DK156173B - PROCEDURE FOR WASHING TEXTILES, METHOD FOR PERFORMING THE PROCEDURE AND PROCEDURE FOR MANUFACTURING THE MEDICINE - Google Patents

Description

DK 156173 B

The main patent No. 151,231 relates to a process for cleaning, including washing, prewashing and bleaching of solid raw materials, especially textiles, by treating these raw materials with an aqueous raft containing water-insoluble, finely divided aluminum silicate having a builder action, as well as at least one compound selected from synthetic surfactants and optionally a bleaching agent, the process being characterized by working with a raft which, as an aluminum silicate and as a suspended phosphate substitute, contains a crystalline or pure-permeable aluminum silicate which contains bound water, is synthetically prepared and has a calcium binding capacity of at least 50 mg CaO / g of anhydrous, active substance, as described in the specification, of which aluminum silicate has the general formula (Kat20) x, A1203, (SiO2) y 15 where Kat is a calcium interchangeable alkali, x is a number of 0.7 to 1.5 and y is a number of 1.3-4.

The potassium binding capacity may even have values of 200 mg CaO / g AS.

20

Preferably, as a cation, sodium may be present. However, it may also be replaced by hydrogen, lithium, potassium, ammonium or magnium as well as the cations of water-soluble organic bases, e.g. bases of primary, secondary or tertiary amines or alkylolamines having a maximum of 2 carbon atoms per or at most 3 carbon atoms per alkylol residue.

The cation exchange compounds defined above to be used in place of the phosphates, especially tripolyphosphate, are hereinafter referred to as aluminum silicates for the sake of simplicity. Preferably, sodium aluminum silicates are used, all indications as to their preparation and use apply in the same way to the other compounds.

Of particular practical interest, compounds of the composition are 0.7-1.1 Na 2 O, Al 2 O 3, 1.3-2.4 SiO 2.

The calcium binding capacity of these substances' is approx. in the range of 100 to 200 mg CaO / g AS.

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The invention relates to the change in the method of washing according to the main patent that the aqueous treatment float for the fabrics contains a surfactant component of 1 part nonionic and 0-3 partion anionic surfactants, the nonionic surfactants being a mixture of various hot ethoxylated compounds, which have an aliphatic hydrocarbon residue of 10-18 carbon atoms, in which by weight of non-ionic compounds having 8-20 ethylene glycol residues in the molecule, 0.2-2 parts by weight of compounds having 2-6 atylene glycol residues in the molecule are found.

10

The use of such surfactant components, the concentration of which is preferably 0.3-3 g / l, in combination with the above-described cation-exchanging aluminum silicates, results in improved dirt removal, especially in the case of greasy oily soils.

1 5 a

The aluminum silicates defined above can be synthetically prepared in a simple manner, e.g. by reaction of water-insoluble silicates with water-soluble aluminates in the presence of water. For this purpose, aqueous solutions of the starting materials may be mixed with each other or a solid state component may be reacted with the other components available as aqueous solution. Also, by mixing the two solid components, the individual aluminum silicates are obtained by the presence of water. Also from A1 (OH) 3, A123 or Si2, aluminum silicates can be prepared by reaction with 25 alkali silicate or aluminate solutions. Finally, such substances are also formed by a melt, but due to the necessary high melting temperatures and the necessity of converting the melt into finely divided products, this process is less interesting for economic reasons.

30

The aluminum silicates transferred by precipitation or otherwise in finely divided state in aqueous suspension can be transferred from heating to temperatures of 50-200eC from amorphous to age or crystalline state, but there is hardly any difference between these two forms. in terms of calcium binding capacity. Except for the drying conditions, this is proportional to the amount of aluminum contained in the aluminum silicates.

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The amorphous or crystalline aluminum silicate in aqueous suspension can be filtered off from the aqueous solution remaining and filtered at temperatures of e.g. 50-800 ° C. Depending on the grounding conditions, the product gets more or less bound water. δ Anhydrous products are obtained at 800 ° C. If the water is to be expelled completely, this is possible at 1 hour heating to 800 ° C. In this way, the AS content of the aluminum silicates is also determined.

Such high cure temperatures are not recommended for the aluminum silicates to be used in the invention. Intentionally, 400 ° C is not exceeded. It is a particular advantage that also products which are dried at substantially lower temperatures of e.g. 80-200 ° C until removal of the adherent liquid water is useful for the purposes of the invention. The aluminum silicates thus obtained containing alternating amounts of bound water appear after probing the dried filter cake as a fine powder whose primary particle size is at most 0.1 mm, but for the most part is substantially lower and goes all the way down to stiffness. , eg. up to 0.1 µ. It should be borne in mind that the primer particles can be agglomerated into sterile formations. The prime particle size is preferably in the range of 50 to 1 µ.

Of the sodium silicates, the aluminosilicates of other cations, e.g. of sodium, magnesium or water-soluble organic bases, 25 are prepared simply by base exchange. The use of these compounds in place of the sodium aluminum silicates may be appropriate if, upon delivery of said cations, a particular effect is obtained, e.g. will affect the solubility state of simultaneously surfactant surfactants.

30

The amount of aluminum silicate required to achieve a good washing or cleaning effect depends on one side of its calcium binding capacity, on the other side of the amount and degree of fouling of the treated material, and of the hardness and amount of the water used. 35 Using hard water, it is appropriate to measure the amount of aluminum silicate such that the residual water hardness is not more than 5e dH (corresponding to 50 mg CaO / 1), preferably 0.5-2® dH (5-20 mg Ca0 / 1). In order to achieve an optimal washing or cleaning effect it can be used 4

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it is recommended, when using heavily soiled undercoats, to use a certain excess of aluminum! 1 icons to also completely or partially bind the hardness contaminants contained in the washed contaminants. Therefore, the application concentration of the aluminum aliquots may be in the range of preferably 0.2-10 g AS / 1, preferably 1-6 g AS / 1.

As already stated in the main patent, the removal of the contaminants is greatly accelerated and / or improved if the coating float is added to a substance which exerts a complexing and / or precipitating effect on it in the water which hardens calcium. As complexing agents for calcium, the compounds of the invention are also suitable for substances with so little complexing ability that until now they should not be considered as typical complexing agents for calcium, but such compounds often had the ability to pre-precipitate the calcium carbonate of aqueous solutions.

15

In portions, little added amounts are used, e.g. 0.05-2 g / l complexing agent or calcium precipitating agent to appreciably accelerate or improve the removal of the contaminants. In particular, they work with added amounts of 0.1-1 g / l. Substantially higher amounts can also be used, but when using phosphorous complexing agents or precipitants, such quantities must be selected so that the phosphorus loading of the wastewater is clearly less than using the currently usual triphosphate based detergents.

25

To the complexing agents or precipitating agents, such inorganic species as e.g. pyrophosphate, triphosphate, boere polyphosphates and metaphosphates.

Organic compounds which serve as complexing agents or calcium precipitating agents are found among the polycarboxylic acids, the urban hydrochloric acids, the aminocarboxylic acids, carboxyalkyl ethers, polyanionic polymeric carboxylic acids and phosphonic acids, these compounds being mostly used in the form of their water-soluble salts.

Examples of polycarboxylic acids are dicarboxylic acid of the general formula H00C- (C2) n -COQH, where n = 0-8, in addition maleic acid, methylene malonic acid, citraconic acid, mesaconic acid, itaconic acid, non-cyclic polycarboxylic acids 35

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with mindsx J carboxyl groups in the molecule such as e.g. tricarballic acid, aconitic acid, ethylene tetracarboxylic acid, 1,1,3,3-propane tetracarboxylic acid, 1,1,3,3,5,5-pentane hexacarboxylic acid, hexane hexacarboxylic acid, cyclic di- or polycarboxylic acids such as cyclopentane tetracarboxylic acid, cyclohexane hexacarboxylic acid, tetrahydrofurant tetracarboxylic acid, phthalic acid, terephthalic acid, benzoltri, tetra or pentacarboxylic acid and medium acid.

Examples of hydroxymono or polycarboxylic acids are glycolic acid, lactic acid, tartaric acid, tartaric acid, methyl tartaronic acid, gluconic acid, glycerin acid, citric acid, tartaric acid, salicylic acid. Examples of aminocarboxylic acids are glycine, glycylglycine, alanine, asparagine, glutamic acid, amino = benzoic acid, iminodiacetic or triacetic acid, hydroxyethyliminodiacetic acid, ethylenediamineteteacetic acid, hydroxyethyl ethylenediaminetriacetic acid, hydroxyethyl ethyl diamine triacetic acid. H-aziridyl carboxylic acid derivatives, e.g. acetic acid, succinic acid, tricarballyl acid, and subsequent saponification or by condensation of polyamines of a molecular weight of 500-10,000 with chloroacetic or bromoacetic salts.

20

Examples of carboxyalkyl ethers are 2,2-oxydiruccinic acid and other ether polycarboxylic acids, especially polycarboxylic acids containing carboxymethyl ethers = groups to which similar derivatives of the following polyhydric alcohols or hydroxycarboxylic acids, which may be belt or fully dihydric glycol, glycerine, ethereal glycol, or triglycols, glycerin, di- or triglycerin, glycerin monomethyl ether, 2,2-dihydroxymethylpropanol, 1,1,1-trihydroxymethylethane, 1,1,1-trihydroxymethylpropane, erythritite, pentaerythritite, glycolic acid, lactic acid, tartaric acid, lactic acid acid, glyceric acid, erythronic acid, malic acid, citric acid, tartaric acid, tri = 30 hydroxyglutaric acid, sugar acid, mucic acid.

As the types of transition to the polyanionic polymers, mention is made of the carboxy methyl ethers of sugar, starch and cellulose.

Among the polyanionic polymers, the polymeric carbonic acids play a special role, e.g. the polymers of acrylic acid, hydroxyacrylic acid, maleic acid, itaconic acid, mesaconic acid, aconitic acid, methylene malonic acid, citraconic acid and the like, the copolymericates of the above-mentioned carboxylic acids mutually or with ethylenically unsaturated compounds such as ethyl acetate 6

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one, propylene, isobutylene, vinyl alcohol, vinyl methyl ether, furan, acrylic, vinyl acetate, acrylamide, acrylonitrile, methacrylic acid, crotonic acid, etc., e.g. The 1: 1 mixture polymers of maleic anhydride and ethylene or propylene or furan.

Other polyanionic polymers of the type such as polyhydroxypolycarboxylic acids or polyaldehyde polycarboxylic acids are substances which are essentially made up of acrylic acid and acrylic units, respectively acrylic acid and rhinyl alcohols, which can be obtained by copolymerization of acrylic acid or acrylic acid acrylic acid or acrylic acid acrylic acid or acrylic acid and on-going Cannizzaro reaction, optionally in the presence of formaldehyde.

Examples of phosphorus-containing organic complexing agents are alkane polyphosphonic acids, amino and byroxyalkane polyphosphonic acids and phosphonic carbonic acids such as e.g. the compounds methane diphosphonic acid, propane-1,2,3-triphosphonic acid, butane-1,2,3,4-tetraphosphonic acid, polyvinylphosphonic acid, 1-aminoethane-1,1-diphosphonic acid, 1-amino-1-phenyl-1, 1-diphosphonic acid, aminotrimethylene = triphosphonic acid, methylamino or ethylaminodimethylenediphosphonic acid, ethylenediamino te trame tylenetetrafic acid, 1-hydroxyacetane-1,1,1-diphosphonic acid, phosphonic acetic acid, phosphonic acetic acid, phosphonic acetic acid, phosphonic acetic acid, phosphonic acetic acid -phosphonopropane-2,3-dicarboxylic acid, 2-phosphonbutane-1,2,4-tricarboxylic acid, 2-phosphonbutane-2,3,4-tricarboxylic acid, and blend polymers of vinylphosphonic acid and acrylic acid.

By virtue of the application of the invention of the aluminum silicates described above, it is possible, without riders, to keep even the phosphorus entrapment of the treatment raft at a rate of 0.6 g / l without the use of phosphorous, inorganic or organic complexing agents or calcium precipitants. , preferably not more than 0.3 g / l of organic and / or inorganic blind in the environment. Good phosphorus-free work can also be done with good results.

The method of the invention, which works using aluminum silicates, can be used in numerous fields of the art and household for the most diverse purification tasks.

35 Examples of such applications are cleaning of tools, appliances, pipelines and containers of wood, plastics, metal, ceramics, glass, etc. industrial or commercial undertakings, cleaning of furniture, walls, floors and articles of ceramics, glass, metal, 7

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wood, kuHsxstef; cleaning of polished and varnished surfaces in the household, etc. A particularly important application is the washing and bleaching of textiles of all kinds in the industry, in commercial laundries, in the household.

5 The textiles to be washed may consist of the most diverse taverns of natural or synthetic origin. For example, hares e.g. cotton, regenerated cellulose or wax, and textiles containing shark-refined cotton wool or synthetic chemical taverns, e.g. polyamide, polyester, polyacrylonitrile, polyurethane, polyvinyl chloride or polyvinylidene chloride. The detergents according to the invention can also be used for the washing of the textile fabrics of synthetic taverns and cotton blends.

By washing and cleaning such substrates using aqueous 15 cleaning floats containing suspended aluminum silicates, the washing or cleaning effect can be enhanced by the usual constituents of such treatment floats. For example, hares e.g. surfactants, surfactant or non-surfactant-like foam stabilizers or inhibitors, textile bleaching agents, neutral or alkaline reacting builders, chemically-acting bleaches, and stabilizers and / or activators thereof, soil carriers, corrosion inhibitors, antimicrobial agents, dyes and fragrances, etc.

Using one or more of the aforementioned substances usually found in washing and cleaning floats, the following concentrations are suitably observed: 0-6, g / l buildup 0-0.4 g / l of active oxygen or equivalent amount of active chlorine.

The pH of the treatment float, depending on the substrate to be washed or purified, may be in the range of 6 to 13, preferably 8.5 to 12.

35

The invention further relates to agents intended for carrying out the process described which contain the aluminum silicates defined above as calcium binding agents. In a further embodiment of the invention, these agents are peculiar to the main patent

TrpH a 4 "irtδ irirtûVinl Αδ ΛίτβΠ'ΡΛΤ» Î-mûyîû / Îû? A Irrtm-nor διτ \ 4 * Λ «ν» 8

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The agents preferably contain from 3 to 40, in particular from 3 to 30% by weight of such a ten-component.

The aluminum silicate content of such agents may range from 5 to 5 to 95, preferably 15 to 60 $.

The compositions of the invention may further contain complexing agents or precipitating agents for calcium, viscous action, depending on the chemical nature of the agent, preferably present at contents of 2-15 $.

The amount of the inorganic phosphates and / or organic phosphorus compounds in the compositions of the invention should not be greater than a total P content of the agent of $ 6, preferably $ 3.

15 In addition, such other compositions of detergents can be found in such agents.

All these percentages are weight percentages. As far as the aluminum silicates are concerned, it is the anhydrous active substance (= AS).

20

Among the other usual components of detergents are e.g. surfactant or non-surfactant-like foam stabilizers or inhibitors, textile antifouling agents, neutral or alkaline-reactive build-up (eg substances, chemical bleaches, and stabilizers and / or activators for these). in small quantities, for example, corrosion inhibitors, antimicrobials are dirt carriers, enzymes, detergents, colorants and fragrances, etc.

The composition of typical textile detergents for use at temperatures in the range of 50 to 100 ° C is within the range of the following recipe: $ 3-30 surfactant components according to the above definition 5-70 $ aluminum silicates (AS calculated) $ 45 complexing agents for calcium 0-50 $ washing alkalis that are not capable of complexing (alkaline builders) 9

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0-50 $ bleach as well as other additives, mostly present in small amounts in textile detergents.

5 The detergent ingredients suitable for use in the compositions of the invention are listed below.

The non-ionic surfactants useful in accordance with the invention are preparation products of 2-6, 8-1S moles of ethylene oxide, respectively, to 1 mole of 10 fatty alcohol, alkylphenol, fatty acid, fatamine, fatty acid amide or alkane sulfonamide. Particularly important are the purely aliphatic, nonionic substances derived e.g. of coconut or tallow fatty alcohols, of oleyl alcohol or of secondary alcohols having 8-18, preferably 12-18 carbon atoms.

15

As non-ionic substances, the ethylene oxide preparation products can also be used for terminal or internal vicinal alkanediols, preferably choosing from 2-4 or 8-14 ethylene glycol ether = residues in the molecule.

20

The anionic surfactants contain in the molecule at least one hydrophobic, organic residue and one water-solubilizing anionic group. The hydrophobic residue is mostly an aliphatic hydrocarbon of 8-26, preferably 10-22 and especially 12-18 carbon atoms or an alkyl aromatic residue. having 6-18, preferably 8-16 aliphatic carbon atoms.

As anionic surfactants, e.g. soaps are used of natural or synthetic, preferably saturated fatty acids, optionally also resin acids or naphthenic acids. Suitable synthetic anionic surfactants are those of the sulfonate, sulfate or synthetic carboxylate type.

As surfactants of the sulfonate type, there may be many alkylbenzene sulfonates (C 1-6 alkyl), mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as e.g. obtains those of monoolefins mec 35 terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation product. Also suitable are alkanesulfonates which can be obtained from alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization, e.g. by bisulfite addition to olefins.

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Other usable sulfonate-type ΐε usides are the esters of α-sulfonic fatty acids, e.g. α-sulfonic acids of hydrated methyl or astyl esters of coconut fatty acid, palm kernel fatty acid or tallow fatty acid.

Suitable surfactant surfactants are sulfuric acid monoesters of primary alcohols (e.g., of coconut fatty alcohols, sebum fat alcohols or oleyl = alcohol) and of secondary alcohols. In addition, sulfated fatty acid alkanolamides, fatty acid monoglycerides or reaction products of 1-4 moles of ethylene oxide with primary or secondary fatty alcohols or alkyl phenols are suitable.

10

Other suitable anionic surfactants are the fatty acid esters, or the amides of hydroxy or aminocarboxylic acids or sulfonic acids, such as fatty acid sarcosides, glycolates, lactates, taurides or ice-etionates.

15

The foaming ability of the surfactants can be increased or decreased by combining suitable surfactant types. A reduction can also be obtained by the addition of non-surfactant-like organic substances.

2o reduced foaming ability, which is desirable when working in machines, is often achieved by combining different surfactant types, e.g. of sulfates and / or sulfonates with non-ionic substances and / or with soap. With soaps, the foam attenuation increases with the saturation rate and C-number in the fatty acid residue. Soaps of the saturated C2 24 fatty acids are particularly suitable for this purpose, as foams.

Since the non-surfactant-like foam inhibitors include ΪΓ-alkylated amino triazines which optionally contain chlorine, which are obtained by reacting 1 mole of cyanuric chloride with 2-3 moles of a mono- and / or dialkylamine with 16-20, preferably 8 -18 carbon atoms in the alkyl residue. Similarly, propoxylated and / or butoxylated aminotriazines, e.g. products obtained by adding 5-10 moles of propylene oxide to 1 mole of melamine and further adding 10-50 moles of butylene oxide to this propylene oxide derivative.

35

Also suitable as non-surfactant-like foam inhibitors are water-insoluble organic compounds such as paraffins or halogen paraffins having melting points below 100 ° C, aliphatic C ^-CAQ ketones, and aliphatic carboxylic acid esters, as optionally in the acid residue or the alcohol residue.

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1 1 or both of these residues also contain at least 18 carbon atoms (e.g., triglycerides or fatty acid fatty alcohol esters). In particular, they can be used to cushion the foam by combinations of sulphate and / or sulfonate type surfactants with soaps. Alkali-stable silicones 5 have also been shown to be useful for dampening the foam.

As the building materials, slightly acidic, neutral and alkaline reacting, inorganic or organic salts are suitable.

According to the invention, usable, weakly acidic, neutral or alkaline reacting salts are e.g. dicarbonates, carbonates, borates or silicates of alkalis, alkali sulfates and alkali salts of organic, non-capillary active sulfonic acids, carbonic acids or sulfocarboxylic acids containing 1-8 carbon atoms. For this, e.g. water-soluble salts of benzolsulfonic acid, toluolsulfonic acid or xylolsulfonic acid, water-soluble salts of sulfoacetic acid, sulfobenzoic acid or sulfodicarbon = acids.

The compounds previously mentioned as complexing agents or precipitating agents for calcium are useful as building agents. Therefore, they may be present in the compositions of the invention also in greater quantities than are necessary to fulfill their function as complexing agents or calcium precipitants.

The constituents of the products which are preferably used as textile detergents or as busbolding detergents, especially the building materials, are selected mostly so that the compositions react neutrally to strongly alkaline, so that the pH of an Ifo solution of the composition for the most are in the range of 7 to 12. Pin-3C detergents are mostly neutral to slightly alkaline reaction (pH7-9 »5), while additives, prewashes and boiling detergents are more strongly alkaline (pH 9.5 -12, preferably 10-11.5). If, for special purification purposes, higher pH values are desired, these can be adjusted using alkali silicates with suitable ÏTa20: SiO2 precursors or etching alkalis.

Among the compounds which serve as bleaching agents which give H2 O2 in water, sodium perborate tetrahydrate (BaBO2, H2O2, 3H2O) and monohydrate (NaBO2, H2O2) are of particular importance. But also other borates, 12

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that give ïï202 are useful, e.g. perboraks. Νε, Β ^ Ογ, 4 H2 O. Some compounds may be replaced in whole or in part by other active oxygen carriers, especially by peroxyhydrates such as peroxycarbonates (Na 2 CO 2, 1.5 H 2 O 2), peroxypyrophosphates, citrate perhydrates, urea H 2 O 2 compounds or melamine H 2 compounds, as well as of persure salts which give H 2 O 2, e.g. caroates (KHS0-), perbenzoates or peroxy = phthalates.

It is convenient to incorporate water-soluble and / or water-insoluble stabilizers for the peroxide compounds together with these in amounts of 0.25-10 wt. As water-insoluble stabilizers, e.g. , 1-8, preferably 2-7% by weight of the total composition, are suitable magnesium silicates Mg0: SiO2 = 4: 1 to 1: 4, preferably 2: 1 to 1: 2 and especially 1: 1, as for the most are obtained by precipitating aqueous solutions. Instead, other alkaline earth metal silicates, cadmium silicates or tin silicates of similar composition may be used. Water-containing oxides of tin are also suitable as stabilizers. Water-soluble stabilizers which may be present with vana-insoluble are organic complexing agents, if the amount may be 0.25-5, preferably 0.5-2.5% by weight of the total composition.

In order to achieve a satisfactory bleaching effect on washing already at temeratars below SO ° C, especially in the range 60-40 ° C, activator-containing bleaching components are preferably incorporated into the compositions.

25

As activators for per-compounds which give H 2 O 2 in water, certain F-aeyl, O-acyl compounds, which with this H 2 O 2, form organic peracids, especially acetyl, propionyl or benzoyl compounds as well as carbonic or pyrocarbon esters, serve. Useful connections include 30 F-diacylated and F, F'-tetraacylated amines, e.g. F, F, F ', F'-tetraacetylmethylenediamine or ethylenediamine, F, F-diacetylaniline and F, F-diacetyl-p-toluidine or 1,3-diacylated hydantoins, alkyl-F-sulfonylcarbonamides - e.g. F-methyl-F-mesylacetamide, F-methyl-F-mesyl = benzamide, F-methyl-F-mesyl-p-nitrobenzamide and F-methyl-F-mesyl-p-methoxysbenzamide, F-acylated cyclic hydrazides , acylated triazoles or urazoles, e.g. monoacetylmaleic acid hydrazide, 0, F, F-trisubstituted hydroxylamines such as e.g. 0-benzoyl-F, F-succinylhydroxylamine, 0-acetyl-F, F-succinylhydroxylamine, 0-p-methoxybenzoyl-F, F-succinyl = iohydroxylamine, 0-p-nitrobenzoyl-F, F-succinylhydroxylamine and 0, F, F- 13

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triacetyl hydroxylamine, II, N'-diacylsulfurylamide such as N, N'-dimethyl-N, N'-diacetylsulfurylamide and N, N * -diethyl-Ν, ΙΤ'-dipropionylsulfurylamide, triacylcyanurates such as triacetyl or tribenzoyl cyanurate; benzoic anhydride, m-chlorobenzoic anhydride, phthalic anhydride, 4-chlorophthalic anhydride, sugar esters such as glucose pentaacetate, 1,3-diacyl-4,5-diacyloxyimidazolidines, e.g.

the compounds 1,3-diformyl-4,5-diacetoxyimidazolidine, 1,3-diacetyl-4,5-diacetoxyimidazolidine, 1,3-diacetyl-4,5-dipropionyloxyimidazolidine, acylated glycoluriles such as e.g. tetrapropionylglycoluril or diacetyl dibenzoylglycoluril, diacylated 2,5-diketopiperazines such as e.g. 1,4-diacetyl-2,5-diketopiperazine, 1,4-dipropionyl-2,5-diketopiperazine, 1,4-dipropionyl-3,6-dimethyl-2,5-diketopiperazine, acetylation products or benzoylation products of propylendinrin = substance eg. 2,2-dimethylpropylenediurea (2,4,6,8-tetraazabicyclo (3.3, 1) -nonane-3,7-dione or its 9,9-dimethyl derivative), sodium salts of p- (ethoxycarbonyloxy) -benzoic acid and p- (propoksykarbonyloksy) zolsulfonsyre-legs.

The active chlorine compounds used as bleach may be inorganic or organic in nature.

In the inorganic active chlorine compounds, alkali hypochlorites, which can be used especially in the form of their mixture salts, e.g. bonding compounds to orthophosphates or to condensed phosphates 25, e.g. for pyro- and polyphosphates or for alkali silicates. If the detergents and detergents contain monopersulfates and chlorides, active chlorine is formed in aqueous solution.

In particular, as organic active chlorine compounds, JJ-30 chlorine compounds may be particularly useful in which one or more chlorine atoms are attached to a nitrogen atom, preferably the third valence of the nitrogen atom leading to a negative group, especially to a CO or SO 2 group. . To these compounds are boron dichloro and trichloro cyanuric acid or their salts, chlorinated alkyl guanides or alkyl biguanides, chlorinated hydantoins and chlorinated melamine.

Further, in the compositions of the invention, there may be dirt carriers which bounce the dirt particles released from the taverns suspended in the float, thereby preventing germination. Suitable for water-soluble 1 4

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collides which are mostly organic in nature, e.g. the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carbonic or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. In addition, soluble starch preparations and other than the above starch products such as e.g. degraded starch, aldehyde starch, etc. Polyvinylpyrrolidone is also useful.

Enzyme preparations to be used are mostly a mixture of 10 enzymes of different effect, e.g. of proteases, carbohydrases, esterases, lipases, oxidoreductases, catalases, peroxidases, ureases, isomerases, lyases, transferases, desmolases or nucleases.

Of particular interest are the enzymes derived from bacterial strains or fungi such as Ba-cillus subtilis or Streptomyces griseus, especially proteases or amylases, which are resistant to alkali, per-compounds and anionic surfactants and are still effective at temperatures up to 70 ° C.

Enzyme preparations are mostly marketed by the manufacturers as 20 aqueous solutions of the active substances or as powders, granules or cold-fueled products. They often contain as a diluent sodium sulfate, sodium chloride, alkali chloro, pyro or polyphosphates, especially tripolyphosphate. Particular attention is paid to stiff-free preparations. They are known in a manner known per se by incorporation 25 of oily or paste-shaped, nonionic substances or by granulation by means of the melting of crystalline salts in their own crystal water.

Enzymes specific to a particular species of debris may be incorporated, e.g. proteases or amylases or lipases. In principle, combinations of enzymes with different effects are used, in particular combinations of proteases and amylases.

The detergents may contain, as optical cleaners for cotton, 35 derivatives of diaminostilbendisulfonic acid or its alkali metal salts. Suitable are e.g. salts of 4,4'-bis (2-anilino-4 * morpholino-1,3,5-triazin-6-ylamino) -stylbenz-2,2'-disulfonic acid or compounds similarly constructed, as instead for the morpholine group carries a diethylamino group, a methylamino group or a 2-methoxyethylamino group.

1 5

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As a clarifier for polyamide taps, there may be Hai cm such as 1,3-diaryl-2-pyrazolines, e.g. the compound 1- (p-sulfamoylphenyl) -3- (p-chlorophenyl) -2-pyrazoline as well as compounds built in a similar manner, which instead of the sulfamoyl group carries e.g. methoxycarbonyl, 2-methoxyethoxycarbonyl, acetylamino or vinylisulfonyl group. Further useful polyamide clarifiers are the substituted amino coumarins e.g. 4-methyl-7-dimethylamino- or 4-methyl-7-diethyl-aminocoumarin. Furthermore, as polyamide clarifiers, the compounds 1- (2-benzimidazolyl) -2- (1-hydroxyethyl-2-benzimidazolyl) -ethylene and 1-ethyl-3-phenyl-7-diethylamino-carbostyril can be used. The compounds suitable for polyester tavern and polyamide tavern are the compounds 2,5-di- (2-benzoxazolyl) -thiophene, 2- (2-benzoxazolyl) -naphtho / 2,3-b7-thiophene and 1,2-di- ( 5-methyl-2-benzoksazolyl) -ætylen. Furthermore, there may be clarifiers of the type substituted 4,4'-distyryldiphenyl, e.g.

The compound 4,4, -bis (4-chloro-3-sulfostyryl) -diphenyl. Mixtures of the aforesaid clarifiers may also be used.

Of particular practical interest, according to the invention are agents of powdered or granular nature which can be prepared by any of the methods known in the art.

The invention also relates to a process for the preparation of the agent. It is the property of the characteristic of claim 22! specified.

Thus, e.g. the powdered aluminum silicates are simply mixed with the other components of the detergent, with oily or paste-shaped products such as non-ionic substances are sprayed onto the powder. Another manufacturing option consists in incorporating the powdered aluminum silicate into the others as a coarse constituent of the agent which is then converted into a powder by crystallization or by drying the water in the heat. After heat drying e.g. Heat-sensitive and moisture-sensitive components such as e.g. bleaching components and activators for these, enzymes, antimicrobials, etc.

3 5

The production of the aluminum silicates used and the determination of the potassium bonding capacity are described in the main patent. The water content was determined by heating the product to 800 ° C for 1 hour.

16

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All percentages are percentages by weight, as far as aluminum silicates are concerned with the anhydrous active substance (= AS).

In the following, some useful aluminum according to the invention is mentioned. silicates: I: 0.9 Na 2 O, 1 Al 2 O 3, 2.04 SiO 2, 4.3 H 2 O (= 21.6% H 2 O)

fully crystalline calcium binding capacity: 150 mg CaO / g AS

10a: 0.9 Na 2 O, 1 Al 2 O 5> 2.04 SiO 2, 2.0 H 2 O (= 11.4% H 2 O) II: 0.8 Na 2 O, 1 AlGO 2, 2.655 SiO 2, 5.2 H 2 O fully crystalline

calcium binding capacity: 120 mg CaO / g AS

Ha: 0.8 lia2, 1 Al2, 2.65 SiO2, 0.2 H2O2 III: 0.9 Na2O, 1 Al2203, 2.04 SiO2, 47 H2 O

calcium binding capacity: 160 mg CaO / g AS

25 V: 1.5 lia220, 1A1203, 2 SiO2, 3H2O (= 14.4% HgO) X-ray amorphous

calcium binding capacity: 140 mg CaO / g AS

VI: 0.9 Na 2 O, 1 Al 2 O 3, 2.04 SiO 2, 6.7 H 2 O (= 6% H 2 O) X-ray amorphous

calcium binding capacity: 145 mg CaO / g AS

VII: 1 Na 2 O, 1 Al 2, 2 SiO 2, 1 HgO (= 6% H 2 O) X-ray amorphous

calcium binding capacity: 150 mg CaO / g AS

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VIII: 0.8 Na 2 O, 1 Al 2 O 3, 2.65 SiO 2, 4 H

calcium binding capacity: 60 ng CaO / g AS

IX: 1 Na 2 O, 1 Al 2, 1 SiO 2, 1.4 H 2 O X-ray amorphous

calcium binding capacity: 120 mg CaO / g AS

10 X: 1 Na 2 O, 1 Al 2 O 3, 5 SiO 2, 2.8 H 2 O X-ray

calcium binding capacity: 100 mg CaO / g AS

XI: approx. 1 Na 2 O, 1 AlgO 2, 6 SiO 2, 3.2 H 2 O X-ray amorphous

calcium binding capacity: 60 mg CaO / g AS

XII: 0.9 Nsl 2 O, 1 Α 1 £ 03, 2 SiO 2, 3 Η £ 0 (= 11 ^ H 2 O) 20 fully crystalline

calcium binding capacity: 160 mg CaO / g AS

XIII: 0.28 Na 2 O, 0.62 K 2 O, 1 Al 2, 2.04 SiO 2, 4.3 H 2 O fully crystalline

calcium binding capacity: 170 mg CaO / g AS

XIV: 1.5 Na 2 O, 1 AlgO 2, 2 SiO 2, x H 2 O

rontgenamorph 30

calcium binding capacity: 120 mg CaO / g AS

XV: 1.5 ffa 2 O, 1 Al 2, 2 SiO 2

Calcium binding capacity: 170 mg CaO / g AS

XVI: 1} 5 Na2Q, 1 Bz ° y 2 SiO2, 1.5 µ20

predominantly crystalline calcium binding capacity: 120 mg CaO / g AS

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XVII: 0.92 Ha 2 O, 1 Al 2 O 3, 1.8 SiO 2, 3.71 H 2 O fully crystalline calcium binding capacity: 180 mg CaO / g AS.

The salt-containing components, salt-like surfactants, other organic salts and inorganic salts contained in the detergents in the examples are provided as sodium salts, unless otherwise expressly stated. The terms or abbreviations used mean: 10 "A3S" the salt of a benzene and sulphonation of the resulting alkylbenzene, alkylbenzene = sulfonic acid having 10-15, preferably 11-13 carbon atoms in the alkyl chain, when condensed by straight chain olefins.

"Alkanesulfonate" means one of paraffins having 11 to 15 carbon atoms by sulfoalkylation produced sulfonate.

"HSt-sulfonate" means a sulfonate made of hydrated tallow fatty acid methyl ester by sulfonation with SO 2.

"Olefin sulfonate" means a sulfonate obtained from α-olefin mixtures of 15-18 carbon atoms by sulfonation with SO 2 and hydrolyzing the sulfonation product with lye, which sulfonate consists essentially of alkenesulfonate and hydroxyalkanesulfonate, but which also contains low amounts of disulfonates.

"Soap" contains as a fatty acid component a cured mixture of equal parts by weight of tallow fatty acid and rapeseed oil fatty acid (^ i5 "C22 ^" "OA + x ÆO" or "TA + x ÆO" or "ΣΑ + x ÆO" or "SA + x ÆO" 30 or "0X0 + x EO" means ethylene oxide (EO) preparation products for a technical oleyl alcohol (OA) or a tallow fatty alcohol (iodine number = 0.5) or for a coconut fatty alcohol (EA) or for a secondary aliphatic (SA) or to a C12-

Cig-alcohol (0X0), the numeral for x showing the molar amount of ethylene oxide stored at 1 mole of alcohol.

The "CTMS" salt of O-carboxymethyl tartronic acid.

"EDTA" salt of ethylenediaminetetraacetic acid.

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The "HEDP" salt of 1-hydroxyethane-1,1-diphosphonic acid.

The "DMDP" salt of dimethylaminomethane diphosphonic acid.

5 "CMC" salt of carboxymethyl cellulose.

The polygonal table contains recipes for some detergents according to the invention, the recipes 1, 2 and 3 being fully air-washable household, industrial and industrial detergents for washing variegated and lifeless textiles at temperatures of 40-100 ° C, preferably 50-100 ° C. The two products according to prescriptions 4 and 5 are intended for commercial and industrial laundries, the former being used for pre-washing and the latter for main washing.

15 1 »component in detergent according to Ex.

Component 1 2 3 4 5 TA + 14 ÆO 3.8 6.5 5.0 - 9.6 TA + 5 ÆO 2.2 3.5 - - 4.4 20 KA + 3 ÆO - _ 2.5 SA + 9 ÆO - _ _ 4.5 SA + 3 ÆO - - _ i, 8 ABS 7.0 25 OS 3.5 HSt sulfonate - 2.5 -

Alkanesulfonate - 3.0 Soap 3.4 3.0 2.0 30

SkuminMbitor - 0.8 - 0.6

Aluminum Silicate I 20.0 - - - _

Aluminum Silicate V - 30.0 Aluminum Silicate VII - 25.0

Aluminum silicate XII - - _ 28.0

Aluminum Silicate XVII - 40.0 ,035P3010 10 ’° - 7» CMTS - 8.0 - 7.5 10.0

DK 156173B

EDTA 0.3 0.3 5 ffa 2 O, 3.3 SiO 2 5.0 5.0 5.5 4.5 4.5 5.0

Na2CO3 - - - 7.0 8.5

IiaB02, H2 O, 3 H2 O 28.5 25.0 28.5

Na2 SO4 0.5 5.1 4.9 29.5 '9.3 MgSiO3 2.0. 2.0 4.0 CMC 1.5 1.6 1.6 1.8 1.5 H 2 O EDTA can be replaced by the same amount of HEDP or DMDP, and Na P-free phosphate substitute soin e.g. salts of citric acid or O-carboxymethyl tartronic acid.

Example 6 A detergent for washing heavily soiled workwear determined the following:

10.0% OA + 10 ÆO

8.0% OA + 5EO 25 45.0% Ua2CO3

22.0% Aluminum Silicate Y 5.5% Na Citrate 1.3% CMC

30 s, 3% H2 O;

EXAMPLE 7 A detergent composed of the following composition is used for washing in particularly hard water:

6.7% 0X0 + 10 ÆO 4.0% 0X0 + 4 ÆO

C / Λ Αλτ A T «« «µ 4 · ν * ^« <î Λ «ί Vrt + TTT T

Claims (22)

1. In the method of washing according to Patent No. 151,231 the change that the aqueous treatment float for the textiles contains a surfactant component of 1 part by weight nonionic and 0-3 parts by weight of anionic surfactants, the nonionic surfactants being a mixture of different high ethocylated compounds having an aliphatic hydrocarbon interest of 10-18 2® carbon atoms in which, by weight, non-ionic compounds having 8-20 ethylene glycol residues in the molecule, 0.2-2 parts by weight of compounds having 2 6 ethylene glycol residues in the molecule. Process according to claim 1, characterized in that the suspended compounds used according to claim 1 have a calcium binding capacity of up to 200 mg CaO / g of active substance. Process according to claim log2, characterized in that the suspended compounds, optionally containing bound water and used according to claim 1, have the composition 0.7-1.1 (Cat220), Al2O3, 1.3-2, 4 SiO2 and a calcium binding capacity of 100-200 mg CaO / g of active substance. S2 DK 156173 A process according to claims 1-3, characterized in that the suspended compounds as cations contain hydrogen, sodium, lithium, potassium, ammonium, magnium or water-soluble organic bases. Method according to claims 1-4, characterized in that the suspended compounds carried a primary particle size of 0.1-100 μ, preferably 1-50 μ. Process according to claim 3, characterized in that the treatment float further contains solutes which can complexly bind calcium and / or precipitate calcium. Process according to claim 6, characterized in that, as complexing agents or precipitating agents for calcium, compounds of the meta and polyphosphates type and of the following organic acids or their salts are used: polycarboxylic acids, hydroxycarboxylic acids, aminocarboxylic acids, carboxyalkylacetes, polyanionic acylters, polyanionic acids carbonic and phosphonic acids. Process according to claims 6 and 7, characterized in that complexing agents or calcium precipitants are used at concentrations of 0.2-2 g / l. Process according to claims 1-8, characterized in that the surfactant component of claim 1 is present in concentrations of 0.3-3 g / l. Process according to claims 1-9, characterized in that the raft contains additional inorganic or organic-building substances in quantities up to 6 g / l. Process according to claims 1-10, characterized in that the float further contains per-compounds in amounts of up to 0.4 g / l of active oxygen and optionally stabilizers and / or activators 2g for the per-compounds. Process according to claims 1 to 11, characterized in that the raft further contains active chlorine compounds equivalent to 0.4 g / l of active oxygen. 23 DK 156173 B Process according to claims 1-12, characterized by a content of inorganic and / or organic phosphorus compounds in such quantities that the phosphorus content of the treatment fleet does not exceed 0.6 g / Ί, preferably 0.3 g / l. A composition according to claim 151,231 for carrying out the method according to claims 1-13, a content of finely divided substances which can bind the hardness of the water according to claims 1-5, characterized in that it contains a surfactant component as defined in claim 1. An agent according to claim 14, characterized by a content of a surfactant component as defined in claim 1 in amounts of 3-40% by weight. 16. A composition according to claims 14 and 15, characterized in that it contains the aluminum silicates as defined in claims 1-5 in amounts of 15 to 95, preferably 15 to 60% by weight. Agent according to claims 14-16, characterized in that it further contains complexing agents or precipitating agents for calcium as claimed in claims 6 and 7 in amounts of 2-15 wt. 20 18. Agent according to claims 14-17, characterized in that it contains, as further washing or purifying compounds, building substances in amounts of 5-60% by weight. 19. An agent according to claims 14-18, characterized in that it contains, as bleaching compounds, further active oxygen compounds in amounts of 10-14% by weight and optionally stabilizers or activators for the active oxygen compounds. An agent according to claims 14-19, characterized in that its composition is within the following prescription: 3-30% by weight of surfactant components according to claim 1 15-60% by weight of aluminum silicates as defined in claims 1-5 (calculated 35 on active substance) 2 -45, preferably 2-15 wt.% Complexing agents for calcium 0-50 wt.% Washing alkali not suitable for complexing 0-50 wt., Bleaches and other additives present only in low-textile detergents. DK 156173 B 21. Agent according to claims 14-20, characterized by a content of organic and / or inorganic phosphorus compounds in such quantities that the total "P content" of the medium does not exceed 6% by weight and preferably 3% by weight. ''. A method of preparing agents according to claims 14-21. characterized in that the powdered aluminum aliquots used according to claims 1 to 5 are mixed with the other ingredients dispensed. 10 15 20 25 30 35