DE10002008A1 - Preparation of a tablet dispersing agent for detergent tablets, comprises compacting swellable materials at specific pressure - Google Patents

Abstract

Preparation of a tablet dispersing agent comprises compacting swellable materials at 50-100,000 bar such that the particle size is below 0.1 mm.

Description

Field of the Invention

The invention is in the field of molded detergents and relates to an improved one Process for the production of tablet disintegrants.

State of the art

The term explosives or disintegrants is to be understood as meaning substances which are added to the shaped bodies in order to accelerate their disintegration when they come into contact with water. Overviews can be found e.g. B. in J. Pharm. Sci. 61 (1972), Römpp Chemilexikon, 9th edition, volume 6, p. 4440 and Voigt "Textbook of pharmaceutical technology" (6th edition, 1987, p. 182-184). These substances increase their volume when water enters, whereby on the one hand the own volume increases (swelling), on the other hand a pressure can be generated by the release of gases, which causes the tablet to disintegrate into smaller particles. Crosslinked polyvinylpyrrolidone (PVP) or microcrystalline cellulose are examples of suitable disintegrants, which are used in a variety of ways, particularly in pharmacy. In order to develop a sufficient explosive effect, ie the rate of dissolution, the disintegrants must first be compacted and usually added to the moldings in comparatively large amounts up to 25% by weight. While this is hardly a problem in the field of pharmacy, such high concentrations cannot be tolerated for use in detergent tablets, since the disintegrants make no contribution to the washing process.

The object of the present invention was therefore to provide new explosives for the one To be provided in detergent tablets, which are different from commercially available products through an improved disintegration effect, d. H. through an increased dissolution speed of the mark the correspondingly manufactured molded article.  

Description of the invention

The invention relates to a method for producing tablet disintegrants, in which swellable substances compacted at pressures in the range of 50 to 100,000 bar and so obtained compacts then crushed in a conventional manner, the majority Proportion of the comminuted material has a particle size below 0.1 mm.

Surprisingly, it was found that those obtained by the process of the invention Chen explosives compared to conventional comparative products, in which the compression by Granulation or roller compaction takes place, characterized by an improved explosive effect, d. H. With the new process products, it is possible to use the same amount of detergent tablets have a higher dissolution rate or the same dissolution rate with reduced Get the amount used.

Explosives

Suitable swelling disintegration aids are, for example, synthetic polymers such as polyvinyl pyrrolidone (PVP) or polyacrylates or natural polymers or modified natural products such as cellulose and starch and their derivatives, alginates or casein derivatives. Disintegrants based on PVP or cellulose are used as preferred disintegrants in the context of the present invention. Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and, formally speaking, is a β-1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxyl hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses. The celulose derivatives mentioned are preferably not used alone as a disintegrant based on cellulose, but rather used in a mixture with cellulose. The content of cellulose derivatives in these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose which is free of cellulose derivatives is particularly preferably used as a disintegrant based on cellulose. As a further disintegration agent based on cellulose or as a component of this component, microcrystalline cellulose can be used. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which only attack and completely dissolve the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses, but leave the crystalline areas (approx. 70%) undamaged. Subsequent disaggregation of the microfine celluloses produced by the hydrolysis provides the microcrystalline celluloses, which have primary particle sizes of approximately 5 μm. Other explosives that may be present in the sense of the invention, such as. B. Kollidon, alginic acid and their alkali metal salts, amorphous or also partially crystalline layered silicates (bentonites), polyacrylates, polyethylene glycols are for example the publications WO 98/40462 (Rettenmaier), WO 98/55583 and WO 98/55590 (Unilever) and WO 98 / 40463, DE 197 09 991 and DE 197 10 254 (Henkel). Reference is expressly made to the teaching of these writings.

The disintegrants obtainable by the process according to the invention can be macro in the shaped body Viewed from a scopic point of view, they are homogeneously distributed, but from a microscopic point of view they form manufacturing causes zones of increased concentration. The detergent tablets can contain the disintegrants in quantities from 0.1 to 25, preferably 1 to 20 and in particular 5 to 15% by weight, based on the moldings per included.

Compacting and shredding

The compacting of the swellable substances can be done in common presses, such as. B. screw presses, hydraulic presses, eccentric presses or rotary presses at pressures in the range of 50 up to 100,000, preferably 100 to 10,000 and in particular 1,000 to 5,000 bar. To one to ensure optimal mixing with the other components of the detergent tablets, emp it is necessary to adjust the granulometry of the disintegrant according to the granulation of the tablet Adjust premix. To crush the material to be pressed come the known methods of State of the art. The comminuted material is preferably sieved and a good grain Fraction in the range between 0.1 and 2, preferably 0.2 and 1.5 and in particular 0.4 and 1 mm decreased.

Industrial applicability

The disintegrants produced using the process according to the invention are obtained Chen detergent tablets can be used for cleaning fibers and textiles Contain additives, such as. B. surfactants, builders, defoamers, graying inhibitors, optical on brighter, polymers, perfumes and the like.  

Anionic surfactants

The detergent tablets can be anionic, nonionic, cationic, amphoteric and / or zwitterio African surfactants contain, but anionic surfactants or combinations of are preferred anionic and nonionic surfactants used. Typical examples of anionic surfactants are Soaps, alkyl benzene sulfonates, alkane sulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfo nate, α-methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, fatty alcohol ether sulfates, glycerol ether sulfa te, hydroxy mixed ether sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, mono- and dial kylsulfosuccinate, mono- and dialkylsulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acid ren and their salts, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, N-acylamino acids such as acyl lactylates, acyl tartrates, acyl glutamates and acyl aspartates, alkyl oligogluco sidsulfate, protein fatty acid condensates (especially vegetable products based on wheat) and Al kyl (ether) phosphates. If the anionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow homolog distribution. Preferential alkylbenzene sulfonates, alkyl sulfates, alkyl ether sulfates, alkane sulfonates, olefin sulfonates, Methyl ester sulfonates, monoglyceride (ether) sulfates and alkali soaps and mixtures thereof are used.

Preferred alkylbenzenesulfonates preferably follow the formula (I)

R ¹ -Ph-SO ₃ X (I)

in which R ^{1 is} a branched but preferably linear alkyl radical having 10 to 18 carbon atoms, Ph is a phenyl radical and X is an alkali metal and / or alkaline earth metal, ammonium, alkyl ammonium, alkanolammonium or glucammonium. Of these, dode cylbenzenesulfonates, tetradecylbenzenesulfonates, hexadecylbenzenesulfonates and their technical mixtures in the form of the sodium salts are particularly suitable.

Alkyl and / or alkenyl (ether) sulfates, which are also referred to as fatty alcohol (ether) or oxo alcohol (ether) sulfates depending on the raw material base, include the sulfation products of primary and / or secondary alcohols or of alkylene oxide adducts with these alcohols understand, which preferably follow the formula (II),

R ² O (CH ₂ CHR ³ O) _a -SO ₃ X (II)

in which R ^{2 is} a linear or branched, aliphatic alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms, R ^{3 is} hydrogen or a methyl group, a is 0 or numbers from 1 to 0, preferably 2 to 10 and X represents an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium. Typical examples of alkyl sulfates that can be used in the context of the invention are the sulfation products of capron alcohol, caprylic alcohol, capric alcohol, 2-ethylhexyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, arylselyl alcohol, elaidyl alcohol Gadoleyl alcohol, behenyl alcohol and erucyl alcohol and their technical mixtures, which are obtained by high pressure hydrogenation of technical methyl ester fractions or aldehydes from Roelen's oxosynthesis. Typical examples of alkyl ether sulfates are the sulfation products of addition products with an average of 1 to 20 and preferably 2 to 10 moles of ethylene and / or propylene oxide onto the abovementioned alcohols. The sulfation products - ie both the sulfated alcohols and the sulfated alcohol polyglycol ethers - can preferably be used in the form of their alkali metal salts and in particular their sodium salts. Alkyl (ether) sulfates based on C _16/18 tallow fatty alcohols or vegetable fatty alcohols of comparable C chain distribution in the form of their sodium salts are particularly preferred. In the case of branched primary alcohols are oxo alcohols, such as those used for. B. are accessible by reaction of carbon monoxide and hydrogen to alpha permanent olefins by the shop process. Such alcohol mixtures are commercially available under the trade names Dobanol® or Neodol®. Suitable alcohol mixtures are Dobanol 91®, 23®, 25®, 45®. Another possibility are oxo alcohols, such as those obtained by the addition of carbon monoxide and hydrogen to olefins after the classic Enichema or Condea oxo process. These alcohol mixtures are a mixture of strongly branched alcohols. Such alcohol mixtures are commercially available under the trade name Lial®. Suitable alcohol mixtures are Lial 91®, 111®, 123®, 125®, 145®.

Monoglyceride sulfates and monoglyceride ether sulfates are known anionic surfactants which can be obtained by the relevant methods of preparative organic chemistry. The usual starting point for their preparation is triglycerides which, if appropriate, are transesterified to the monoglycerides after ethoxylation and subsequently sulfated and neutralized. It is also possible to implement the partial glycerides with suitable sulfating agents, preferably gaseous sulfur trioxide or chlorosulfonic acid. If desired, the neutralized substances can be subjected to ultrafiltration in order to reduce the electrolyte content to a desired level. The monoglyceride (ether) sulfates to be used in accordance with the invention preferably follow the formula (III)

in the R ⁴ CO for a linear or branched acyl radical having 6 to 22 carbon atoms, R5 for hydrogen or a methyl group, R ⁶ for hydrogen or R ⁴ CO, b1, b2 and b3 in total for 0 or for numbers from 1 to 30 , preferably 2 to 10, and X represents an alkali or alkaline earth metal. Typical examples of suitable within the meaning of the invention, monoglyceride (ether) sulfates are the Umsetzungspro-products of lauric acid, coconut fatty, palmitic acid, stearic acid monoglyceride, oleic acid monoglyceride and tallow fatty and their Ethylenoxidad-products with sulfur trioxide or chlorosulfonic acid in the form of their sodium salts. Monoglyceride sulfates of the formula (III) are preferably used in which R ⁴ CO is a linear acyl radical having 8 to 18 carbon atoms and R ^{6 is} R ⁴ CO.

Finally, alkali soaps are to be understood as meaning fatty acid salts of the formula (IV)

R ⁷ CO-OX (IV)

in which R ⁷ CO represents a linear or branched, saturated or unsaturated acyl radical having 6 to 22 and preferably 12 to 18 carbon atoms and again X stands for alkali and / or alkaline earth metal, ammonium, alkylammonium or alkanolammonium. Typical examples are the sodium, potassium, magnesium, ammonium and triethanolammonium salts of caproic acid, caprylic acid, 2-ethyl hexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaoleic acid, petol acid, linoleic acid, linoleic acid , Linolenic acid, Elaeo stearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures. Coconut or palm kernel fatty acid is preferably used in the form of its sodium or potassium salts.

Nonionic surfactants

Typical examples of nonionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycols ether, fatty acid polyglycol ester, fatty acid amide polyglycol ether, fatty amine polyglycol ether, alkoxylated Triglycerides, mixed ethers or mixed formals, alk (en) yl oligoglycosides, fatty acid N-alkyl glucamides, Pro tein hydrolyzates (especially vegetable products based on wheat), polyol fatty acid esters, sugars esters, sorbitan esters, polysorbates and amine oxides. If the nonionic surfactants polyglycol ether ket ten contained, these can be a conventional, but preferably a narrowed homolog have distribution. Fatty alcohol polyglycol ethers, alkoxylated fatty acids are preferred alkyl esters, alkyl oligoglucosides and / or fatty acid N-alkyl polyhydroxyalkylamides.

The preferred fatty alcohol polyglycol ethers follow the formula (V)

R ⁸ O (CH ₂ CHR ⁹ O) _n1 H (V)

in which R ^{8 represents} a linear or branched alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms, R ^{9 represents} hydrogen or methyl and n1 represents numbers from 1 to 20. Typical examples are the addition products of an average of 1 to 20 and preferably 5 to 10 moles of ethylene and / or propylene oxide onto capro alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostyl alcohol , Elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures. Addition products of 3, 5 or 7 moles of ethylene oxide onto technical coconut oil alcohols are particularly preferred.

Suitable alkoxylated fatty acid lower alkyl esters are surfactants of the formula (VI)

R ¹⁰ CO- (OCH ₂ CHR ¹¹ ) _n2 OR ¹² (VI)

in which R ¹⁰ CO stands for a linear or branched, saturated and / or unsaturated acyl radical with 6 to 22 carbon atoms, R ¹¹ for hydrogen or methyl, R ¹² for linear or branched alkyl radicals with 1 to 4 carbon atoms and n2 for numbers from 1 to 20 stands. Typical examples are the formal insert products of an average of 1 to 20 and preferably 5 to 10 moles of ethylene and / or propylene oxide in the methyl, ethyl, propyl, isopropyl, butyl and tert-butyl esters of caproic acid, calcium acid , 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid and behenic acid and behenic acid and behenic acid. The products are usually prepared by inserting the alkylene oxides into the carbonyl ester bond in the presence of special catalysts, such as, for. B. Calcined hydrotalcite. Reaction products of an average of 5 to 10 moles of ethylene oxide into the ester linkage of technical coconut fatty acid methyl esters are particularly preferred.

Alkyl and alkenyl oligoglycosides, which are also preferred nonionic surfactants, usually follow the formula (VII),

R ¹³ O- [G] _p (VII)

in which R ^{13 represents} an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G represents a sugar radical having 5 or 6 carbon atoms and p represents numbers from 1 to 10. They can be obtained according to the relevant procedures in preparative organic chemistry. As representative of the extensive literature, reference is made here to the documents EP 0301298 A1 and WO 90/03977. The alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose. The preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides. The index number p in the general formula (VII) indicates the degree of oligomerization (DP), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10. While p must always be an integer in a given compound and especially here can assume the values p = 1 to 6, the value p for a certain alkyl oligo glycoside is an analytically determined arithmetic parameter, which usually represents a fractional number. Alkyl and / or alkenyl oligoglycosides with an average degree of oligomerization p of 1.1 to 3.0 are preferably used. From an application point of view, preference is given to alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4. The alkyl or alkenyl radical R ¹³ can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms. Typical examples are butanol, capronic alcohol, capric alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as those obtained in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis. Alkyl oligoglucosides of chain length C ₈ -C ₁₀ (DP = 1 to 3) are preferred, which are obtained as a preliminary step in the separation of technical C ₈ -C ₁₈ coconut fatty alcohol by distillation and with a proportion of less than 6% by weight of C ₁₂ - Alcohol may be contaminated and alkyl oligoglucosides based on technical C _9/11 oxo alcohols (DP = 1 to 3). The alkyl or alkenyl radical R ¹³ can also be derived from primary alcohols having 12 to 22, preferably 12 to 14, carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol and the technical mixtures described above, which can be obtained as well as their technical mixtures. Alkyl oligoglucosides based on hardened C _12/14 coconut alcohol with a DP of 1 to 3 are preferred.

Cationic and amphoteric surfactants

Typical examples of cationic surfactants are, in particular, tetraalkylammonium compounds, such as, for example, dimethyldistearylammonium chloride or hydroxyethyl hydroxycetyldimmonium chloride (Dehyquart E) or esterquats. These are, for example, quaternized fatty acid retriethanolamine ester salts of the formula (VIII),

in which R ¹⁴ CO represents an acyl radical with 6 to 22 carbon atoms, R ¹⁵ and R ¹⁶ independently of one another for hydrogen or R ¹⁴ CO, R ^{15 represents} an alkyl radical with 1 to 4 carbon atoms or a (CH ₂ CH ₂ O) _m4 H- Group, m1, m2 and m3 in total for 0 or numbers from 1 to 12, m4 for numbers from 1 to 12 and Y for halide, alkyl sulfate or alkyl phosphate. Typical examples of ester quats which can be used in the context of the invention are products based on caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, isostearic acid, stearic acid, oleic acid, elaidic acid, arachic acid, behenic acid and erucic acid and their technical mixtures, as they occur, for example, in the pressure splitting of natural fats and oils. Technical C _12/18 coconut _fatty acids and in particular partially hardened C _16/18 tallow or palm fatty acids as well as high elaidic acid C _16/18 fatty acid cuts are preferably used. The fatty acids and the triethanolamine can be used in a molar ratio of 1.1: 1 to 3: 1 to produce the quaternized esters. With regard to the application properties of the ester quats, an application ratio of 1.2: 1 to 2.2: 1, preferably 1.5: 1 to 1.9: 1, has proven to be particularly advantageous. The preferred esterquats are technical mixtures of mono-, di- and triesters with an average degree of esterification of 1.5 to 1.9 and are derived from technical C _16/18 - tallow or palm fatty acid (iodine number 0 to 40 ). From an application point of view, quaternized fatty acid triethanolamine ester salts of the formula (VIII) have proven to be particularly advantageous in which R ¹⁴ CO is an acyl radical having 16 to 18 carbon atoms, R ^{15 is} R ¹⁵ CO, R ^{16 is} hydrogen, R ^{17 is} a methyl group , m1, m2 and m3 for 0 and Y for methyl sulfate.

In addition to the quaternized fatty acid triethanolamine ester salts, quaternized ester salts of fatty acids with diethanolalkylamines of the formula (IX) are also suitable as esterquats.

in which R ¹⁸ CO for an acyl radical with 6 to 22 carbon atoms, R ¹⁹ for hydrogen or R ¹⁸ CO, R ²⁰ and R ²¹ independently of one another for alkyl radicals with 1 to 4 carbon atoms, m5 and m6 in total for 0 or numbers from 1 to 12 and Y again represents halide, alkyl sulfate or alkyl phosphate.

Finally, the quaternized ester salts of fatty acids with 1,2-dihydroxypropyl dialkylamines of the formula (X) should be mentioned as a further group of suitable ester quats,

in which R ²² CO for an acyl radical with 6 to 22 carbon atoms, R ²³ for hydrogen or R ²² CO, R ²⁴ , R ²⁵ and R ²⁶ independently of one another for alkyl radicals with 1 to 4 carbon atoms, m7 and m8 in sum for 0 or Numbers from 1 to 12 and X again represents halide, alkyl sulfate or alkyl phosphate.

Finally, suitable ester quats are substances in which the ester bond is replaced by an amide bond and which preferably follow the formula (XI) based on diethylenetriamine,

in which R ²⁷ CO represents an acyl radical having 6 to 22 carbon atoms, R ^{28 represents} hydrogen or R ²⁷ CO, R ²⁹ and R ³⁰ independently of one another alkyl radicals having 1 to 4 carbon atoms and Y again represents halide, alkyl sulfate or alkyl phosphate. Such amide ester quats are available on the market, for example, under the Incroquat® (Croda) brand.

Examples of suitable amphoteric or zwitterionic surfactants are alkyl betaines, alkyl amido betaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines. Examples of suitable alkyl betaines are the carboxyalkylation products of secondary and in particular tertiary amines which follow the formula (XII)

in which R ³¹ for alkyl and / or alkenyl radicals with 6 to 22 carbon atoms, R ³² for hydrogen or alkyl radicals with 1 to 4 carbon atoms, R ³³ for alkyl radicals with 1 to 4 carbon atoms, q1 for numbers from 1 to 6 and Z for a Alkali and / or alkaline earth metal or ammonium. Typical examples are the carboxymethylation products of hexylmethylamine, hexyldimethylamine, octyldimethylamine, De cyldimethylamin, dodecylmethylamine, dodecyldimethylamine, Dodecylethylmethylamin, C kyldimethylamin _12/14 -Kokosal, myristyldimethylamine, cetyldimethylamine, stearyldimethylamine, Stearylethylmethyl amine, oleyl dimethyl amine, C _16/18 tallow alkyl dimethyl amine and technical mixtures thereof .

Carboxyalkylation products of amidoamines which follow the formula (XIII) are also suitable,

in which R ³⁴ CO for an aliphatic acyl radical having 6 to 22 carbon atoms and 0 or 1 to 3 double bonds, R ³⁵ for hydrogen or alkyl radicals with 1 to 4 carbon atoms, R ³⁶ for alkyl radicals with 1 to 4 carbon atoms, q2 for numbers of 1 to 6, q3 for numbers from 1 to 3 and Z again represents an alkali and / or alkaline earth metal or ammonium. Typical examples are reaction products of fatty acids with 6 to 22 carbon atoms, namely caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, gadoleic acid and arachinic acid, arachinic acid Erucic acid and its technical mixtures, with N, N-dimethylaminoethylamine, N, N-dimethylaminopropylamine, N, N-diethylaminoethylamine and N, N-diethylamino nopropylamine, which are condensed with sodium chloroacetate. It is preferred to use a condensation product of C _8/18 coconut fatty acid N, N-dimethylaminopropylamide with sodium chloroacetate.

Imidazolinium betaines are also suitable. These substances are known substances that can be obtained, for example, by cyclizing condensation of 1 or 2 moles of fatty acid with polyhydric amines such as aminoethylethanolamine (AEEA) or diethylene triamine. The corresponding carboxyalkylation products are mixtures of different open-chain betaines. Typical examples are condensation products of the above-mentioned fatty acids with AEEA, preferably imidazolines based on lauric acid or again C _12/14 coconut fatty acid, which are subsequently betainized with sodium chloroacetate.

Builder

The washing, rinsing, cleaning and finishing agents according to the invention can furthermore additionally che inorganic and organic builder substances, for example in amounts of 10 to 50 and above preferably 15 to 35 wt .-% - based on the agent - contain, as an inorganic builder punch mainly zeolites crystalline layered silicates, amorphous silicates and - if permitted - also Phosphates, e.g. B. tripolyphosphate are used. The amount of co-builder is based on that allowance for preferred amounts of phosphates.

The fine crystalline, synthetic and bound water-containing zeolite which is frequently used as a detergent builder is preferably zeolite A and / or P. As zeolite P, for example, zeolite MAP ^(R) (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and / or P and Y are also suitable. Of particular interest is also a cocrystallized sodium / potassium aluminum silicate composed of zeolite A and zeolite X, which as VEGOBOND AX® (commercial product from Condea Augusta S. p. A.) is commercially available. The zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture. In the event that the zeolite is used as a suspension, it may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C ₁₂ -C ₁₈ fatty alcohols with 2 to 5 ethylene oxide groups , C ₁₂ -C ₁₄ fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula NaMSi _x O _{2x + 1} . yH ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and are preferred values for x 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application EP 0164514 A1. Preferred crystalline layered silicates of the formula given are those in which M is sodium and x is 2 or 3. In particular, both β- and δ-sodium disilicate are Na ₂ Si ₂ O ₅ . yH ₂ O is preferred, β-sodium disilicate being able to be obtained, for example, by the process described in international patent application WO 91/08171. Further suitable layered silicates are known, for example, from patent applications DE 23 34 899 A1, EP 0026529 A1 and DE 35 26 405 A1. Their usability is not limited to a special composition or structural formula. However, smectites, in particular bentonites, are preferred here. Suitable layered silicates, which belong to the group of water-swellable smectites, are e.g. B. those of the general formulas

(OH) ₄ Si _8-y Al _y (Mg _x Al _4-x ) O ₂₀ montmorrilonite
(OH) ₄ Si _8-y Al _y (Mg _6-z Li _z ) O ₂₀ hectorite
(OH) ₄ Si _8-y Al _y (Mg _6-z Al _z ) O ₂₀ saponite

with x = 0 to 4, y = 0 to 2, z = 0 to 6. In addition, small amounts of iron can be incorporated into the crystal lattice of the layered silicates according to the above formulas. Furthermore, due to their ion-exchanging properties, the layered silicates can contain hydrogen, alkali, alkaline earth ions, in particular Na ⁺ and Ca ²⁺ . The amount of water of hydration is usually in the range of 8 to 20% by weight and depends on the swelling condition or the type of processing. Usable layered silicates are known for example from US 3,966,629, US 4,062,647, EP 0026529 A1 and EP 0028432 A1. Layer silicates are preferably used which are largely free of calcium ions and strongly coloring iron ions due to an alkali treatment.

The preferred builder substances also include amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2, 6, which are delayed release and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray genamorphic”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles provide washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates, which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE 44 00 024 A1. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray morphous silicates.

It goes without saying that the generally known phosphates are also used as builder substances possible if such use should not be avoided for ecological reasons. Ge the sodium salts of orthophosphates, pyrophosphates and in particular are particularly suitable the tripolyphosphate. Their content is generally not more than 25% by weight, preferably not more than 20 wt .-%, each based on the finished agent. In some cases it has been shown that in particular tripolyphosphates even in small amounts up to a maximum of 10% by weight, based on the finished agents, in combination with other builder substances for a synergistic improvement of secondary washing power.

Co-builder

Examples of usable organic builders that can be used as co-builders are the polycarboxylic acids which can be used in the form of their sodium salts, such as citric acid, adipic acid, Bern tartaric acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, as well as mixtures from these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, Succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these. The acids too in itself can be used. In addition to their builder action, the acids typically have  also the property of an acidifying component and thus also serve to set a low lower and milder pH value of detergents or cleaning agents. Citro in particular Nenoic acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of the to call sen.

Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary processes, for example acid-catalyzed or enzyme-catalyzed. They are preferably hydrolysis products with average molecular weights in the range from 400 to 500,000. A polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, DE being a customary measure for is the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100. Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 can be used. A preferred dextrin is described in British patent application GB 9419091 A1. The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP 0232202 A1, EP 0427349 A1, EP 0472042 A1 and EP 0542496 A1 as well as from international patent applications WO 92/18542, WO 93/08251, WO 93/16110, WO 94 / 28030, WO 95/07303, WO 95/12619 and WO 95/20608 are known. An oxidized oligosaccharide according to German patent application DE 196 00 018 A1 is also suitable. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

Other suitable cobuilders are oxydisuccinates and other derivatives of disuccinates, preferably wise ethylenediamine disuccinate. Glyce are also particularly preferred in this context rindisuccinate and glycerol trisuccinate, as described, for example, in the US patent publications US 4,524,009, US 4,639,325, in European patent application EP 0150930 A1 and Japanese patent application JP 93/339896. Suitable amounts are used in zeolite-containing and / or silicate-containing formulations at 3 to 15% by weight. More usable Organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which optionally also in lactone form and which have at least 4 carbon atoms and contain at least one hydroxy group and a maximum of two acid groups. Such cobuilders are described, for example, in international patent application WO 95/20029.

Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or Polymethacrylic acid, for example those with a molecular weight of 800 to 150,000 (on  Acid sourced and measured against polystyrene sulfonic acid). Suitable copolymeric polycar Boxylates are especially those of acrylic acid with methacrylic acid and acrylic acid or Methacrylic acid with maleic acid. Copolymers of acrylic acid have been found to be particularly suitable Maleic acid proven to contain 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid. Their relative molecular weight, based on free acids, is generally from 5,000 to 200,000 preferably 10,000 to 120,000 and in particular 50,000 to 100,000 (each measured against Po lystyrene sulfonic acid). The (co) polymeric polycarboxylates can either be as a powder or as an aqueous Solution are used, with 20 to 55 wt .-% aqueous solutions are preferred. Granules Polymers are usually mixed into one or more basic granules afterwards. In particular Biodegradable polymers made from more than two different mono are also particularly preferred mer units, for example those which according to DE 43 00 772 A1 as monomers salts of acrylic acid re and maleic acid and vinyl alcohol or vinyl alcohol derivatives or according to DE 42 21 381 C2 contain as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives. Other preferred copolymers are those described in German patent applications DE 43 03 320 A1 and DE 44 17 734 A1 and preferably monomers acrolein and acrylic have acid / acrylic acid salts or acrolein and vinyl acetate. Are also preferred as others Builder substances include polymeric aminodicarboxylic acids, their salts or their precursors call. Polyaspartic acids or their salts and derivatives are particularly preferred.

Other suitable builder substances are polyacetals, which are reacted with dialdehydes Polyolcarboxylic acids, which have 5 to 7 carbon atoms and at least 3 hydroxyl groups for example as described in European patent application EP 0280223 A1 can. Preferred polyacetals are made from dialdehydes such as glyoxal, glutaraldehyde, terephthalalde hyd and their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid re received.

In addition, the agents can also contain components that make the oil and fat washable made of textiles. The preferred oil and fat dissolving components include for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose a proportion of methoxyl groups from 15 to 30 wt .-% and of hydroxypropoxyl groups from 1 to 15% by weight, based in each case on the nonionic cellulose ether, and those from the prior art Technology known polymers of phthalic acid and / or terephthalic acid or their deriva ten, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of these. Particularly preferred of these are the sulfonated derivatives of phthalic acid and terephthalic acid polymers.

Other suitable ingredients of the agents are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates, normal water glasses, which have no outstanding builder properties, or mixtures of these; In particular, alkali carbonate and / or amorphous alkali silicate, especially sodium silicate with a molar ratio Na ₂ O: SiO ₂ of 1: 1 to 1: 4.5, preferably of 1: 2 to 1: 3.5, are used. The content of sodium carbonate in the final preparations is preferably up to 40% by weight, advantageously between 2 and 35% by weight. The content of sodium silicate in the agents (without special builder properties) is generally up to 10% by weight and preferably between 1 and 8% by weight.

In addition to the ingredients mentioned, the agents can include other known additives, for example Salts of polyphosphonic acids, optical brighteners, enzymes, enzyme stabilizers, defoamers, ge rings contain amounts of neutral filler salts as well as colors and fragrances and the like.

Bleaching agents and bleach activators

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. The bleaching agent content of the agents is preferably from 5 to 35% by weight and in particular up to 30% by weight, advantageously using per borate monohydrate or percarbonate.

As bleach activators, compounds which are aliphatic under perhydrolysis conditions oxocarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or ge optionally substituted perbenzoic acid result, are used. Substances that are suitable O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl carry groups. Multi-acylated alkylenediamines, in particular tetraacetylethylene, are preferred diamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or isononanoyl oxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5- dihydrofuran and those from German patent applications DE 196 16 693 A1 and DE 196 16 767 A1 known enol esters as well as acetylated sorbitol and mannitol or their in the European The patent application EP 0525239 A1 describes mixtures (SORMAN), acylated sugars derivatives, especially pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaa cetyllactose and acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N- acylated lactams, for example N-benzoylcaprolactam, from the international patent applications  WO 94/27970, WO 94/28102, WO 94/28103, WO 95/00626, WO 95/14759 and WO 95/17498 are known. The hydrophilic sub. Known from German patent application DE 196 16 769 A1 substituted acylacetals and those in German patent application DE 196 16 770 and the internatio Nale patent application WO 95/14075 described acyllactams are also preferably used puts. The combinations known from German patent application DE 44 43 177 A1 conventional bleach activators can be used. Such bleach activators are common Quantity range, preferably in amounts from 1% by weight to 10% by weight, in particular 2% by weight to 8% by weight, based on the total average. In addition to the conventional ones listed above Len bleach activators or in their place can also those from the European patent specifications EP 0446982 B1 and EP 0453 003 B1 known sulfonimines and / or bleach-boosting agents transition metal salts or transition metal complexes as so-called bleaching catalysts be included. The transition metal compounds in question include in particular those Manganese, iron, cobalt, rutheni known from German patent application DE 195 29 905 A1 um or molybdenum salt complexes and those from German patent application DE 196 20 267 A1 Known N-analog connections, which is known from German patent application DE 195 36 082 A1 manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes, which in the German Patent application DE 196 05 688 A1 described manganese, iron, cobalt, ruthenium, molybdenum, Titanium, vanadium and copper complexes with nitrogen-containing tripod ligands, derived from the German Patent application DE 196 20 411 A1 known cobalt, iron, copper and ruthenium amine complexes, the manganese, copper and cobalt described in German patent application DE 44 16 438 A1 Complexes described in the European patent application EP 0272030 A1 cobalt Complexes, the manganese complexes known from European patent application EP 0693550 A1, the manganese, iron, cobalt and copper known from European patent EP 0392592 A1 fer complexes and / or those in the European patent EP 0443651 B1 or the European Patent applications EP 0458397 A1, EP 0458398 A1, EP 0549271 A1, EP 0549272 A1, EP 0544490 A1 and EP 0544519 A1 described manganese complexes. Combinations of bleach activators and Transition metal bleaching catalysts are, for example, from the German patent application DE 196 13 103 A1 and the international patent application WO 95/27775 are known. Bleaching enhancer Transition metal complexes, in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, are in usual amounts, preferably in an amount up to 1 wt .-%, especially of 0.0025% by weight to 0.25% by weight and particularly preferably from 0.01% by weight to 0.1% by weight, in each case based on the entire mean.

Enzymes and enzyme stabilizers

Enzymes in particular come from the class of hydrolases, such as proteases, Estera sen, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases  and mixtures of the enzymes mentioned. All of these hydrolases carry in the Laundry for removing stains, such as stains containing protein, fat or starch, and Graying at. Cellulases and other glycosyl hydrolases can be removed by removing pilling and microfibrils help to maintain color and increase the softness of the textile. To bleach or to inhibit color transfer, oxidoreductases can also be used. Especially from bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens enzymatic active ingredients obtained. Preferably who the proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus the, used. There are enzyme mixtures, for example from protease and amylase or Pro tease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipoly enzymes or protease having a table action, lipase or enzymes and cellulase having a lipolytic action, in particular, however, protease- and / or lipase-containing mixtures or mixtures with lipolytic acting enzymes of particular interest. Examples of such lipolytic enzymes are the well-known cutinases. Peroxidases or oxidases have also been found in some cases proven. Suitable amylases include in particular α-amylases, iso-amylases, pul lulanases and pectinases. Cellobiohydrolases, endoglucanases are preferably used as cellulases and β-glucosidases, which are also called cellobiases, or mixtures thereof. Because the different cellulase types differ in their CMCase and avicelase activities the desired activities can be set by targeted mixtures of the cellulases. The enzymes can be adsorbed on carriers and / or embedded in coating substances around them protect against premature decomposition. The percentage of enzymes, enzyme mixtures or enzyme Granules can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.

In addition to the mono- and polyfunctional alcohols, the agents can contain further enzyme stabilizers. For example, 0.5 to 1% by weight sodium formate can be used. It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme. In addition to calcium salts, magnesium salts also serve as stabilizers. However, the use of boron compounds, for example boric acid, boron oxide, borax and other alkali metal borates such as the salts of orthoboric acid (H ₃ BO ₃ ), metaboric acid (HBO ₂ ) and pyrobic acid (tetraboric acid H ₂ B ₄ O ₇ ), is particularly advantageous. .

Graying inhibitors

Graying inhibitors have the task of susceptible to the dirt detached from the fiber in the fleet keep swinging and prevent the dirt from re-opening. Here are what Suitable water-soluble colloids mostly organic in nature, for example the water-soluble polymer salts  Carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch ke 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. Next Soluble starch preparations and starch products other than those mentioned above can be used the, e.g. B. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone is also useful. Prefers However, cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarb oxymethyl cellulose and mixtures thereof, and polyvinyl pyrrolidone, for example in amounts of 0.1 up to 5 wt .-%, based on the agent used.

Optical brighteners

The agents can contain derivatives of diaminostilbenedisulfonic acid or their alkali metal salts as optical brighteners. Are suitable for. B. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which instead of morpholino- Group carry a diethanolamino group, a methylamino group, anilino group or a 2-methoxyethylamino group. Furthermore, brighteners of the substituted diphenylstyle type may be present, e.g. B. the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4'- (2-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used. Uniform white granules are obtained if the agents, in addition to the usual brighteners, are used in customary amounts, for example between 0.1 and 0.5% by weight, preferably between 0.1 and 0.3% by weight, even small amounts , for example 10 ^-6 to 10 ^-3 wt .-%, preferably around 10 ^-5 wt .-%, of a blue dye. A particularly preferred dye is Tinolux® (commercial product from Ciba-Geigy).

Polymers

Suitable soil-repellants are substances which preferably Contain ethylene terephthalate and / or polyethylene glycol terephthalate groups, the molar ratio Ethylene terephthalate to polyethylene glycol terephthalate can range from 50:50 to 90:10. The molecular weight of the linking polyethylene glycol units is in particular in the range of 750 to 5000, d. that is, the degree of ethoxylation of the polymers containing polyethylene glycol groups can be approximately 15 up to 100. The polymers have an average molecular weight of about 5000 to 200,000 and can have a block, but preferably a random structure. Preferred polymers are those with molar ratios of ethylene terephthalate / polyethylene glycol terephthalate from about 65:35 to about 90:10, preferably from about 70:30 to 80:20  preferred are those polymers which link polyethylene glycol units with one mole molecular weight from 750 to 5000, preferably from 1000 to about 3000 and a molecular weight of Have polymers from about 10,000 to about 50,000. Examples of commercially available polymers are Products Milease® T (ICI) or Repelotex® SRP 3 (Rhône-Poulenc).

Defoamer

Wax-like compounds can be used as defoamers. As "waxy" sol che understood compounds that have a melting point at atmospheric pressure above 25 ° C (room temperature temperature), preferably above 50 ° C and in particular above 70 ° C. The waxy Ent foaming agents are practically insoluble in water, d. H. at 20 ° C in 100 g of water solubility below 0.1% by weight. In principle, all known from the prior art wax-like defoamer substances can be included. Suitable wax-like compounds are in for example bisamides, fatty alcohols, fatty acids, carboxylic acid esters of mono- and polyhydric alcohol len as well as paraffin waxes or mixtures thereof. Alternatively, of course, you can also use them Purpose known silicone compounds are used.

Suitable paraffin waxes are generally a complex mixture of substances without a sharp melting point. For characterization, one usually determines its melting range by differential thermal analysis (DTA), as described in "The Analyst" 87 (1962), 420, and / or its freezing point. This is the temperature at which the paraffin changes from the liquid to the solid state by slow cooling. Paraffins which are completely liquid at room temperature, that is to say those having a solidification point below 25 ° C., cannot be used according to the invention. The soft waxes, which have a melting point in the range from 35 to 50 ° C., preferably include the group of petrolates and their hydrogenation products. They are made up of microcrystalline paraffins and up to 70% by weight of oil, have an ointment-like to plastically solid consistency and represent bitumen-free residues from petroleum processing. Distillation residues (petrolatum stocks) of certain paraffin-based and mixed-base crude oils that form petroleum jelly are particularly preferred to be processed further. It is furthermore preferred to use bitumen-free, oil-like to solid hydrocarbons separated from distillation residues of paraffin- and mixed-base crude oils and cylinder oil distillates by means of solvents. They are of semi-solid, quick, sticky to plastic-solid consistency and have melting points between 50 and 70 ° C. These petrolates represent the most important starting point for the production of micro waxes. Also suitable are the solid hydrocarbons with melting points between 63 and 79 ° C, which are separated from the highly viscous, paraffin-containing lubricating oil distillates during the dewaxing. These petrolates are mixtures of microcrystalline waxes and high-melting n-paraffins. For example, the paraffin wax mixtures known from EP 0309931 A1 of, for example, 26% by weight to 49% by weight of microcrystalline paraffin wax with a solidification point of 62 ° C. to 90 ° C., 20% by weight to 49% by weight can be used. Hard paraffin with a solidification point from 42 ° C to 56 ° C and 2% by weight to 25% by weight soft paraffin with a solidification point from 35 ° C to 40 ° C. Paraffins or paraffin mixtures which solidify in the range from 30 ° C. to 90 ° C. are preferably used. It should be noted that, even at room temperature, solid paraffin wax mixtures can contain different proportions of liquid paraffin. In the paraffin waxes which can be used according to the invention, this liquid fraction is as low as possible and is preferably absent entirely. Particularly preferred paraffin wax mixtures at 30 ° C have a liquid fraction of less than 10% by weight, in particular from 2% by weight to 5% by weight, at 40 ° C a liquid fraction of less than 30% by weight, preferably of 5 % By weight to 25% by weight and in particular from 5% by weight to 15% by weight, at 60 ° C. a liquid fraction of 30% by weight to 60% by weight, in particular 40% by weight % to 55% by weight, at 80 ° C a liquid content of 80% by weight to 100% by weight, and at 90 ° C a liquid content of 100% by weight. The temperature at which a liquid content of 100% by weight of the paraffin wax is reached is still below 85 ° C., in particular at 75 ° C. to 82 ° C., in particularly preferred paraffin wax mixtures. The paraffin waxes can be petrolatum, microcrystalline waxes or hydrogenated or partially hydrogenated paraffin waxes.

Suitable bisamides as defoamers are those which differ from saturated fatty acids with 12 to 22, preferably derived from 14 to 18 carbon atoms and from alkylenediamines with 2 to 7 carbon atoms. Appropriate nete fatty acids are lauric, myristic, stearic, arachic and behenic acid and mixtures thereof, such as it is obtained from natural fats or hardened oils, such as tallow or hydrogenated palm oil are. Suitable diamines are, for example, ethylenediamine, 1,3-propylenediamine, tetramethy lendiamine, pentamethylenediamine, hexamethylenediamine, p-phenylenediamine and toluenediamine. Before pulled diamines are ethylenediamine and hexamethylenediamine. Bisamides are particularly preferred Bismyristoylethylenediamine, bispalmitoylethylenediamine, bisstearoylethylenediamine and mixtures thereof and the corresponding derivatives of hexamethylenediamine.

Suitable carboxylic acid esters as defoamers are derived from carboxylic acids with 12 to 28 carbon atoms. In particular, these are esters of behenic acid, stearic acid, hydroxystearic acid, oleic acid, palmitic acid, myristic acid and / or lauric acid. The alcohol portion of the carboxylic acid ester contains a mono- or polyhydric alcohol with 1 to 28 carbon atoms in the hydrocarbon chain. Examples of suitable alcohols are behenyl alcohol, arachidyl alcohol, coconut alcohol, 12-hydroxystearyl alcohol, oleyl alcohol and lauryl alcohol, and also ethylene glycol, glycerol, polyvinyl alcohol, sucrose, erythritol, pentaerythritol, sorbitan and / or sorbitol. Preferred esters are those of ethylene glycol, glycerol and sorbitan, the acid part of the ester being selected in particular from behenic acid, stearic acid, oleic acid, palmitic acid or myristic acid. Suitable esters of polyvalent alcohols include xylitol monopalmitate, Pentarythritmonostearat, monostearate of glycerol, ethylene glycol and rat sorbitan, sorbitan Sorbitanmonolau, Sorbitandilaurat, sorbitan, sorbitan dioleate, and sorbitan mixed tallow and diesters. Glycerol esters which can be used are the mono-, di- or triesters of glycerol and the carboxylic acids mentioned, the mono- or diesters being preferred. Glycerol monostearate, glycerol monooleate, glycerol monopalmitate, glycerol monobehenate and glycerol distearate are examples of this. Examples of suitable natural esters as defoamers are beeswax, which mainly consists of the esters CH ₃ (CH ₂ ) ₂₄ COO (CH ₂ ) ₂₇ CH ₃ and CH ₃ (CH ₂ ) ₂₆ COO (CH ₂ ) ₂₅ CH ₃ , and carnauba wax, which is a mixture of carnaubaic acid alkyl esters, often in combination with small amounts of free carnaubaic acid, other long-chain acids, high molecular weight alcohols and hydrocarbons.

Suitable carboxylic acids as a further defoamer compound are in particular behenic acid, stea rinic acid, oleic acid, palmitic acid, myristic acid and lauric acid as well as their mixtures as they are natural fats or optionally hardened oils, such as tallow or hydrogenated palm oil are. Saturated fatty acids with 12 to 22, in particular 18 to 22, carbon atoms are preferred.

Suitable fatty alcohols as a further defoamer compound are the hydrogenated products of be written fatty acids.

Dialkyl ethers may also be present as defoamers. The ethers can be asym be constructed metrically or symmetrically, d. H. two identical or different alkyl chains preferably contain 8 to 18 carbon atoms. Typical examples are di-n-octyl ether, di-i- octyl ether and di-n-stearyl ether, particularly suitable are dialkyl ethers which have a melting point above Have 25 ° C, especially above 40 ° C.

Other suitable defoamer compounds are fatty ketones, which are based on the relevant methods of preparative organic chemistry can be obtained. One goes to their manufacture example of carboxylic acid magnesium salts, which at temperatures above 300 ° C below Elimination of carbon dioxide and water are pyrolyzed, for example according to the German Publication DE 25 53 900 OS. Suitable fat ketones are those obtained by pyrolysis of the Ma magnesium salts of lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, Elaidic acid, petroselinic acid, arachic acid, gadoleic acid, behenic acid or erucic acid become.

Other suitable defoamers are fatty acid polyethylene glycol esters, which are preferably basic homogeneously catalyzed addition of ethylene oxide to fatty acids can be obtained. Especially done the addition of ethylene oxide to the fatty acids in the presence of alkanolamines as catalysts. The use of alkanolamines, especially triethanolamine, leads to an extremely selective ethoxylation fatty acids, especially when it comes to producing low-ethoxylated compounds len. Within the group of fatty acid polyethylene glycol esters, those which have one are preferred Have melting point above 25 ° C, especially above 40 ° C.  

Within the group of wax-like defoamers, the paraffin waxes described are particularly preferably used alone as wax-like defoamers or in a mixture with one of the other wax-like defoamers, the proportion of paraffin waxes in the mixture preferably making up more than 50% by weight, based on the wax-like defoamer mixture . The paraffin waxes can be applied to carriers if necessary. All known inorganic and / or organic carrier materials are suitable as carrier materials. Examples of typical inorganic carrier materials are alkali carbonates, aluminosilicates, water-soluble layer silicates, alkali silicates, alkali sulfates, for example sodium sulfate, and alkali phosphates. The alkali silicates are preferably a compound with a molar ratio of alkali oxide to SiO ₂ of 1: 1.5 to 1: 3.5. The use of such silicates results in particularly good grain properties, in particular high abrasion stability and nevertheless high dissolution rate in water. The aluminosilicates referred to as carrier material include in particular the zeolites, for example zeolite NaA and NaX. The compounds referred to as water-soluble layered silicates include, for example, amorphous or crystalline water glass. Silicates which are commercially available under the name Aerosil® or Sipernat® can also be used. Examples of suitable organic carrier materials are film-forming polymers, for example polyvinyl alcohols, polyvinyl pyrrolidones, poly (meth) acrylates, polycarboxylates, cellulose derivatives and starch. Usable cellulose ethers are, in particular, alkali carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose and so-called cellulose mixed ethers, such as, for example, methyl hydroxyethyl cellulose and methyl hydroxypropyl cellulose, and mixtures thereof. Particularly suitable mixtures are composed of sodium carboxymethyl cellulose and methyl cellulose, the carboxymethyl cellulose usually having a degree of substitution of 0.5 to 0.8 carboxymethyl groups per anhydroglucose unit and the methyl cellulose having a degree of substitution of 1.2 to 2 methyl groups per anhydroglucose unit. The mixtures preferably contain alkali carboxymethyl cellulose and nonionic cellulose ether in weight ratios of 80:20 to 40:60, in particular 75: 25 to 50:50. Also suitable as a carrier is native starch, which is composed of amylose and amylopectin. Starch is called native starch, as it is available as an extract from natural sources, for example from rice, potatoes, corn and wheat. Native starch is a commercially available product and is therefore easily accessible. Carrier materials which can be used individually or more than one of the abovementioned compounds, in particular selected from the group of alkali metal carbonates, alkali metal sulfates, alkali metal phosphates, zeolites, water-soluble sheet silicates, alkali metal silicates, polycarboxylates, cellulose ethers, polyacrylate / polymethacrylate and starch. Mixtures of alkali carbonates, in particular sodium carbonate, alkali silicates, in particular sodium silicate, alkali sulfates, in particular sodium sulfate and zeolites are particularly suitable.

Suitable silicones are common organopolysiloxanes, which contain fine-particle silica in turn can also be silanized. Such organopolysiloxanes are, for example described in European patent application EP 0496510 A1. Are particularly preferred  Polydiorganosiloxanes and in particular polydimethylsiloxanes, which are known from the prior art are. Suitable polydiorganosiloxanes have an almost linear chain and an oligo Degree of merization from 40 to 1500. Examples of suitable substituents are methyl, ethyl, propyl, Isobutyl, tert. Butyl and phenyl. Also suitable are amino, fatty acid, alcohol, polyether, epoxy, fluorine, glycoside and / or alkyl modified silicone compounds that are both liquid at room temperature as well as resinous. Simethicones, which are Mi mixtures of dimethicones with an average chain length of 200 to 300 dimethylsiloxane Units and hydrogenated silicates. As a rule, the silicones in general contain and Polydiorganosiloxanes in particular fine-particle silica, which can also be silanized. In particular For the purposes of the present invention, silicic acid-containing dimethylpolysiloxanes are suitable. Advantage the polydiorganosiloxanes have a Brookfield viscosity at 25 ° C (spindle 1, 10 rpm) in the range from 5000 mPas to 30000 mPas, in particular from 15000 to 25000 mPas. Before the silicones are preferably used in the form of their aqueous emulsions. As a rule, you give the silicone to the water provided with stirring. If desired, one can increase the viscosity ity of the aqueous silicone emulsions thickeners, as known from the prior art are admit. These can be inorganic and / or organic in nature, particularly preferred are nonionic cellulose ethers such as methyl cellulose, ethyl cellulose and mixed ethers such as methyl hy doxyethylcellulose, methylhydroxypropylcellulose, methylhydroxybutylcellulose and anionic car boxycellulose types such as the carboxymethylcellulose sodium salt (abbreviation CMC). Especially ge suitable thickeners are mixtures of CMC to non-ionic cellulose ethers in a weight ratio 80: 20 to 40: 60, in particular 75: 25 to 60: 40. As a rule and especially when adding the be written thickener mixtures are recommended use concentrations of about 0.5 to 10, in particular Special from 2.0 to 6 wt .-% - calculated as a thickener mixture and based on aqueous silicones emulsion. The content of silicones of the type described in the aqueous emulsions is advantageous in the range from 5 to 50% by weight, in particular from 20 to 40% by weight - calculated as Sili cone and based on aqueous silicone emulsion. According to a further advantageous embodiment, he keep the aqueous silicone solutions as thickeners starch, which is accessible from natural sources, for example from rice, potatoes, corn and wheat. The starch is advantageously in amounts of 0.1 to 50 wt .-% - based on silicone emulsion - contain and especially in a mixture with the already described thickener mixtures of sodium carboxymethyl cellulose and a nich tional cellulose ether in the amounts already mentioned. For the production of the aqueous silicone mul sions one expediently proceeds in such a way that the thickening which may be present pre-swell medium in water before adding the silicones. Incorporation of the silicones expediently takes place with the aid of effective stirring and mixing devices.  

Fragrances

As perfume oils or fragrances, individual fragrance compounds, e.g. B. the synthetic pro Products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used the. Fragrance compounds of the ester type are e.g. B. benzyl acetate, phenoxyethyl isobutyrate, p-tert.- Butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate, linalyl benzoate, Benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate and benzylsa licylate. The ethers include, for example, benzyl ethyl ether, the aldehydes z. B. the linear Alka nale with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitro nellal, lilial and bourgeonal, to the ketones z. B. the Jonone, α-Isomethylionon and Methylcedrylke clay, to the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpi neol, the hydrocarbons mainly include terpenes such as limonene and pinene. Before however, mixtures of different odoriferous substances are used, which together address one Generate the appropriate fragrance. Such perfume oils can also contain natural fragrance mixtures, as they are accessible from plant sources, e.g. B. pine, citrus, jasmine, patchouly, rose or Ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, Cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.

The fragrances can be incorporated directly into the agents according to the invention, but it can also be advantageous to apply the fragrances on carriers, which the adhesion of the perfume on the Wä strengthening and slower fragrance release for long-lasting fragrance of textiles For example, cyclodextrins have proven themselves as such carrier materials, the cyclo dextrin-perfume complexes can also be coated with other auxiliaries.

Positioning means

If desired, the final preparations can also contain inorganic salts as fillers or fillers hold, such as sodium sulfate, which is preferably in amounts of 0 to 10, in particular 1 to 5 wt .-% - based on agent - is included.

Tableting

The production of the washing obtainable using the disintegrants produced according to the invention Medium tablets are usually made by tableting or press agglomeration. The part received Chen-shaped press agglomerates can either be used directly as a detergent or after  usual methods are post-treated and / or processed. To the usual aftercare include, for example, powdering with finely divided ingredients from washing or cleaning agents, which generally further increases the bulk density. A preferred aftertreatment provides however, also the procedure according to German patent applications DE 195 24 287 A1 and DE 195 47 457 A1 represents dusty or at least finely divided ingredients (the so-called Fine fractions) of the particulate process end products produced according to the invention, which as Serve the core, be glued and thus create means that these so-called fine fractions as Have outer shell. In turn, this advantageously takes place by melting agglomeration. For melt agglomeration of the fine fractions on the disclosure in the German Patent applications DE 195 24 287 A1 and DE 195 47 457 A1 referenced. In the preferred embodiment Form of the invention, the solid detergents are in tablet form, these tablets Especially for storage and transport reasons, preferably rounded corners and Have edges. The base of these tablets can be circular or rectangular, for example his. Multi-layer tablets, especially tablets with 2 or 3 layers, which are also colored may be different, are particularly preferred. Blue-white or green-white or blue-green-white Tablets are particularly preferred. The tablets can also be pressed and uncompressed Shares included. Moldings with a particularly advantageous dissolution rate are obtained if the granular constituents have a proportion of particles which have a diameter possess water outside the range of 0.02 to 6 mm, less than 20, preferably less have than 10 wt .-%. A particle size distribution in the range from 0.05 to 2.0 and is preferred particularly preferably from 0.2 to 1.0 mm.

Examples Example H1

Finely divided cross-linked polyvinylpyrrolidone (Collidon® CL, BASF) was by means of a hydraulic press at a pressure of 1,700 bar. The resulting compacts were mechanically crushed and the grain fraction between 0.4 and 1 mm was sieved from it.

Example H2

Microcrystalline cellulose (Technocell®) was extracted using a hydraulic press at ei compressed at a pressure of 5,200 bar. The resulting compacts were crushed mechanically and from it the grain fraction between 0.4 and 1 mm was sieved.

Application tests

The two explosives H1 and H2 and the two uncompressed starting materials were used in detergent formulations. The accessory Preparations were pressed into tablets (weight 40 g), packed airtight and then for 2 weeks Chen stored at 40 ° C. The composition of the detergent tablets is shown in Table 1. Formulations 1 and 2 are according to the invention, formulations V1 and V2 are used for comparison. For To assess the dissolution behavior, the tablets were placed on a wire rack, which was in water (0 ° d, 25 ° C). The tablets were completely surrounded by water. The was measured Disintegration time from immersion to complete dissolution. The disintegration times are also from Ta see belle 1.  

Table 1

Test formulation for detergent tablets and solubility tests (figures in% by weight, water ad 100%)

Claims (4)

1. A process for the preparation of tablet disintegrants, in which swellable substances Press presses compacted in the range from 50 to 100,000 bar and the compacts obtained in this way finally crushed in a conventional manner, the majority of the crushed good has a particle size below 0.1 mm. 2. The method according to claim 1, characterized in that Po as swellable substances lyvinylpyrrolidone, polyacrylates, celluloses and / or starches and their derivatives. 3. The method according to claims 1 and / or 2, characterized in that the Kompak tion at pressures in the range of 100 to 10,000 bar. 4. The method according to at least one of claims 1 to 3, characterized in that sieve a fine grain fraction in the range between 0.1 and 2 mm from the comminuted material.