Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/38—Cationic compounds
  • C11D1/62—Quaternary ammonium compounds
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
  • D06M13/46—Compounds containing quaternary nitrogen atoms
  • D06M13/463—Compounds containing quaternary nitrogen atoms derived from monoamines
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
  • D06M2200/50—Modified hand or grip properties; Softening compositions

Definitions

• the invention relates to quaternary ammonium compounds in which the ammonium nitrogen atom carries one or two long-chain ester residues or amide residues of etherified hydroxycarboxylic acids, a process for the preparation of such quaternary ammonium compounds and their use in textile aftertreatment agents.
• Quaternary ammonium compounds which contain one or two long-chain and three or two short-chain aliphatic hydrocarbon residues in the molecule have long been used as textile softeners for treating textiles, in particular for post-treating washed laundry, but also in softening detergents and used in tumble aids. Treatment with such compounds gives the textiles a soft and full feel. When used, however, the treated textile material shows a significantly lower absorbency compared to untreated textiles. Terry towels, tea towels or diapers that have been repeatedly treated with such quaternary ammonium compounds after washing are therefore due to their reduced or delayed water absorption in their performance properties impaired. These adverse effects are due to the fact that the quaternary ammonium compounds applied to the fibers are not or not completely removed during the subsequent washing and therefore the repeated aftertreatment leads to an accumulation of the quaternary ammonium compounds on the fiber.
• DE-OS 34 02 146 relates to quaternary ammonium compounds with one or two long-chain ester radicals, the acid component of which is derived from branched carboxylic acids of the so-called "Guerbet type".
• the quaternary ammonium compounds known from DE-OS 34 02 146 do have the above ten disadvantages not or only in a weakened form; however, they can either only be prepared in several complicated process steps or are produced in the form of dilute dispersions which cannot be used for the preparation of the textile softener concentrates which have recently become interesting. In addition, they have the disadvantage that they are poorly soluble or poorly dispersible in aqueous systems or tend to hydrolyze therein. This particularly affects those compounds which contain ester bonds.
• the object of the invention was to provide raw materials for textile aftertreatment agents which do not have the disadvantages of the prior art.
• Raw materials for textile aftertreatment agents should be available which, in addition to good solubility in aqueous systems, also had the ability to be made up into concentrates for textile aftertreatment agents. Due to the high demand for such concentrates, the so-called "tenfold concentrates" were of particular interest.
• the raw materials for textile aftertreatment agents should also have the property of not changing the absorbency of the fabrics treated with them, so that this is still completely retained even after several washing or aftertreatment cycles.
• care should also be taken to use only raw materials that are accessible from natural sources and are therefore renewable.
• the invention thus relates to quaternary ammonium compounds of the general formula (I) in the R1 is an alkyl radical with 1 to 4 C atoms or a hydroxyalkyl radical with 1 to 4 C atoms
• R2 for an alkyl radical with 1 to 4 carbon atoms, a hydroxyalkyl radical with 1 to 4 carbon atoms or a phenalkyl radical with 1 to 3 carbon atoms in the alkyl group
• R3 and R4 which may be the same or different, represent a radical of the general formula (II) in the m is an integer in the range from 1 to 3, n and p independently of one another integers in the range from 1 to 12 with a sum (p + n) in the range from 2 to 20,
• A is a group -O- or -NH-
• R5 and R6 can be hydrogen or a saturated or unsaturated alkyl radical having 1 to 22 carbon atoms with the proviso that R5 is H when R6 is the alkyl
• the invention also relates to a process for the preparation of quaternary ammonium compounds of the general formula (I) in the R1 is an alkyl radical with 1 to 4 C atoms or a hydroxyalkyl radical with 1 to 4 C atoms, R2 for an alkyl radical with 1 to 4 carbon atoms, a hydroxyalkyl radical with 1 to 4 carbon atoms or a phenalkyl radical with 1 to 3 carbon atoms in the alkyl group and R3 and R4, which may be the same or different, represent a radical of the general formula (II) in the m is an integer in the range from 1 to 3, n and p independently of one another integers in the range from 1 to 12 with a sum (p + n) in the range from 2 to 20, A is a group -O- or -NH- and R5 and R6 can be hydrogen or a saturated or unsaturated alkyl radical having 1 to 22 carbon atoms with the proviso that R5 is H when R6 is the al
• the invention also relates to the use of the quaternary ammonium compounds of the above general formula (I) as textile aftertreatment agents for synthetic and natural fibers and structures made therefrom.
• the new quaternary ammonium compounds which have special properties that make them suitable as raw materials for textile aftertreatment agents, have the general formula (I)
• the radical R 1 connected to the ammonium nitrogen atom in the quaternary ammonium compounds according to the invention can stand for an alkyl radical with 1 to 4 C atoms or a hydroxyalkyl radical with 1 to 4 C atoms.
• the groups R 1 are therefore the groups methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, and also hydroxymethyl, hydroxyethyl, hydroxypropyl or hydroxybutyl.
• the R 1 radicals in the quaternary ammonium compounds according to the invention are the hydroxyalkyl radicals having 1 to 4 carbon atoms; Particularly preferred radicals for which R 1 in the general formula (I) can stand are the radicals methyl, hydroxyethyl and 2-hydroxypropyl.
• the R2 radicals in the general formula (I) of the quaternary ammonium compounds according to the invention are alkyl radicals having 1 to 4 C atoms or hydroxyalkyl radicals having 1 to 4 C atoms, that is to say, the same groups which have been given above for the radical R1.
• the R 2 radicals are the alkyl radicals having 1 to 4 carbon atoms; the particularly preferred substituent R 2 on the ammonium nitrogen of the compounds of the general formula (I) according to the invention is the methyl radical.
• the radical R2 can also represent a 2-hydroxyethyl radical and a phenalkyl radical with 1 to 3 carbon atoms in the alkyl group. Examples of such radicals are the benzyl radical, the phenylethyl radical or the phenylpropyl radical.
• radicals R3 and R4 can be the same or different. Quaternary ammonium compounds in which the radicals R3 and R4 are the same. According to the invention, R3 and R4 represent a radical of the general formula (II)
• m represents an integer in the range from 1 to 3; a methylene, ethylene or propylene group is therefore directly connected to the ammonium nitrogen atom.
• group -A- which can mean an -O bridge or -NH bridge; depending on whether in the quaternary ammonium compounds according to the invention an ester bond or an amide bond establishes the bond between the original amine and the original hydroxyether carboxylic acid.
• n and p independently of one another represent integers in the range from 1 to 12, the sum (n + p) being an integer in the range from 2 to 20.
• unsaturated or (after epoxidation) natural fatty acids bridged with an oxygen bridge are used as natural starting materials for the preparation of the quaternary ammonium compounds of the general formula (I) which, according to the invention, should not have a number of C atoms of more than 24, the range of the olefinic double bond or later epoxy grouping being in the middle of the molecule, usually with the C atoms 9/10 or 13/14, depending on the natural source of the respective fatty acids.
• the meanings for n and p are usually in the range of integers from 1 to 7, so that a sum (n + p) is in the range of 2 to 14.
• R5 and R6 can be hydrogen or a saturated or unsaturated alkyl radical having 1 to 22 carbon atoms, but it should be noted that R5 is hydrogen if R6 is the alkyl radical with a number of carbon atoms in the above range and vice versa.
• R5 is hydrogen if R6 is the alkyl radical with a number of carbon atoms in the above range and vice versa.
• the alkyl or alkenyl radical for which R5 or R6 in the above general formula (II) can stand, is a radical having 1 to 22 carbon atoms.
• the alkyl radicals are therefore the radicals methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, behenyl or corresponding unsaturated aliphatic radicals and also the branched isomers of the alkyl or alkenyl radicals mentioned in question.
• the straight-chain alkyl or alkenyl radicals are preferred as R5 or R6.
• R5 or R6 alcohols derived from natural sources, in particular fatty alcohols, are used as alcohols for the ring opening reaction of the epoxides are set, the alkyl or alkenyl radicals are usually straight-chain.
• Alkyl or alkenyl radicals R5 or R6 having 12 to 18 carbon atoms are particularly preferred, and in particular the C18 radical can also be mono- or polyunsaturated, since these are inexpensively produced in large quantities from native fats or oils in large-scale industrial processes can be. It is also possible to use fatty alcohol mixtures such as those obtained in the hydrogenation of native fats or oils.
• the distribution of the number of carbon atoms in the alkyl chain is in a more or less large, for example, by distillation or the like determinable range, so that mixtures are used for ring opening, the different alkyl radicals are also in the product, ie in the radicals R5 or R6.
• Such mixtures, for which R5 or R6 stand are, for example, tallow alkyl, coconut alkyl or soy alkyl residues which can be both completely saturated and, depending on their native composition, partially unsaturated.
• the quaternary ammonium compounds of the general formula (I) according to the invention are prepared by a process, the individual steps of which are known in part from the prior art.
• the preparation of the quaternary ammonium compounds (I) proceeds as follows:
• Epoxy fatty acid esters of the general formula (III) in the R7 represents an alkyl radical with 1 to 6 carbon atoms and n and p have the above meaning, are reacted according to methods known per se with an alcohol of the general formula (IV) R5-OH (IV) in the R5 represents a saturated or unsaturated alkyl radical having 1 to 22 carbon atoms.
• unsaturated fatty acids such as those that can be obtained inexpensively on a large scale, for example in the transesterification of animal and / or vegetable fats or oils, they are epoxidized by customary processes, for example using H2O2 or peroxycarboxylic acid, and the individual compounds or carboxylic ester mixtures obtained - as described - implemented with an alcohol of the general formula (IV).
• the ester grouping of the epoxy fatty acid ester of the general formula (III) used can be a methyl, ethyl, propyl, butyl, pentyl or hexyl grouping, both the straight-chain alkyl radicals and the branched isomers being encompassed by the radical R7.
• the starting epoxy fatty acid esters have a number of carbon atoms in the fatty acid part which corresponds to the number of fatty acids derivatized in natural fats or oils.
• Fatty acids with 12 to 24 carbon atoms from the natural sources mentioned above are preferably used; In principle, however, it is also possible to use fatty acids with a significantly lower number or with a higher number of carbon atoms.
• Ammonium compounds of the general formula (I) use the natural mixtures of fatty acids of different carbon numbers or positions of the olefinic double bond or (after epoxidation) of the oxirane ring; Methods for producing such mixtures from native sources are known from the prior art and are not the subject of the present invention.
• the alcohols used to open the oxirane ring have the general formula (IV), in which R5 represents a saturated or unsaturated alkyl radical having 1 to 22 carbon atoms.
• R5 represents a saturated or unsaturated alkyl radical having 1 to 22 carbon atoms.
• the alcohols which can be used individually can be straight-chain or branched; it is also possible to use mixtures of alcohols which are inexpensive in large quantities after the - optionally partial - hydrogenation of native fats and / or oils on an industrial scale.
• They are single compounds or mixtures of straight-chain or branched alcohols from the group consisting of methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol and octadecanol or - If accessible - the corresponding unsaturated homologs, and of the latter in particular oleyl alcohol, linoleyl alcohol and linolenyl alcohol, can be used.
• the reaction of the ring opening of the oxirane ring takes place in a manner known per se, for example under the catalytic action of a mineral acid or carboxylic acid.
• the hydroxyether carboxylic acid esters formed in the course of this ring opening reaction are saponified in a subsequent saponification reaction to free hydroxyether carboxylic acids in accordance with the reaction equation (2) below.
• the saponification reaction also takes place according to methods known per se from the prior art and can use the catalytic action of an acid or base.
• the esterification or amidation reaction can be carried out in such a way that both terminal amino or hydroxyl groups of the amine (V) are reacted with one molecule of the hydroxyether carboxylic acid; in this case, the stoichiometric factor q in front of the hydroxyether carboxylic acid in reaction equation (3) is 2.
• amine (V) should be selected in the range from 3.5: 1 to 2: 1. This form of amidation or esterification produces amides or esters in which the two substituents which are bonded to the amino nitrogen via an alkylene group are identical.
• amine (V) molar ratio it is also possible to adjust the hydroxyether carboxylic acid: amine (V) molar ratio to a value of approximately 1: 1.
• amine (V) only one of the terminal amino groups of the amine (V) is amidated or a hydroxyl group of the amine (V) is esterified.
• the stoichiometric factor q before the hydroxyether carboxylic acid is equal to 1 in the reaction equation (3).
• amines are formed in which only one of the terminal amino radicals is amidated or only one of the terminal hydroxyl radicals is esterified.
• reaction equation (3) A procedure according to reaction equation (3) is preferred in which the molar ratio of hydroxyether carboxylic acids: amine (V) is in the range from 2: 1 to 2.5: 1, so that products are formed in which both terminal amino residues amidate or both terminal hydroxyl residues are esterified.
• amines (V) can be used in which the radical R 1 ⁇ is hydrogen or a radical which corresponds to the meaning given above for R1.
• R 1 ⁇ is hydrogen
• alkyl radicals with 1 to 4 carbon atoms or hydroxyalkyl radicals with 1 to 4 carbon atoms are also suitable.
• R 1 ⁇ is hydrogen
• the secondary amine obtained according to reaction equation (3) is also used Alkoxylated ethylene oxide or propylene oxide in an approximate molar ratio of 1: 1. Then tertiary amines are formed which carry an ethoxy or propoxy group instead of the hydrogen atom.
• reaction equation (3) instead of saponifying the hydroxyether carboxylic acid ester obtained according to reaction equation (1) only in accordance with reaction equation (2) and reacting the corresponding hydroxyether carboxylic acid formed thereby with the amine (V), it is also possible, according to the following reaction equation (3a), to directly react the hydroxyether carboxylic acid ester with the amine ( V) to implement, which can advantageously save the saponification step according to reaction equation (2) in suitable cases.
• the amidation or esterification reaction regardless of whether the unsaponified carboxylic acid ester (product of reaction equation (1)) or the carboxylic acid formed after saponification according to reaction equation (2) is used - is carried out according to methods known per se from the prior art, for example at elevated temperature; the tempera tures are usually in the range from 180 to 220 ° C, preferably at 200 ° C.
• a water separator is usually used to remove the water of reaction or alcohol formed during the reaction directly from the educt / product mixture and thus to shift the equilibrium of the reaction towards the products.
• the reaction is usually carried out under protective gas.
• the hydroxyethercarboxamide obtained is usually ethoxylated or propoxylated by reaction with ethylene oxide or propylene oxide in a molar ratio of 1: 1, so that tertiary amines are subsequently formed which, as substituents R 1, are an ethoxy or propoxy grouping wear.
• quaternizing reagents are therefore those in which R 2 can stand for an alkyl radical with 1 to 4 C atoms, a hydroxyalkyl radical with 1 to 4 C atoms or a phenalkyl radical with 1 to 3 C atoms in the alkyl group.
• X stands for the anion of an inorganic acid.
• the radicals R 1 are, in particular, the groups methyl, ethyl, propyl, butyl, hydroxyethyl, hydroxypropyl, hydroxybutyl and benzyl, phenylethyl or phenylpropyl, where the alkyl radicals mentioned can be either straight-chain or branched. From the group mentioned, those quaternizing reagents are preferred for the quaternizing reaction in which R 2 is an alkyl radical having 1 to 4 carbon atoms; preferred alkylation reagents (VI) use the methyl group as the quaternizing group (II).
• the quaternizing reagents are derived from inorganic or organic acids; X ⁇ stands for the anion of an inorganic or organic acid. Examples include chloride, methosulfate, formate, acetate, propionate, etc. Preferred quaternizing reagents contain, as group X ⁇ , the chloride ion or the acetate ion, of which the chloride ion is particularly preferred.
• quaternizing reagents include methyl chloride, benzyl chloride, dimethyl sulfate or acetic acid, of which methyl chloride can most often be used with advantage.
• the amino nitrogen would only be protonated; in this case, the quaternization is carried out in the presence of ethylene oxide or propylene oxide, so that the fourth group on the ammonium nitrogen atom also has an organic, in in this case is a hydroxyethyl or R-hydroxypropyl group.
• reaction is carried out in a solvent in which both the starting materials and the products dissolve to the extent necessary for the reaction.
• solvents polar organic solvents such as alcohols with 1 to 6 carbon atoms are known from the prior art; isopropanol is preferably used.
• This mixture which is preferred as alcohol Isopropanol is involved, has a volume composition of 3 to 4 volumes of alcohol per volume of water.
• the reaction is usually carried out at elevated temperature and under elevated pressure, for example in an autoclave. Values from 50 to 150 ° C., preferably 100 ° C., can be specified as the temperature range; the pressures in the autoclave are usually 1.5 to 6 bar. However, as in the prior art, it is also possible to carry out the reaction in the absence of a solvent. Which reaction conditions are to be set depends primarily on the "quaternization ability" of the quaternization reagent. If methyl chloride is used, for example, moderate reaction conditions may be sufficient so that the solvent may even be dispensed with.
• the quaternary ammonium compounds of the general formula (I) obtained in the manner described by the reaction equations (1) to (4) can now, if desired, be isolated from the reaction solution in a last process step by methods known per se. This can be done, for example, by precipitation and subsequent filtering, recrystallization, distillation or in other ways known to those skilled in the art. However, it is also possible to use the more or less concentrated solutions obtained in the course of the quaternization reaction directly for the use according to the invention.
• the quaternary ammonium compounds of the general formula (I) according to the invention are liquid to pasty Substances and can be excellently dissolved or dispersed in water or water / alcohol mixtures, the viscosity of the solutions or dispersions usually being lower than that of the quaternization products (I) themselves.
• the compounds obtained are extremely stable to hydrolysis and are outstandingly suitable for textile aftertreatment concentrates process or use immediately as a textile treatment agent.
• the concentrates have excellent storage stability and behave exactly like freshly prepared concentrates even after extreme temperature fluctuations (freezing and subsequent thawing or high-temperature treatment).
• the use of the quaternary ammonium compounds of the general formula (I) as textile aftertreatment agents for synthetic and natural fibers and structures made therefrom is also an object of the present invention.
• the new compounds of the general formula (I) prepared by the process according to the invention can be used, for example, as textile softeners which can be used both in the rinsing bath and during the washing process or during drying in automatic tumble dryers. It was found that when the compounds of the general formula (I) are used according to the invention, the agent does not accumulate on the fiber and thus the absorbency of the fiber is not changed sustainably.
• the fibers treated with the quaternary ammonium compounds of the general formula (I) according to the invention have a significantly better absorbency than fibers which have been treated with very good plasticizer compounds according to the prior art.
• the agent for the aftertreatment of textiles, using the inventive Compounds of the general formula (I) can be prepared, for example, have the following compositions: 2 to 80% by weight of ammonium compounds of the general formula (I) according to the invention; 20 to 98% by weight of carriers, solvents and / or diluents; 0 to 20 wt% emulsifier; 0 to 3% by weight preservative; 0 to 5% by weight of fragrances; 0 to 1% by weight of dyes and The rest up to 100% by weight: viscosity adjuster, opacifier, optionally acidic compounds and other additives.
• the compounds of the general formula (I) according to the invention are added to detergents of corresponding composition which contain at least one detergent-active compound, they can have a softening effect.
• Such detergents are preferably based on formulations with nonionic surfactants. If the process products are applied together with customary auxiliaries and additives to textile fabrics as carriers, these can also be used as tumbling aids.
• step (b) 256.7 g (0.4 mol) of the free hydroxyether carboxylic acid (molar mass 641.8, calculated from the acid number of 87.4) prepared according to step (b) were mixed with 26.2 g (0.2 mol) of dipropylenetriamine (DPTA) heated to 200 ° C for 5 h in a 0.5 l stirrer with water separator, nitrogen blanket and contact thermometer. During this time, 6.6 g (calculated: 7.2 g) of water distillate had been obtained. The yield was 272.0 g; Key figures: SZ: 3.1; AZ: 34.6.
• DPTA dipropylenetriamine
• step (a) 290.2 g (0.24 mol) of the product obtained after step (a) (molar mass: 1209, calculated from AZ) were treated with methyl chloride at 5 to 6 bar and 89 to 91 ° C. in a stirred autoclave in the absence of a solvent. After 2 hours the amine number had dropped from 46.4 to 2.1. Yield: 275 g of a 100% product.
• the AZ (determined with perchloric acid in glacial acetic acid) was 73.0, from which an average molecular weight of the ester product was calculated to be 768.6.
• the yield was 407.4 g.
• step (a) the hydroxyether carboxylic acid obtained in the present example, step (a), was esterified in a molar ratio of 1: 1 with triethanolamine.
• the resulting triethanolamine monoester had the following key figures: AZ: 68.8, from which a molecular weight of 815.4 was calculated ; SZ: 0.97; OHZ: 233.
• step (b) 203.9 g (0.25 mol) of the product obtained in step (b) were mixed with 15.0 g (0.25 mol) of acetic acid and 57.5 g of water. After purging with nitrogen, the mixture was heated to 80 ° C. in an autoclave and 16.5 g (0.37 mol) of ethylene oxide were added. During the reaction time of 3.5 h, the pressure dropped from 3.0 to 2.5 bar. The acid number dropped to 5.0. The product was removed hot from the autoclave after it had been let down. After cooling, phase separation occurred.
• Example 1 The products of Examples 1 to 5 were dispersed in a concentration of 0.3 g / l water.
• Cotton terry toweling which had previously been treated with a solution of sodium tripolyphosphate (4 g / l water) for 96 hours and was very hard was brought into contact with these dispersions for 5 minutes, after which the treatment liquor was separated by centrifugation for 10 seconds has been. After drying, the terry samples were tested for their softness in comparison to the hard starting material (untreated or differently pretreated samples) by 6 people who were experienced in assessing the softness of textiles (touch marks). The grades were carried out on two pieces of tissue pretreated in the same way with active ingredient (double determination). All terry towels that had been treated with the quaternary ammonium salts according to the invention were assessed as soft and with a pleasant, full feel.
• a molton fabric pretreated in the same way for 120 hours and therefore very hard was assessed as well after the treatment with the same dispersions as the terry toweling fabric.
• a prewashed terry fabric was pretreated by usual prewashing five times and then impregnated with the aftertreatment agent to be tested, just like the fabric "hardened” with sodium tripolyphosphate, for 5 minutes.
• the evaluation in the grip test also revealed a soft, pleasant, full grip.
• the treated textiles had excellent absorbency after drying.
• the results of the handle assessment can be found in detail in Table 2 below.

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• Oil, Petroleum & Natural Gas (AREA)
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• 1986
  • 1986-11-14 DE DE19863638918 patent/DE3638918A1/de not_active Withdrawn
• 1987
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