|Publication number||US3768968 A|
|Publication date||Oct 30, 1973|
|Filing date||Jan 18, 1972|
|Priority date||Jan 20, 1970|
|Also published as||DE2002286A1, DE2002286B2, DE2002286C3|
|Publication number||US 3768968 A, US 3768968A, US-A-3768968, US3768968 A, US3768968A|
|Inventors||W Kunze, F Schon, Der Eltz H Van, W Birke|
|Original Assignee||Hoechst Ag|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (4), Referenced by (4), Classifications (10)|
|External Links: USPTO, USPTO Assignment, Espacenet|
United States Patent [1 van der Eltz et al.
[ 1 Oct. 30, 1973 POLYESTER DYE WITH DYE IN METHYLENE CHLORIDE AND A CHLOROFLUOROALKANE Inventors: Hans-Ulrich van der Eltz; Walter Birke, both of Frankfurt, Main; Wolfgang Kunze, Hofheim, Taunus; Franz Schiin, Frankfurt, Main, all of Germany Farbwerke Hoecht Aktiengesellschaft, Frankfurt, Main, Germany Filed: Jan. 18, 1972 Appl. No.: 107,587
Foreign Application Priority Data Jan, 20, 1970 Germany P 20 02 286.0
US. Cl. 8/175, 8/41 A, 8/41 B,
8/41 C, 8/169, 8/176 Int. Cl D06p l/68 Field of Search 8/94, 175, 142
References Cited UNITED STATES PATENTS 4/1964 Castle 8/94 3,473,175 9/1965 Sieber 68/18 R 3,081,140 3/1963 Ford 3,105,769 10/1963 Elleren 8/142 Primary Examiner-Donald Levy Attorney-Curtis, Morris & Safford in which R represents the radical of the formula FCl C-CFCl, Cl C, Cl HC or F ClC-CFCl-, or in a preferably azeotropic mixture of said halogenated solvent with an alcohol, ester, ketone and/or a halogenated hydrocarbon, and then fixing the dyestuff on the textile material by the action of heat.
8 Claims, No Drawings POLYESTER DYE WITH DY-E IN METHYLENE CHLORIDE AND A CHLOROFLUOROALKANE is due to the fact that the water absorbedby the textile material has first tobe brought to the vaporization temperature of water, which requires aconsiderable amount of energy owing to the high specific heat of water (l kcal per kg of water per degree Centigrade of rise of temperature). A substantially higher energy amount has then to be applied for vaporizing the water at 100C about 539' kcal per kg of water at 100C). All these drying operations, moreover, imply the risk that both the textile material and the dyestuffs are adversely affected by the action of heat. In practice, drying has, therefore, to be effected relatively carefully, and a necessary consequence thereof is a low processing speed of the textile material. Another detrimental result of the drying operation is the migration of the dyestuffs. Besides this, the aqueous bath remaining after dyeing still contains a substantial amount of unconsumed dyestuffs and adjuvants which cause considerable difficulties and additional technical expense in the necessary removal of waste water.
It has, therefore, already been proposed to dye from organic liquids, for example esters, such as ethyl acetate; ethers, such as diisopropyl ether; hydrocarbons, such as benzene, and halogenated hydrocarbons, such as perchloro ethylene, trichloro-ethane, carbon tetrachloride, chloroform and trichloro-ethylene (cf. German Offenlegungsschrift No. l 914 055 Some of these solvents are, however, inflammable and sometimes their vapors are explosive. Moreover, some of these solvents have a damaging effect on the fibers and on the dyestuffs, and what is more, the major part of the solvents hitherto used is rather poisonous. It is, therefore, absolutely necessary to operate in explosionproo'f plants and/or to take expensive technical precautions in order to prevent injuries to health by solvent vapors. I
It has now been found that fast dyeings are obtained on synthetic textile materials in a very simple and economic manner by treating said textile material with solutions or dispersions of organic dyestuffs in halogev nated methane or ethane derivatives of the general formula in which R is a group of the formula FCl CCFCl, Cl C-,Cl HC or F ClCCFCl, and then fixing the dyestuffs on the textile material by the action of heat.
According to the process of the invention, the abovementioned halogenated solvents, i.e., 1,2,2-tr'ifluorotrichloro-ethane, monofluoro-trichloro-methane, monofluoro-dichloro-methane and l ,1 ,2,2-tetrafluorodichloro-ethane, are preferably used in the form of pure substances. Among these solvents, trifluorotrichloro-ethane and monofluoro-trichloro methane are generally preferred. In some cases, it is also advantageous to use the above-cited halogenated solvents in admixture with other organic solvents, especially with alcohols, esters, ketones and halogenated hydrocar-- bons. Examples of such secondary solvents are especially methanol, ethanol, ethers of glycols, for example, diethylene-glycol monobutyl ether and methylene chloride. In case mixtures of solvents are used, a weight ratio of from 50 to 99%, preferably to 99%, of the halogenatedmethane or ethane derivatives to l 50%, preferablyl 15%, of the other organic solvents is chosen. If secondary solvents are used, preferably such compounds are selected'which result together with the halogenated solvents as azeotropic mixtures since they behave as uniform substances both in the liquid and in the vapor phases. Hence, there is no decrease in the amount of one of the components during the dyeing operation and the recovering of the solvent. The use of the foregoing solvent mixtures, preferably azeotropic mixtures, is especially advantageous for such cases in which the dyestuff to be applied is only unsatisfactorily soluble in halogenated methane or ethane derivatives alone. Azeotropic mixtures are preferably used in the case of l,2,2-trifluoro-trichloro-ethane since there it is possible to benefit from the resulting boiling point depression and also to use solvents which, as such, are inflammable but in the azeotropic mixture are not. Examples of such azeotropic mixtures are mixtures consisting of 1,2,2-trifluoro-trichloro-ethane and methanol (6% by weight of methanol, boiling point 399C at 760 mm Hg), acetone (12.5% by weight of acetone, boiling point 45C at 760 mm Hg), methylene chloride (49.5% by weight of methylene chloride, boiling point 37 C at 760 mm Hg) and chloroform (7.2% by weight of chloroform, boiling point 47.4C at 760 mm Hg).
As synthetic textile material to be dyed there is especially mentioned material made from polyesters, above all, polyethylene-glycol terephthalate, polyamides, polypropylene, polyacrylonitrile, polyvinyl chloride, cellulose-2 v-acetate and cellulose-tri-acetate. The above-mentioned textile materials may also be blended with other fibrous materials, especially with cellulose fibers or wool; such articles are, for example, mixed fabrics composed of polyethylene-glycol terephthalate and cotton or polyethylene-terephthalate and wool. The synthetic material may be available for dyeing in a variety of forms, for example, combed material, cables, filaments, woven and knit fabrics. Films, sheets and fleeces may also be colored according to the process of the invention.
The dyestuffs to be used for the process of the invention are organic dyestuffs which can be dissolved or dispersed in the above-mentioned solvents or mixtures of solvents and which are absorbed by the synthetic fibrous material during the subsequent heat treatment, especially disperse dyestuffs that have hitherto been used for the dyeing of the above-cited synthetic materials from aqueous media. Moreover, dyestuffs which cannot be applied from aqueous media or which provide only unsatisfactory results according to the conventional method, may now also be employed, especially those known as oilor alcohol-soluble dyestuffs. The dyestuffs suitable for the present invention may belong to different classes of compounds, for example azo dyestuffs, especially monoand disazo dyestuffs, polyazo dyestuffs, dyestuffs of the anthraquinone series, nitro dyestuffs, dyestuffs of the quinophthalone series, such as 3-hydroxy-quinophthalone or 4-bromo- 3-hydroxy-quinophthalone, indigoid dyestuffs as well as components of azo dyestuffs which produce the final azo dyestuff on the fiber by coupling, furthermore perinone, oxazine, nitroso, stilbene, benzothioxanthene and benzoxanthene dyestuffs. Finally, metal complex dyestuffs of the azo series may also be used as far as they can can be dissolved or dispersed in the abovementioned solvents or mixtures of solvents.
If the syestuffs are soluble in the solvents used, it is generally not necessary to add adjuvants. If they are not or are only sparingly soluble, the addition of a suitable dispersing agent that promotes and/or stabilizes fine distribution is advantageous. The addition of a tenside is also advantageous if it should be difficult for the dye to penetrate heavy-weight and tightly woven materials. Tensides of this type are especially oxalkylated, in particular oxethylated, fatty alcohols or fatty acids, alkylpolyglycol ethers, aryl-polyglycol ethers and/or alkylaryl-polyglycol ethers or the sulfonates thereof. These tensides are generally added in an amount of from about 0.1 to 5%, preferably from 0.5 to 1%, calculated on the weight of the solvent.
The process of the invention may be carried out batchwise or continuously, the continuous operation being preferred. The material to be dyed is treated with the organic dyebath in known manner by padding, for example, on a foulard machine, slop-padding or spraying. The temperature applied during this operation has practically no influence on the dyeing result; it is generally within the range of from about to 60C, preferably room temperature. If treatment of the goods with the liquor is carried out at a temperature above the boiling point of the solvent or mixture of solvents, this operation is performed in a pressure-resistant dyeing apparatus under the pressure establishing itself in each case. Finally, dyestuff application may also be carried out at the boiling point of the solvent, and the vapors of the solvent resulting in this proceeding are then condensed by a suitable reflux device and recycled continuously to the dyeing apparatus.
After its treatment with the dyeing liquor the textile material is, if necessary, squeezed to the desired content of impregnation solution of from about 50 to 150%, advantageously about 70 to 90%, calculated on the dry weight of the fibrous material.
The dyestuff amount in the solution or dispersion comprising the dyebath is generally from about 0.001 to 5% by weight and depends, especially, on the color intensity desired, on the material to be dyed or on the dyestuff used. The optimum amount to be used can easily be determined for each individual case by means of corresponding preliminary tests.
The textile material treated with the dyebath is then preferably dried, for example, by hot air, an inert gas such as nitrogen or air, that is drown through the material, or by a moderate heating with infrared radiation. The solvent vapors formed are again liquified in suitable devices by cooling or compression and cooling. The recovered solvents are then available again for the dyeing process. Thus, it is possible according to the invention to operate with a limited amount of solvents. Where required, slight losses that cannot be avoided in any case are compensated for by feeding in fresh solvent.
The dyestuffs thus applied are fixed onthe textile material by the action of heat in a manner usual for each individual synthetic material, generally at a temperature of from about 100 to 240C.
Said heat treatment can be performed with superheated steam or vapors of organic solvents at a temperature of from about to C. Fixing can also be performed in melts made from molten metals, paraffins, waxes, oxalkylation products of alcohols or fatty acids or in eutectic mixtures of salts at temperatures of from about 100 to 220C. Preferably, dyestuff fixation is carried out by means of dry heat, i.e., according to the so-called Thermosol process, at about to 220C. The fixation temperature to be applied depends, especially, on the textile material to be dyed.
Although the textile material is preferably dried as mentioned above prior to fixing, it is also possible to perform the drying operation and the thermal treatment in a single step.
An after-treatment of the dyeings obtained according to the invention is generally not necessary but, when tensides have additionally been used, such an aftertreatment of the textile material may be advantageous and is suitable performed by washing the material once more with the solvent or solvent mixture already used in the dyeing operation. Of course, another methane or ethane derivative of the aforementioned formula may also be used for this purpose. A reductive aftertreatment for the elimination of unfixed dyestuff, as generally necessary in conventional processes, is not required for the process of the invention, except in special cases.
The dyeings obtainable according to the claimed process have at least the same fastness properties as dyeings produced from aqueous media according to the conventional method have.
The technical advantage of this invention over the prior art technique using aqueous dyebaths resides, especially, in the fact that a substantially lower energy amount is required for the drying operation than with the usual dyeing methods from aqueous media. For example, the specific heat of methane and ethane derivatives used according to the invention amounts to about 0.2 0.25 kcal per kg per degree centigrade whereas, in comparison thereto, water has a specific heat of l kcal per kg per degree centigrade. Thus, in order to heat the dyeing medium to its boiling point, only a fraction of the heat amount needed for "water is required according to the invention and, moreover, the liquids used in the claimed process have substantially lower boiling points than water. Above all, the energy amount of be applied for the vaporization of the dyeing liquid is substantially smaller according to the invention than according to the conventional method. In order to varporize 1 kg of water at the boiling point, about 539 kcal have to be spent, whereas the heat of vaporization at the boiling point of the solvents of the above formula is from about 33 to 58 kcal per kg. Hence, the energy consumption according-to the invention is only a fraction of that to be spent for the drying operation according to the dyeing process from aqueous media. Moreover, due to the favorable energy balance, it is possible to use in the claimed process drying devices of a simpler type and, since drying can be performed substantially quicker than with the conventional process, the processing speed of the goods is substantially higher. Another very substantial advantage of the invention is that there are no difficulties involved wiJh waste water purification. Furthermore, according to the invdntion, almost no corrosion is observed on the dyeing machines as it is when water is used. Another advantage is the successful use of dyestuffs that could not be used for the dyeing from aqueous media or which provided only unsatisfactory results. I 7
When dyeing from an aqueous bath, most of the dyestuffs have to be applied in the form of preparations since the crude dyestuff yields only poor results. According to the process of the invention, however, dyestuffs that are soluble in the solvents used can be applied without any pre-treatment or any additive.
In comparison to known processes in which also organic solvents are used, the process of the invention has the advantage that the solvents or solvent mixtures used are not inflammable and almost not poisonous. For example, the MAK-values (maximum allowable concentration of industrial atmospheric contaminants at the work place) of the above-cited methane or ethane derivatives are about'l ,000 ppm (cf. Ullmanns Encyklopaedie der technischen Chemie, Vol. 2/2 (1968) pages 620 to 624; cf. also Threshold Limit Values). In contradistinction thereto, the organic solvents-used in the known processes are inflammable and/or they are comparatively strong poison having MAK-values of 100 ppm and, in many cases, even less. For example, benzene has a MAK-value of 25 ppm and carbon tetrachloride only of 10 ppm. Furthermore, the solvents used according to the invention have a substantially lower surface tension than the solvents hitherto used for the same purpose, and therefore the textile material is much better wetted in the dyebath. Hence, the dyeings obtained, although produced with the same dyestuff amount, have a far greater color intensity than the dyeings obtained by the known process. In contrast to the known process, the use of the above-mentioned solvents or solvent mixtures does not damage the fibers.
The devices mentioned in the following Examples are closed ones so that no vapors of solvents can escape. If the dyeing temperature is above the boiling point of the solvent or solvent mixture used, the treatment is performed in pressure-resistant dyeing apparatuses under the pressure that establishs itself in each case. Although not referred to particularly in the following Examples, the solvent vapors formed during the drying operation are condensed and recovered by cooling or by compression and cooling. The solvents thus recovered can then be used again. The Colour Index Numbers referred to in the Examples relate to Colour Index, Volume IIl, 2nd edition (1956); the percentages indicating the squeezing effect are by weight of the dry fibrous material.
The following Examples serve to illustrate the invention.
E X A M P L E 1 Three Grams of the dyestuff of the formula (C.l. No. 26105 Solvent Red 24) were dissolved in 1 liter of trichloro-fluoromethane at about 20C. A mixed fabric composed of polyester fibers and wool was padded with this dyestuff solution on a foulard machine at the cited temperature, with a squeezing effect of Subsequently, the fabric was dried at room temperature by yaporization of the solvent. The dyestuff was then fixed by means of a thermosol treatment for 45 seconds at 190C. An intense red dyeing on the polyester portion of the fibre blend was obtained. A reductive after-treatment of the dyeing was not required.
E X-A M P L E 2 Three Grams of the dyestuff of the formula (C.I. No. 11360 Solvent Brown 3) were pasted up with 10 cc. of diethylene-glycol monobutyl ether and then this paste was diluted to 1 liter with trichlorofluoromethane at about 20C. A fabric made from texturized polyester fibers was padded with this bath at a squeezing effect of 80%. The fabric was dried by drawing off the solvent vapors in an appropri-' ate apparatus. Subsequently, the material was thermosoled for 30 seconds at C for fixing the dyestuff. An orange brown dyeing was obtained.
EXAMPLES Two Grams of the dyestuff of the formula EXAMP'LE4 Twenty Grams of the commercial disperse dyestuff of the formula were dispersed in 1 liter of trichloro-fluoromethane at about 15C. A blended fabric made from polyester fibers and cotton was padded with this dyestuff dispersion at room temperature. The fabric was dried by drawing off the solvent in an appropriate apparatus.
Subsequently, the dyestuff was fixed on the fabric by a thermosol treatment for 1 minute at 200C. A red dyeing on the polyester portion of the blend was obtained.
EXAMPLES Five Grams of the commercial disperse dyestuff of the formula were pasted up with 40 ml of benzoic acid methyl ester and stirred into 960 ml of trichloro-fluoromethane at about 20C. A fabric made from polyester fibers was impregnated with this padding liquor and treated fur-' ther as disclosed in Example 4. An orange dyeing ,was obtained.
E X A M P L E 6 Three Grams of the disperse dyestuff of the formula CHz-CHz-OH were pasted up with 30 ml of diethylene-glycol monobutyl ether. Subsequently, the mixture was diluted to 1 liter with trichloro-fluoromethane at about 20C. A polyester fabric was padded with this bath and treated further as disclosed in Example 4. A brown dyeing was obtained.
EXAMPLE7 Ten Grams of the commercial disperse dyestuff of the formula .lIzN )(l)\ (1)11 I Br l 110 NH:
were dispersed in 1 liter of l,2,2-trifluoro-trichloroethane at about 30C. A fabric made from polyester fibers was padded with this bath on a foulard machine. The material was then dried by drawing off the solvent vapors in vacuo by means of an appropriate apparatus. Subsequently, the dyestuff was fixed on the fiber by a thermosol treatment for 1 minute at 190C. A blue dyeing was obtained.
E x A M P L E 8 Three Grams of the dyestuff of the formula ple 7. A brown dyeing was obtained.
E X A M PL E 9 Two Grams of the dyestuff of the formula (C.I. No. 12700 Solvent Yellow 16) were dissolved at about 25C in 1 liter of 1,2,2-trifluoro-trichloro-ethane. A fabric made from texturized polyester fibers was padded with this dyestuff solution. The fabric was dried by drawing off the solvent vapors under reduced pressure. Subsequently, the dyeing was finished by a thermosol treatment for 40 seconds at C. A yellow dyeing was obtained.
E X A M P L E 10 Five Grams of the dyestuff of the formula (C.I. No. 12055 Solvent Yellow 14) were dissolved at about 25C in 1 liter of an azeotropic mixture consisting of 94% of l,2,2-trifu1oro-trichloroethane and 6% of methanol. This solution was then applied by padding on a foulard machine to a blended fabric made from polyester fibers and cotton. Half of the impregnated blended fabric was dried under reduced pressure. The other half of the fabric was dried with hot air of 40C on a conventional drying device. Subsequently, both halves were thermosoled for 45 seconds at C, for fixing the dyestuff. In both cases, orange red dyeings were obtained.
E X A M P L E l 1 Two Grams of the dyestuff of the formula J Qt;
(C.I. No. 26150 Solvent Black 3) were dissolved at about 30C in 1 liter of an azeotropic mixture consisting of 94% of l,2,2-trifluoro-trichloroethane and 6% of methanol. A fabric made from polyester fibers was padded with this bath. Drying and after-treatment of the fabric were performed as disclosed in Example 10. A grey dyeing was obtained. E x A M P L E 15 2.5 Grams of the disperse dyestuff of the formula E X A M P L E 12 Three Grams of the dyestuff of the formula CHz U1b O11 N=N N CH -CHz-OH (3H3 ClHa H0 01 were dissolved in 40 ml of diethylene-glycol monobutyl ether and the solution was then diluted to 1 liter with trichloro-fluoromethane at about 20C. A polyamide- 6,6 fabric was impregnated with this padding liquor on a foulard machine, then dried with hot air of about 40C in a drying device and thermosoled for 30 seconds (C.l. No. 26105 Solvent Red 24) o were dissolved at about C in 1 liter of trichloroat 190 A red rown dyeing was obtained. fluoro-methane. A combed material made from poly- E X A M P L E 16 propylene fibers i padded wlth .thlspyestuff Solutlon Ten Grams of the commercial disperse dyestuff of on a foulard machine and then dried in the air. Subsethe formula quently, the dyestuff was fixed for 30 seconds at 140C 0 I by means of a heat treatment. A red dyeing was obv V V H V tained.
When, in the above Example, the same amount of N:NN=NOH monofluoro-dichloromethane or 1, l ,2,2-tetrafluorodichloro-ethane was used instead of trichloro- 25 fluoromethane, almost the same results were obtained.
E x A M P L E 13 were dispersed at about 25C in 1 liter of 1,2,2-trifiuoro-trichloro-ethane. A staple fiber yarn made from polyvinyl chloride fibers having high resistance to heat, was padded with this dyestuff dispersion on a foulard machine and dried at about 50C. Subsequently, the yarn was thermosoled for seconds at a temperature NH N=N-N=N/ of 130C. An orange brown dyeing was obtained.
0 We claim: 7 U l. A process for the dyeing of a textile material made NH of fibers of linear aromatic polyester which comprises impregnating said textile material with a dyebath consisting essentially of an organic dyestuff dissolved or dispersed in a halogenated methane or ethane of the formula Two Grams of the dyestuff of the formula (CI. No. 26150 Solvent Black 3) were dissolved at about 30C in 1 liter of an azeotropic mixture consisting of 94% of 1,2,2-trifiuorotrichloroethane and 6% of methanol. A staple fiber fab- R F I'iC made from cellulose 2 1% acetate fibers was wherein R is CFCI CFCI2, CC|3, 1 v or padded with this dyebath on a foulard machine and 1 and methylene chloride, and fixing then dried at about 50C. Subseq n ly the p y g said dyestuff on or in said fibers by applying heat to said was treated for 30 seconds at 160C, for fixing the dyetextile material. stuff. A grey dyeing was obtained. 2. A process according to claim 1 wherein said halogenated methane or ethane and said methylene chlo- E X A M P L E 14 ride are an azeotropic mixture thereof.
3. A process according to claim 1 wherein said halogenated methane or ethane and said methylene chloride are in a weight ratio of 50% to 99% of the former to 50% to 1% of the latter.
Two Grams of the dyestuff of the formula m 4. A process according to claim 1 wherein said halo- H genated methane or ethane and said methylene chlo- N=Nii 1 1 5 5 ride are in a weight ratio of to 99% of the former to. 15% to 1% of the latter.
( 5. A process according te claim 1 wherein said textile H3 material is impregnated with said dyebath in an amount of about 50% to about by weight of said material.
6. A process according to claim 1 wherein said textile (Cl NO 12700 Solvent Yellow 16) 60 material is impregnated with said dyebath in an amount were dissolved in 1 liter of l,2,2-trifluoro-trichlorox lgg zzggr z zz z i g' g fi z gijggg 3:2
ehtane' Subsequently this bath was applied by padding bath COEltfllIlS about 0.152: to about 5% by weight 0 f a on a foulard machine at about 40C to a fabric made surface active agent.
from cellulose-triacetate fibers. After the pad-dyeing 65 A process according to claim 1 wherein said had been dried in the air, a thermosol treatment was bath contains about 0.5% to about 1% by weight f 3 performed for 30 seconds at C. A yellow dyeing urfa e i e t;
was obtained. 1r 4r
|Cited Patent||Filing date||Publication date||Applicant||Title|
|US3081140 *||Oct 21, 1958||Mar 12, 1963||John Ford||Process for coloring polyvinyl materials|
|US3105769 *||Oct 17, 1960||Oct 1, 1963||Ellerin Erwin H||Solution for reconditioning typewriter ribbons and the like and methods of reconditioning such ribbons|
|US3129053 *||May 21, 1962||Apr 14, 1964||Du Pont||Dispersions of organic dyes and pigments in fluoroalcohols|
|US3473175 *||Feb 14, 1968||Oct 21, 1969||American Permac Inc||Process and apparatus for the controlled treatment of textiles|
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US3900287 *||Jan 9, 1973||Aug 19, 1975||Du Pont||Exhaust disperse dyeing of synthetic polymers utilizing a saturated liquid fluorocarbon|
|US4065259 *||Apr 23, 1976||Dec 27, 1977||E. I. Du Pont De Nemours And Company||Fluorocarbon dye dispersion for exhaust disperse dyeing|
|US4098947 *||Feb 20, 1975||Jul 4, 1978||Joachim Schmidt||Copy paper|
|US5149138 *||Aug 27, 1990||Sep 22, 1992||Zemsky Michael D||Method of applying a fluorescent marking composition|
|U.S. Classification||8/491, 8/532, 8/933, 8/615|
|Cooperative Classification||Y10S8/933, D06P1/924, D06P1/928|
|European Classification||D06P1/92D, D06P1/92B2|