KR800001074B1 - Washing compositions containing aluminosilicates and nonionics and method of washing textiles - Google Patents

Abstract

Mixts. of ethoxylated alcs. having d.p. 8-20 and d.p 2-6 were used with aluminosilicates (Ca ion sequestrant) to prep. detergents esp. useful for removing oily soils. A detergent comprised polyethyene glycol monooleyl ether(I; d.p.10) 10, I(d.p 5) 8, Na2CO3 45, aluminosilicates 22, Na citrate 5.5, CM-cellulose 1.3 and H2O 8.3%

Description

Washing compounds and fabrics containing aluminum silicates and nonionics

The present invention relates to a process for washing, bleaching and cleaning solid materials, in particular fabrics, by using a bath containing a substance that can bind to the objects causing the hard water. In this process, finely divided water-insoluble compounds are suspended in an aqueous treatment solution. These compounds have a calcium binding capacity of at least 50 mg / g of anhydrous active substance (= AS), including bound water, and have the following general formula: .

(Cat ₂ / nO) xMe ₂ O ₃ (SiO ₂ ) y

Where Cat represents an n-valent cation and is exchangeable with calcium, x represents a number between 0.7-1.5, Me represents boron or aluminum, and y represents a number between 0.8-6, especially between 1.3-4.

The calcium binding capacity may reach 200 mg of calcium oxide per gram of AS. Sodium is the preferred cation but it is not only hydrogen, lithium, potassium, ammonium or magnesium but also has 3 or less carbon atoms for alkylol groups, for example having up to 2 carbon atoms for primary, secondary or tertiary alkylamines or alkylolamines. It can also be replaced by cations of water-soluble organic bases such as alkylolamines having the following carbon atoms.

The cation exchangeable compounds specified above used in the present invention in place of phosphates, in particular tripolyphosphates, will be referred to hereinafter as “aluminum silicates”. Sodium aluminum silicates are mainly used. All details of their preparation and use apply explicitly to the other compounds claimed.

Compounds having compositions of 0.7-1.1 Na ₂ O, Al ₂ O ₃ , 1.3-2.4 SiO ₂ are of particular practical concern. The calcium binding strength of these materials is in the range of 100-200 mg CaO / g AS.

A more advanced process of the invention, wherein the aqueous treatment solution for fabrics contains one part weight of nonionic material and 0-3 parts weight of anionic surfactant wherein the nonionic surfactants are carbon A mixture of highly ethoxylated different compounds having 10-18 aliphatic hydrocarbon groups, wherein 2-6 ethylene in a molecule per part of nonionic compound having 8-20 ethylene glycol ether groups in the molecule There are compounds weighing 0.2-2 parts with glycol ether groups.

This surface active ingredient, mainly used at concentrations of 0.1-3 g / l, is used in combination with the cation exchangeable aluminum silicates described above to remove dirt, particularly fatty or oily soils.

The aluminum silicates specified above are prepared synthetically by simple methods, for example obtained by reacting water soluble silicates with water soluble aluminates in the presence of water. For this purpose, the aqueous solutions of the starting materials can be mixed with each other or the components present in solid state can be reacted with other components present in the aqueous solution. In addition, by mixing the two materials, all of which are present as solids, the aluminum silicates described above are obtained when water is present. Aluminum silicates can also be prepared by reacting Al (OH) ₃ , Al ₂ O ₃ or SiO ₂ with alkali metal silicates or aluminate solutions. Finally, such materials are also obtained from molten materials. However, this process is less economical because it requires a high dissolution temperature and also the melt must be converted to a finely divided product.

Aluminum silicates, prepared by precipitation or converted to finely divided states in aqueous suspensions by other processes, are converted from amorphous to crystalline by heating to a temperature of 50-200 ° C. However, there is little difference in calcium binding strength between these two forms. If drying conditions are a separate issue, the crystalline form is proportional to the amount of aluminum contained in the aluminum silicate.

The amorphous or crystalline aluminum silicate present in the aqueous suspension can be separated from the aqueous solution by filtration and dried to a temperature of 50-805 ° C. This product has some bond water depending on the dry state. Anhydrous product is obtained at 800 ° C. If the water must be completely removed, this is possible by heating at 800 ° C. for one hour. In this way the AS content of the aluminum silicates is also determined.

Such high drying temperatures are not suitable for the aluminum silicates used in the present invention: it should not exceed 400 ° C or higher. It is of particular advantage that products dried at significantly lower temperatures, for example 80-200 ° C. until the adhesive water is removed, are useful for the purposes of this invention. Aluminum silicates containing various binding water, prepared after pulverizing the dried filter cake, are obtained as fine powders whose initial particle size does not exceed 0.1 mm and is usually less than 0.1 μm as a fine powder product. To this. It should be noted that the initial particles can aggregate to a larger structure. The initial particle size is mainly in the range 50-1μ.

Other cations such as potassium, magnesium or aluminum silicates of water soluble organic bases are prepared by base exchange from sodium aluminum silicates in a simple manner. The use of such compounds in place of sodium aluminum silicates is appropriate when special effects are obtained by transferring such cations, for example when it is desirable to affect the solution state of surface active substances present at the same time.

The amount of aluminum silicate required to achieve good cleaning and overcleaning effects depends on its calcium binding capacity, the degree of entertainment of the materials to be treated, and the hardness and amount of water used. If hard water is used, the aluminum silicate is used so that the residual amount of water is less than or equal to German hardness of 5 ° (corresponding to 50 mg CaO / l), especially of German hardness of 2 ° to 0.5 ° (corresponding to 5-20 mg CaO / l). It is convenient to adjust the amount. It is appropriate to use a rather excess aluminum silicate to achieve the optimum cleaning and cleaning effect, in order to fully or partially bond the material that produces the hardness contained in the separated impurities, especially in the case of heavily soiled materials. As a result, the concentration of aluminum silicate used is usually 0.2-10 g AS / l, in particular 1-6 g AS / l.

The removal of impurities is substantially accelerated or improved by placing the entertaining material in a treating solution which acts to form or precipitate complex salts to calcium present in the water as a material producing hardness. Although materials forming complexes to calcium used in the present invention have poor complexation-forming ability and are not considered as representative complexing salts for calcium, these materials often have the ability to delay the precipitation of calcium carbonate from aqueous solutions. Have

Small amounts of added salts, for example 0.05-2 g / l calcium, are used to significantly accelerate or improve the removal of impurities. In particular, the addition amount of 0.1-1 g / l is used. In practice, higher amounts may be used, but when complex salt-forming or precipitated substances containing phosphoric acid are used, the amount of addition is clearly less likely to be carried by the shell than the phosphorus obtained by using a cleaning agent based on the triphosphate present. So that the quantity must be chosen.

Complex salt-forming or precipitated materials may be inorganic compounds such as pyrophosphate, triphosphate, high density polyphosphate and metaphosphates.

Organic compounds as complex salts and precipitates for calcium are found in polycarboxylic acids, hydroxy carboxylic acids, aminocarboxylic acids, carboxyalkyl ethers, polyanionic polymerizable carboxylic acids and phosphonic acids. The compounds are usually used in the form of water soluble salts.

Examples of the polycarboxylic acids include dicarboxylic acids of the general formula HOOC- (CH ₂ ) n-COOH (n = 1-8), as well as maleic acid, methylenemalonic acid, citraconic acid, mesaconic acid, itaconic acid, tricar Acyclic polycarboxylic acids having at least three carboxyl groups in the molecule, such as valelylic acid, aconitic acid, ethylenetetracarboxylic acid, 1,1,3,3-propane-tetracarboxylic acid, 1,1,3 , 3,5,5-pentane-hexacarboxylic acid, hexanehexacarboxylic acid, and pentane-tetracarboxylic acid, cyclohexane, hexacarboxylic acid, tetrahydrofuran-tetracarboxylic acid, phthalic acid, terephthalic acid, benzene There are cyclodi- or poly-carboxylic acids such as tri, benzenetetra- or benzenepenta-carboxylic acids and melittinic acid.

Examples of hydroxymono- or hydroxypoly-carboxylic acids are glycolic acid, lactic acid, malic acid, tartonic acid, methyl tartonic acid, gluconic acid, glycerin acid, citric phosphoric acid, tartaric acid, salicylic acid and the like.

Examples of aminocarboxylic acids include glycine, glycylglycine, alanine, asparagine, glutamic acid, aminobenzoic acid, aminodi- or tri-acetic acid, hydroxyethyl-iminodiacetic acid, ethylenediamino-tetraacetic acid, hydroxyethyl-ethylene In addition to diamino-triacetic acid and diethylenetriamine-pentaacetic acid, high-density homologues can be cited, including polymerization and subsequent saponification of N-aziridyl carboxylic acid derivatives such as acetic acid, succinic acid, tricarvallic acid saponification) or polyamines having a molecular weight of 500-10,000 are condensed with chloracetic acid or bromic acid salts.

Examples of carboxyalkyl ethers are polycarboxylic acids containing 2,2-oxydisuccinic acid and other ether polycarboxylic acids, especially carboxymethyl ether groups, including the following polyhydric alcohols, hydroxy and Corresponding derivatives of acids belong, and they can be fully or partially etherified with glycolic acid.

Glycol, di- or tri-glycols, glycerin, di- or tri-glycerine, glycerin monomethyl ether, 2,2-dihydroxymethylpropanol, 1,1,1-trihydroxymethylethane, 1,1, 1-trihydroxymethylpropane, erythritol, pentaerythritol, glycolic acid, lactic acid, tartaric acid, methyl tartronic acid, glycerin acid, erytronic acid, malic acid, citric acid, tartaric acid, trihydroxyglutaric acid, sakaric acid, Viscous acid and the like.

As transition forms for polyanionic polymers, carboxy methyl ethers of sugar, starch, cellulose can be mentioned.

Among polyanionic polymers, polymerizable carboxylic acids play a special role, for example, polymers such as acrylic acid, hydroxyacrylic acid, maleic acid, itaconic acid, mesaconic acid, aconitic acid, methylenemalonic acid and citraconic acid, and the like. Cross-copolymers or copolymers with ethylenically unsaturated compounds described above, such unsaturated compounds are for example ethylene, propylene, isobutylene, vinyl alcohol, vinyl methyl ether, furan, acrolein, vinyl acetate, acryl Amides, acrylonitrile, methacrylic acid, crotonic acid, and the like, and also copolymers, for example, 1,1-copolymers prepared from maleic anhydride and ethylene or propylene or furan.

Still other polyanionic polymers in the form of polyhydroxy polycarboxylic acids or polyaldehyde-polycarboxylic acids are actually materials formed from acrylic acid and acrolein units or acrylic acid and vinyl alcohol units, and they are of acrylic acid and acrolein. By co-polymerization or subsequent to the polymerization of acrolein, possibly by reaction with canniza in the presence of formaldehyde.

Examples of phosphorus-containing organic complex salt-forming substances include alkanpolyphonic acid oils, amino- and hydroxy-alkanepolyphosphonic acids, and methanediphosphonic acid, propane-1,2,3-tri as phosphonocarboxylic acids. Forsylic acid, butane-1,2,3,4-tetraphosphonic acid, polyvinylphosphonic acid, 1-aminoethane-1,1-diphosphonic acid, 1-amino-1-phenyl 1,1-diphosphonic acid, Aminotrimethylenetriphosphonic acid, methylamino- or ethylamino-dimethylenediphosphonic acid, ethylene diamino-tetramethylenetetraphosphonic acid, 1-hydroxyethane-1,1-di-phosphonic acid, phosphonoacetic acid, phosph Phonopropionic acid, 1-phosphonoethane-1,2-dicarboxylic acid, 2-phosphonopropane-2,3-dicarboxylic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, Copolymers from vinylphosphonic acid and acrylic acid together with 2-phosphonobutane-2,3,4-tricarboxylic acid.

By using the aluminum silicates described above according to the present invention, it is possible to maintain the phosphorus content of the treated liquid at 0.6g / l or less, especially the organic or inorganically bound phosphorus content at 0.3g / l or less, The value can be maintained even when phosphorus-containing inorganic or organic double salt formation or precipitates are used. Good results are obtained even when there is no phosphorus in the treatment liquid.

The process according to the invention using aluminum silicates can be used for various cleaning operations in many technical fields and at home. Examples of such applications include cleaning instruments and tools, devices, tubing and wood, plastics, metals, ceramics and glass containers in the industry and related fields, and furniture, walls, floors, or ceramics in the home. And cleaning, polishing and lacquer surfaces of glass, metal, wood or plastics. A particularly important application is to wash and bleach all kinds of fabrics in industrial, industrial laundries, and at home.

Fabrics to be cleaned consist of various natural or synthetic fibers. These include cotton, regenerated cellulose or linen, as well as synthetic fibers such as highly treated cotton or polyamide, polyester, polyacrylonitrile, polyurethane, polyvinylchloride or polyvinylidenechloride fibers. The cleaning composites according to the invention can also be used to wash fabrics composed of fibers that are “easy to handle” or do not require ironing as a blend of synthetic fibers and cotton.

In cleaning and cleaning such materials using aqueous cleaning baths containing suspended aluminum silicate, the cleaning and cleaning effects can be improved by using conventional components having such a treatment bath. Such ingredients may include surface active materials, surface active or non-surface active foam stabilizers or inhibitors, fabric softeners neutral or alkaline reaction enhancers, chemically acting bleaches, as well as stabilizers or accelerators thereof, dirt carriers, corrosion Inhibitors, antimicrobial agents, enzymes, colorants, dyes and agents.

The following concentrations are suitable for the use of one or more of the aforementioned materials usually present in washes and cleaning solutions.

0-6 g / l reaction enhancer,

0-0.4 g / l free radicals or the same amount of active chlorine.

The pH value of the treatment bath is between 6-13, in particular 8.5-12, depending on the material being cleaned or cleaned.

The present invention also relates to compounds which carry out this process, which includes the aluminum silicates specified above as calcium binders.

Compounds usually contain 3-40%, in particular 3-30%, of various types of surface active ingredients.

The aluminum silicate content of such compounds is in the range of 5-95%, in particular 15-60%.

The compounds according to the present invention also include inorganic phosphates or organic phosphorus compounds present in the compounds forming phosphorus formations or precipitates for calcium, the activity of which depends on its chemical properties, usually between 2-15%. It has a content of

The amount of inorganic phosphate or organic phosphorus compounds present in the compounds according to the invention should not be greater than the total phosphorus content of 6%, in particular 3%, of the compound.

Alternatively, other components of the cleaning compound may be present in that compound.

All these percentage data are percentages calculated by weight; In the case of aluminum silicates this percentage relates to the anhydrous active ingredient (= AS).

Other components of the cleaning compound include surface or inactive foam stabilizers or inhibitors, fabric softeners, neutral or alkaline reaction enhancers, chemical bleaches, as well as stabilizers or promoters. In general, the components present in low doses are corrosion inhibitors antimicrobials, soil carriers, enzymes, colorants, dyes, flavorings, and the like.

Compound compositions used in the temperature range of 50-100 ° C. as representative fabric cleaning compounds are in the following ranges.

3-30% of the surface active ingredients described above.

5-70% aluminum silicate (corresponding to AS).

Complexing agents with 2-45% calcium.

Washing alkali (alkali enhancer) unable to form 0-50% of complex salts.

0-50% bleach as well as other additives present in small amounts in conventional fabric cleaning compounds.

Nonionic surface-active compounds (= nonionic materials) used in accordance with the present invention may comprise 2-6 moles or 8-18 moles of ethylene oxide in one roll of fatty alcohol, alkylphenol, fatty acid, fatty amine, fatty acid amide or Products added to alkanesulfonamide and the like. Of particular importance are pure aliphatic nonionics derived from, for example, coconut or resin fatty alcohols, oleyl alcohols or secondary alcohols having 8-18, preferably 12-18 carbon atoms.

Products in which ethylene oxide is added to terminal or non-terminal adjacent alkanediols may also be used as nonionic materials, with those having 2-4 or 8-14 ethylene glycol ether groups in the molecule being preferred.

Anionic surfactants contain at least one hydrophobic organic residue and a water soluble anionic group in the molecule.

Hydrophobic residues are aliphatic hydrocarbon residues having 8-26, preferably 10-22, in particular 12-18 carbon atoms, or aromatic residues having 6-18, preferably 8-16 aliphatic carbon atoms.

Available anionic surfactants include soaps made from natural or synthetic saturated fatty acids or soaps made from resin or naphthenic acids. Suitable synthetic anionic surfactants are sulfonate, sulfate and synthetic carboxylate forms.

Suitable surfactants in the form of sulfonates are mixtures of alkylbenzenesulfonates (C _9-15 -alkyl), alkenes and hydroxyalkane-sulfonates as well as disulfonates, which are terminal or non-terminal double bonds. It is obtained from monoolefins having a sulfonated as gas sulfatrioxide, and then hydrolyzed the sulfonated product with alkali or acid again. Still other suitable surfactants are alkanesulfonates, which can be obtained by sulfochlorination or sulfoxidation from alkanes followed by hydrolysis or neutralization, or by adding bisulfite to olefins. . Another useful surfactant in the form of sulfonates is esters of alpha-sulfo-fatty acids, for example alpha-sulfonic acids prepared from hydrogenated methyl or ethyl esters of coconut, palm seed or resin fatty acids. Can be.

Suitable surfactants in the form of sulfuric acids are sulfuric acid monoesters of primary alcohols (eg coconut fatty alcohols: resin fatty alcohols or oleyl alcohols) and secondary alcohols. Also suitable are reaction products of sulfated fatty acid alkanol amides, fatty acid monoglycerides or 1-4 moles of methylene oxide with primary or secondary alcohols or alkylphenols.

Suitable as other anionic surfactants are fatty acid esters, or amides of hydroxy-, amino-carboxylic or sulfonic acids, for example fatty acid sarcosides, glycolates, lactates, other Urides or isethionates.

Foaming power of the surfactant component is increased or decreased by the combination of suitable surfactants. The decrease is when the non-surfactant organic material is added.

The reduced foaming capacity required for mechanical operation is often due to the use of different types of surfactants in combination, for example in the combination of sulfates or sulfonates with nonionics or soaps. In the case of soaps, the degree of saturation of the foam-inhibited fatty acid group and the increase in carbon number increase. Saturated C _{20-24 -fatty} acid soaps are particularly suitable as foam inhibitors.

Some N-alkylated aminotriazines containing chlorine are 2-3 moles of mono-or having 6-20, preferably 8-18 carbon atoms in 1 mole cyanuric chloride and alkyl residues. Obtained by reacting di-alkylamines, they belong to non-interface-activated foam inhibitors.

Propoxylated or butoxylated aminotriazines have a similar action, for example, adding 5-10 moles of propylene oxide to 1 mole of melamine and 10-50 moles of butylene oxide to the preceding propylene oxide. It is obtained by adding to a derivative.

Paraffins or halogenated paraffins having a melting point of 100 ° C. or lower, ketones of aliphatic C _18-20 , aliphatic carboxylic acid esters having at least 18 carbon atoms in acid or alcohol residues (e.g. Cerides or fatty acid-fatty acid alcohol esters) are suitable as non-interface-active foam inhibitors. They are used in particular in combination with surfactants in the form of sulfates or sulfonates and soaps for foam reduction. Alkali-stable silicones have also been shown to be effective in inhibiting foam.

Weak acids, neutral and alkali reactive inorganic or organic salts are suitable as enhancers.

Weak acids, neutral or alkali reactive salts are suitable for the present invention, for example bicarbonates, carbonates, borate or silicates of alkali metals, alkali metal sulfates and organic non-interface-active sulfonic acids Alkali metal salts, carboxylic acids and sulfocarboxylic acids having 1-8 carbon atoms, and the like. Examples of these are water-soluble salts of benzene-, toluene-, or xylene-sulfonic acids and water-soluble salts of sulfoacetic acid, sulfobenzoic acid or sulfodicarboxylic acids.

The compounds mentioned above as complexing agents or precipitants for calcium are useful as enhancers. They may thus be present in the compounds according to the invention in an amount greater than necessary to act as a complexation or precipitating agent for calcium.

Most of the compounds, in particular reinforcing materials used as fabric cleaning composites or household cleaning composites are allowed to undergo a neutral to strong alkali reaction such that the pH of the 1% solution of these materials is generally in the range of 7-12. In this case, the good cleaning components usually have a neutral to mild alkali reaction (pH = 7-9.5), while the washing combinations when rinsing, pre-cleaning and boiling are more strongly alkaline (pH = 9.5-12, usually Is adjusted to 10-11.5).

If for special cleaning purposes a higher pH value is required, these can be easily adjusted using alkali metal silicates or caustic alkalis with a suitable Na ₂ O: SiO ₂ ratio.

Sodium perborate tetrahydrate (NaBO ₂ · H ₂ O ₂ · 3H ₂ O) and monohydrate (NaBO ₂ · H ₂ O ₂ ) are of special importance for compounds that act as bleaches by producing hydrogen peroxide in water. However, other borate salts that produce hydrogen peroxide are also useful, for example perborax (Na ₂ B ₄ O ₇ .4H ₂ O ₂ ). Such compounds may be partially or completely substituted by other active oxygen mediators, for example peroxycarbonates (Na ₂ CO ₃ .1.5H ₂ O ₂ ), peroxy, in particular as peroxyhydrates. pyrophosphate acids, citrate buffer hydrate acids, urea-of Caro (Caro) acid (KHSO _5), perbenzoate flow or a peroxy phthalates as peracid salts that the addition of hydrogen peroxide and compounds - hydrogen peroxide - or melamine-hydrogen peroxide Salts.

It is advisable to combine the usual water-soluble or water-insoluble stabilizers for peroxy-compounds with the latter in an amount of 0.25-10% by weight. Suitable water soluble stabilizers comprise a ratio of 1-8, preferably 2-7%, of the total product weight, usually with a magnesium silicate ratio of magnesium oxide: silicon dioxide 4: 1-1: 4, preferably 2: 1-1: 2 and especially 1: 1 are suitable, and these are obtained by deposition from an aqueous solution. Alkaline earth metals, cadmium or tin silicates having the corresponding compositions can be used instead.

Oxides of tin containing water are also suitable as stabilizers. Water-insoluble stabilizers may be present with water-soluble stabilizers, which are organic complex salt formers, the amount of which consists of 0.25-5, preferably 0.5-2.5% of the total product weight.

During washing, bleaching components containing accelerators are incorporated into the preparation to obtain a satisfactory bleaching action at temperatures below 80 ° C., in particular at 60-40 ° C.

Certain N-acyl and O-acyl compounds that form organic peracids as hydrogen peroxide act as accelerators for compounds that produce hydrogen peroxide in water, particularly acetyl-, propionyl- or benzoyl compounds with carboxylic acid or pyrocarbide. Main acid esters can be mentioned. Useful among other compounds are as follows.

N-diacylated and N, N'-tetraacylated amines, for example N, N, N ', N'-tetraacetyl-methylenediamine or ethylenediamine, N, N-diacetylaniline and N, N- Diacetyl-p-toluidine or 1,3-diacylated hydantoin, alkyl-N-sulfonyl-carbonamides, for example N-methyl-N-acetamide, N-methyl-N-mesyl- Benzamide-N-methyl-Nmesyl-p-nitrobenzamide, and N-methyl-N-mesyl-p-methoxybenzamide, N-acylated cyclic hydrazides, acylated triazoles, or As urasols, for example monoacetylmaleic acid hydrazide, O, N, N, trisubstituted hydroxylamines, for example O-benzoyl-N, N-succinyl-hydroxylamine, O-acetyl-N , N-succinyl-hydroxylamine, Op-methoxybenzoyl-N, N-succinyl-hydroxylamine, Op-nitrobenzoyl-N, N-succinyl-hydroxylamine and O, N, N-tri Acetyl-hydroxylamine, N, N'-diacyl-sulfurylami As the Drew, for example, N, N'-dimethyl-N, N'-diacetyl-sulfuryl amide, and N, N'-diethyl-N, N'-diacetyl-sulfuryl amide, and N, N '-Dimethyl-N, N'-dipropionyl-sulfurylamide, as triacyl-cyanurate, for example as triacetyl- or tribenzoyl-cyanurate, carboxylic anhydride, for example , Benzoic anhydride, m-chlorobenzoic anhydride-, phthalic anhydride, 4-chlorophthalic anhydride, sugar esters, for example glucose penta acetate, 1,3-diacyl-4,5-diacyloxy As imidazolidines, for example, 1,3-formyl-4,5-diacetoxy-imidazolidine, 1,3-diacetyl-4,5-diacetoxy-imidazolidine, 1 , 3-diacetyl-4,5-dipropionyloxy-imidazolidine, acylated glycolurils, for example tetrapropionylglycoluril or diacetyl-dibenzoyl-cyclyluril, diacylation 2,5-diketopiperazines, for example 1,4-diacetyl-2,5-diketopiperazine, 1,4-dipropionyl-2,5-diketopiperazine, 1,4- Dipropionyl-3,6-dimethyl-2,5-diketopiperazine, propylenediurea or 2,2-dimethyl-propylene diurea (2,4,6,8-tetraaza-bicyclo (3,3 (1) -nonane-3,7-dione or a 9,9-dimethyl derivative thereof), acetylated or benzoylated products, p- (ethoxycarbonyloxy) -benzoic acid and p- (propoxycarbonyl Sodium salts of oxy) -benzenesulfonic acid;

Active chlorine compounds that act as bleach are inorganic or organic compounds.

Suitable inorganic active chlorine compounds include alkali metal hypochlorides, in particular in the form of their mixed salts, orthophosphates or condensed phosphates such as pyro- and poly-phosphates, or alkali metal silicates. This is the case in the form of addition of compounds. If the cleaning agent and the cleaning aid contain monopersulfates and chlorides, active chlorine is formed in the aqueous solution.

Suitable organic chlorine compounds are in particular N-chloro compounds, in which one or two chlorine atoms are bonded to nitrogen atoms and the trivalent nitrogen atoms are in particular linked to anionic groups such as CO- or SO ₂ -groups. These compounds include dichloro- and trichloro-cyanuric acids or salts thereof, chlorinated alkylguanides or alkylbiguanides, chlorinated hydantoins and chlorinated melamines.

The article according to the invention also first comprises carriers, which dissociate from the fibers and catch the dirt suspended in the bath to prevent graying. Water-soluble claddings, which are usually organic components, are suitable for this purpose, for example water-soluble salts of polymerizable carboxylic acids, glues, gelatin, starch or cellulose ethercarboxylic acids or salts of ethersulfonic acids, or cellulose or starch. Salts of the sulfuric acid ester of are mentioned. Water-soluble polyamides containing acid groups also include salts of cellulose or sulfate esters throughout. Water soluble polyamides containing acid groups are also suitable for this purpose.

In addition to those mentioned above, water-soluble starch preparations and starch products may also be used, such as low starch, aldehyde starch. Polyvinylpyrrolidone is also available.

Enzyme agents used are usually mixtures of enzymes having different functions, for example, proteases, carbohydrases, esterases, lipases, redox elements, catalases, peroxidases, ureases. , Isometases, lyases, transferases, desmolases, or nucleases. Enzymes obtained from bacteria or fungi strains such as Bacillus subtilis or Streptomyces griesus are of particular interest, in particular proteases or amylases being relatively stable against alkalis, complexes and anionic surfactants. It is active even at temperatures up to < RTI ID = 0.0 >

Enzyme preparations are usually sold by manufacturers as aqueous solutions or powders of active substances, granules or cold-sprayed agents. They contain sodium sulfate, sodium chloride, alkali metal auto-, pyro-, or polyphosphates, in particular tripolyphosphates, as diluents or admixtures. Dust free formulations are of particular value. They are obtained by well-known methods, either by combining with oily or pasty-type bioactive agents or by granulating by dissolving the salts with their own moisture contained in the crystals.

The enzymes are formulated with specific enzymes such as proteases, amylases or lipases, depending on the particular type of soil, for example, it is preferable to combine enzymes having different functions, in particular proteases and amylases.

The cleaning compounds contain an optical lubricant for cotton, in particular diaminostilbene disulfonic acid or derivatives of alkali metal salts thereof. For example, 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino) -stilben-2,2'-disulfonic acid or its As salts of the analogous structural compounds of, they have a diethanolamino group, a methylamino group or a 2-methoxyethylamino group and the like instead of a morpholino group.

Suitable lubricants for polyamide fibers are those in the form of 1,3-diaryl-2-pyrazoline, for example 1- (p-sulfamoylphenyl) -3- (p-chlorphenyl) -2 -Pyrazoline and similar structural compounds thereof include, for example, methoxycarbonyl-, 2-methoxyethoxycarbonyl-, acetylamino or vinylsulfonyl group instead of sulfamoyl group. Substituted amino coumarins such as 4-methyl-7-dimethylamino- or 4-methyl-7-diethylaminocoumarin are also suitable as polyamide colorants. Also, 1- (2-benzimidazolyl) -2- (1-hydroxyethyl-2-benzimidazolyl) -ethylene and 1-ethyl-3-phenyl-7-diethylamino-carbostyryl compounds Also useful as polyamide colorants. 2,5-di- (2-benzoxazolyl) -thiophene; 2- (2-benzoxazolyl) -naphtho [2,3-b] -thiophene and 1,2-di- (5-methyl-2-benzoxazolyl) ethylene, and the like It is suitable as a coloring agent. There are also coloring agents in the form of substituted 4,4'-distyryldiphenyl, for example 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl.

Mixtures of the above-mentioned coloring agents are also used.

Powdered to granular materials according to the invention are prepared from all processes known in the art and are of particular interest in practical terms.

Thus, for example, powdered aluminum silicates can be mixed with other cleaning ingredients in a simple manner, while nonionic agents, for example, spray the same oily or pasty products onto the powder. Another possible method of preparation is to combine powdered aluminum silicates with other components present in the aqueous slurry state, which are converted to powders by drying the moisture by a crystallization process or by heating. After high temperature drying (eg in rollers or spray towers), components sensitive to heat and moisture (eg bleaching agents and their accelerators, enzymes, antimicrobials, etc.) can be combined with each other.

Example 1

A method for producing aluminum silicates and a method for determining calcium binding strength to be used are described in Canadian Patent No. 10,566,52. Moisture content was determined by heating the product at 800 ° C. for one hour.

All percentage data is weight percentage. In the case of aluminum silicates it relates to anhydrous active material (AS).

Many of the aluminum silicates available in accordance with the present invention are listed below.

Salt components contained among the washing components of the examples (salt surfactants, inorganic salts as well as other organic salts) existed as sodium salts unless otherwise noted.

The following terms and abbreviations have the following meanings:

"ABS" refers to salts of alkylbenzenesulfonic acids having 10-15, usually 11-13, carbon atoms in alkyl bonds, which are obtained by condensation of side-chain olefins with benzene and sulfonated alkylbenzenes thus obtained.

"Alkanesulfonate" is a sulfonate obtained by sulfoxydecone paraffins having 10 to 15 carbon atoms.

"Hst-sulfonate" is a sulfonate obtained by sulfonating hydrogenated resin fatty acid methyl ester with SO ₃ .

“Olefin sulfonates” are sulfonates obtained by sulfonating alpha-olefin mixtures having 15-18 carbon atoms with SO ₃ and hydrolyzing sulfonates with alkalis, which are in fact alkenesulfonates and hydroxy alkanesulfonates But also contains small amounts of disulfonates.

“Soap” is a fatty acid component that contains a solid mixture of resin and rape oil fatty acids (C ₁₆ -C ₂₂ ) in the same weight ratio.

“OA + xEO”, “TA + xEO”, “KA + xEO”, “SA + xEO” and “OXO + xEO” are industrial oleyl alcohol (OA), resin fatty alcohol (IV = 0.5), coconut fatty alcohol (KA), secondary aliphatic C _{11-15 -alcohol} (SA), and products made by adding ethylene oxide (EO) to C ₁₂ -C ₁₈ -alcohol (OXO) obtained by oxo synthesis, respectively, and are indicated by x Denotes the number of ethylene oxide molecules added to 1 mole of alcohol.

"CTMS" refers to a salt of O-carboxymethyl-tartron acid, "EDTA" is a salt of ethylenediaminetetraacetic acid, "HEDP" is a salt of 1-hydroxyethane-1,1-diphosphonic acid and "DMDP Is a salt of dimethylaminomethane-diphosphonic acid and “CMC” is a salt of carboxymethylcellulose.

The following table shows the structure of the cleaning components according to the invention. Where 1,2,3 denotes the finished cleaning compound, which is used for washing dyed or white fabrics at 40 ° -100 ° C., usually at 50 ° -100 ° C., at home, in industrial processes or in industry. to be.

Two compounds, 4 and 5, are used in commercial and industrial laundries, the former being used in the pre-cleaning process and the latter being used in the main washing process.

EDTA can be replaced by the same amount of HEDP or DMDP, and Na ₂ P ₃ O ₁₀ can be replaced by the same amount of phosphorus-free phosphate substituents such as citric acid or salts of O-carboxymethyl-tartaric acid Do.

Example 2

The cleaning ingredients used for the cleaning of heavily soiled workwear have the following compositions.

Example 3

In particular, the detergent components used in hard water have the following composition:

The detergent component according to the invention has a good ability to wash fat, which fact is for example seen in the collar and sleeves of dress shirts, especially in the case of shirts made of unwieldy cotton or polyester blend fabrics. As such, there is also a good effect of cleaning work clothes of fat-tainted work clothes, for example, those working in the kitchen, Fuzhou, service stations and car workshops.

Claims (1)

In the process of washing or bleaching fabrics by treating them with an aqueous solution, the aqueous solution includes materials capable of binding substances which cause curing in water, which are finely differentiated water-insoluble compounds, It has a calcium binding capacity of at least 50mgCaO / gAS, and its general formula is (Cat ₂ / nO) x, Me ₂ O ₃ , (SiO ₂ ) y, where Cat represents a cation of valence n and can be exchanged with calcium. Where x is a number of 0.7-1.5, Me is a boron or aluminum and y is a number of 0.8-6, suspended in a water treatment solution, where the aqueous treatment solution for textiles is 1 part of nonionic and 0 -3 weight parts of anionic surfactants, while non-ionic surfactants contain different highly ethoxy having aliphatic hydrocarbon groups with 10-18 carbon atoms A mixture of two compounds containing 0.2-6 weight parts of 2-6 ethylene glycol ether groups in the molecule per weight of non-ionic compound having 8-20 ethylene glycol ether groups in the molecule. A process for preparing a cleaning compound, characterized in that it contains.