, cutlery, etc. was obtained by hot atomization of an aqueous mixture of the ingredients in the following composition obtain:

30.0% by weight ABS, 3.0% by weight KA-ÄO sulfate, 1.0% by weight coconut fatty acid diethanolamide, 3.0% by weight sodium tripolyphosphate, 4ϊ 8.0% by weight sodium poly-flt-hydroxyacrylate,

See viscosity ηS = 0.15, 3.0% by weight Na ₂ B ₄ O ₇ · 10 H ₂ O, 1.0% by weight boric acid, remainder sodium sulfate and water.

specific

Claims (6)

Patent claims: 1. Washing and cleaning agents containing at least one surfactant from the group of anionic, zwitterionic and nonionic surfactants and builder substances, characterized in that that the structural substances are at least partially made up of water-soluble salts of polymeric «-hydroxy- and α-aminoacrylic acids, the reaction products of oJJ-dihalopropionic acids or their esters, in particular of a ^ -dibromopropionic acid or its esters, in aqueous Medium with basic agents from the group of hydroxides, carbonates, acetates, the Alkalis, especially sodium, ammonia, primary, secondary and tertiary amines or quaternary ammonium hydroxides. 2. Means according to claim 1, characterized in that they are the alkali salts as the structural substances Poly-at-hydroxyacrylic acids, especially the sodium salts, contain. 3. Composition according to claim 1 and 2, characterized in that it is at least 1 wt .-%, preferably at least 3% by weight, based on the total amount of the preparation, from the claims 1 defined polycarboxylates. 4. Means according to claim 1 and 2, characterized in that the structural substances from
90-5, preferably 90-40% by weight of the polycarboxylates defined in claim 1 and 10-95, preferably 10-60% by weight of others common structural substances exist. 5. Composition according to claim 1 -4, characterized in that the amount of structural substances according to claim 3 preferably 0.5 to 7 times and in particular 1 to 5 times the total Surfactants. 6. Bleaching detergent according to claims 1-5, characterized in that it has a bleaching component contains, including any stabilizers and / or activators for per compounds that may be present 2-40, preferably 7-35% by weight of the total detergent. Wastewater-originating phosphate content of the detergent is due It was therefore the demand for Low-phosphate or phosphate-free detergents and cleaning agents that do not contain any of the phosphate-containing products were collected Detergents and cleaning agents have said disadvantages. The aim of the invention is therefore to provide detergents and cleaning agents, their skeletal substances, to date consisted of a substantial part of tripolyphosphates, without the use of tripolyphosphate or under Redevelopment of the tripolyphosphate content. Detergents and cleaning agents for the purposes of the invention are, for. B. Preparations for washing and / or bleaching of fiber and textile materials and for cleaning equipment, apparatus, pipelines, vessels, hard Surfaces of all kinds in industry, in commercial operations and in the household, such as B. mild detergent for hand and machine washing, high-temperature detergents, especially for drum washing machines, prewash detergents, Bleaching agents, cleaning agents for surfaces made of ceramic, glass, metal, plastic, wood, etc. In the applicant's German patent application P 20 61 584.3, water-soluble salts of polymeric «-hydroxy- and α-aminoacrylic acids and their use as complexing agents suggested. The polymers mentioned are process products that can be treated by treatment of a ^ -dihalopropionic acids or their esters, in particular α, / 3-dibromopropionic acid or its Ester, obtained in an aqueous medium with basic agents. As a basic acting agent occur especially the hydroxides, carbonates and acetates of alkalis, especially sodium. Furthermore can Ammonia, primary, secondary and tertiary amines or quaternary ammonium hydroxides can be used. Accordingly, it can be assumed that the process products mentioned from the ", j9-dihalopropionic acid by polymerization with elimination of hydrogen halide, formation of polylactones and formation of salts arise with the introduction of the hydroxyl or an amino group. The polycarboxylates obtainable by the process mentioned are mainly composed of units of the formula