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Publication numberUS3884626 A
Publication typeGrant
Publication dateMay 20, 1975
Filing dateApr 6, 1973
Priority dateMar 16, 1971
Publication numberUS 3884626 A, US 3884626A, US-A-3884626, US3884626 A, US3884626A
InventorsHansruedi Hoster, Branimir Milicevic
Original AssigneeCiba Geigy Ag
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Process for the dyeing of textile material containing amino or amide groups
US 3884626 A
Abstract
A process for the dyeing of textile material containing amino or amide groups, especially polyamide such as nylon is disclosed which comprises dyeing said material in a homogeneous solution of one or several water-soluble reactive dyestuffs, in a mixture of a chlorinated aliphatic hydrocarbon, especially trichloroethylene or perchloroethylene, with up to 50 percent of a hydrophilic solvent, especially N,N-dimethylformamide, during about 30 to 50 minutes at a dyeing temperature of about 40 DEG to 130 DEG C. The thus obtained dyeings have excellent fastness properties and the procedure is characterised in shortening the dyeing time compared with the conventional dyeing process.
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Description  (OCR text may contain errors)

United States Patent [191 Hoster et al.

[ May 20, 1975 PROCESS FOR THE DYEING OF TEXTILE MATERIAL CONTAINING AMINO OR AMIDE GROUPS [75] Inventors: I-Iansruedi Hoster, Dornach;

Branimir Milicevic, Riehen, both of [21] Appl. No.: 348,657

Related U.S. Application Data [63] Continuation of Ser. No. 124,981, March l6, 1971,

abandoned.

[52] U.S. Cl 8/54; 8/1 A; 8/1 E; 8/94; 8/163; 8/171; 8/174 [51] Int. Cl D06p 3/14 [58] Field of Search 8/1 A, 54, 94, 163, 174, 8/1 E, 86, I71

[56] References Cited UNITED STATES PATENTS 3,510,243 5/l970 Seuret et al 8/39 3,556,708 l/l97l Randall 8/163 X 3,663,161 5/1972 Litzler et al. l. 8/174 3,738,803 6/1973 Blanc et al 8/174 X OTHER PUBLICATIONS Milicevic, Textile Chemists & C0l., 3/11/70, Vol. 2, No. 5, pp. 87-90 and 95-98.

WAS White, Amer. Dyestuff Reporter, 7/3/67, pp. 18-23.

Primary ExaminerBenjamin R. Padgett Assistant ExaminerP. A. Nelson Attorney, Agent, or FirmWenderoth, Lind & Ponack [57] ABSTRACT A process for the dyeing of textile material containing amino or amide groups, especially polyamide such as nylon is disclosed which comprises dyeing said material in a homogeneous solution of one or several water-soluble reactive dyestuffs, in a mixture of a chlorinated aliphatic hydrocarbon, especially trichloroethylene or perchloroethylene, with up to 50 percent of a hydrophilic solvent, especially N,N-dimethylformamide, during about 30 to 50 minutes at a dyeing temperature of about 40 to 130C. The thus obtained dyeings have excellent fastness properties and the procedure is characterised in shortening the dyeing time compared with the conventional dyeing process.

13 Claims, No Drawings PROCESS FOR THE DYEING OF TEXTILE MATERIAL CONTAINING AMINO OR AMIDE GROUPS This is a continuation. of application Ser. No. 124,98l, filed Mar. l6, l97l. now abandoned.

DETAILED DISCLOSURE With regard to the more stringent regulations applying in many places for the protection of the water against contamination, the dyeing of textile material using conventional methods has the disadvantage that large quantities of water are used and subsequently contaminated during the dyeing process. It has, therefore, already been suggested that textile materials be dyed in dye baths prepared from organic solvents.

The present invention relates now to this problem. The object of the invention is therefore a process for the dyeing of textile material containing amino or amide groups characterised in that dyeing is performed in a homogeneous solution of one or several dyestuffs containing in each case at least one free sulphonic acid group and at least one fibre-reactive group in a chlorinated aliphatic hydrocarbon, preferably boiling at a temperature of at least 70C, in a mixture with up to 50 percent of a hydrophilic solvent, preferably at the boiling point of the Organic mixture of solvents.

Suitable dyestuffs usable according to the invention are dyestuffs containing not only at least one sulphonic acid group but also at least one fibre-reactive group. The dyestuffs can belong to the most diverse classes of dyestuffs such as to those of the mono-, disand polyazo dyestuffs; of the anthraquinone, perinone, quinophthalone, oxazine, nitro, phthalocyanine, stilbene and methine dyestuffs, including the styryl. azamethine. polymethine and azostyryl dyestuffs.

To be mentioned as fibre-reactive groupings, e.g. reactive groupings capable of reacting with the substrate to form a covalent bond, there are mentioned the chloromaleinylamino groups. the propiol groupings. monoand dichlorocrotonylamino groups. bromoor chloroacrylamino groups, acrylamino groups, vinyl-sulphone groups and, in particular. the groupings containing a labile substituent, which, with accompaniment of the bonding electron pair, are easily split off, e.g. aliphati cally bound sulphuric acid ester groups or thiosulphuric acid ester groups, and aliphatically bound sulphonyl or sulphonyloxy groups, or halogen atoms, particularly an aliphatically bound chlorine atom. These labile substituents are advantageously in aor B-position of an aliphatic radical which is bound by way of an aminocarbonyl or aminosulphonyl group to the dyestuff molecule; in the case of the dyestuffs under consideration, which contain halogen atoms as labile substituents, these exchangeable halogen atoms can also be, e.g. in an acetyl radical, or in the 01- or B-position of a propionyl radical. Examples of such radicals are. e.g. chloroor oaB-dichloroor dibromopropionylamino groups, or a-chloroacetylamino groups. Preferably, however; the cleavable halogen atoms are in a heterocyclic radical preferably containing 2 to 3 ring-hetero atoms, especially ring nitrogen atoms, e.g. in a phthalazine, pyridazine, pyridai'onc, quinoxaline, quinazoline, oxazole, thiazole. in particular, however, in a pyrimidine or especially triaZine ring, e.g. in a grouping of the formula wherein Z represents a hydrogen atom, an optionally substituted amino group, an etherified oxy or mercapto group, or a halogen atom, or an alkyl, aryl or aralkyl group, A represents halogen or alkylsulphonyl and E represents hydrogen or halogen. The halogen atoms are, e.g. fluorine or bromine atoms, preferably however, chlorine atoms. Of particular interest is the use of dyestuffs containing the grouping of formula l halogen wherein Z representsa chlorine atom, an NH -group, of the radical of an aliphatic or aromatic amine or alcohol; also such fibre-reactive groups of which the cleavable substituent is a quaternary ammonium or hydrazinium group bound especially to a carbon atom of a heterocyclic radical, i.e. a group of the formula (3 -carboxyphenylsulphonyl-l )-triazinyl-6-, 2- carboxymethylsulphonylpyrimidinyl-4-, 2- methylsulphonyl-6-methyl-pyrimidinyl-4-, 2- phenylsulphonyl-6-ethyl-pyrimidinyl-4-, 2,6- bismethylsulphonyl-pyrimidinyl-6-, 2,6-bismethylsulphonyl-S-chloropyrimidinyl-4-, 2,4-bismethylsulphonyl-py'rimidinyl-S-sulphonyl, 2-

methylsulphonyl-pyrimidinyl-4-, pyrimidinyl-4-, 2-trichloromethylsulphonyl-6-methylpyrimidinyl-4-. 2-methylsulphonyl-5-chloro-6-methylpyrimi dinyl-4-, 2-methylsulphonyl-5-bromo-6-methylpyrimidin'yl-4-, 2-methylsulphonyl-5-chloro-6-ethylpyrimidinyl-4-, Z-methylsulphonyl-5-chloro-6- chloromethylpyrimidinyl-4-, 2-methylsulphonyl-4- Z-phenylsulphonyl- 3 chloro-6-methylpyrimidine-S-sulphonyl-Z- methylsulphonyl--nitro--methylpyrimidinyl-4-, 2,5,-

methylsulphonyl-S-sulphopyrimidinyl-4-,

methylsulphonyl-6-carbomethoxy-pyrimidinyl-4-, 2-

methylsulphonyl-S-carboxy-pyrimidinyl-4-, 2- methylsulphonyl-S-cyano-6-methoxy-pyrimidinyl-4-,

2-methylsulphonyl-5-chlor0pyrimidinyl-4-, 2- sulphoethylsulphonyl-6-methyl-pyrimidinyl-4-, 2- methylsulphonyl-S-bromopyrimidinyl-4-. 2- phenylsulphonyl-S-chloropyrimidinyl-4-, Z-carboxymethylsulphonyl-S-chloro-6-methyl-pyrimidinyl-4-, 2- methylsulphonyl-6-chloropyrimidine-4- and -5- carbonyl, 2,6-bis-(methylsulphonyl)-pyrimidine-4- or -5-carbonyl, 2-ethylsulphonyl-o-chloropyrimidine-5- carbonyl, 2,4-bis-( methylsulphonyl )-pyrimidine-5- sulphonyl, 2-methylsulphonyl-4-chloro-o-methylpyrimidine-S-sulphonyl or -carbonyl, 2,4-dichloro-5- fluoro-pyrimidine-6-yl, 2-chlorobenZothiazole-5- or -6- carbonyl or -5- or -6-sulphonyl, 2-arylsulphonylor 2- alkylsulphonylbenzothiazole-S- or -6-carbonyl or -5- or -6-sulphonyl radical, such as Z-methylsulphonylor 2- ethylsulphonylbenzothiazole-S- or -6-sulphonyl, or -carbonyl, 2-phenylsulphonylbenzothiazole-5- or -6- sulphonyl or carbonyl radical, and the corresponding derivatives of 2-sulphonylbenzothiazole-S- or -6- carbonyl or sulphonyl radical, containing on the condensed benzene ring sulpho groups such as 2-chlorobenzothioazole-S- or -6-carbonyl or -sulphonyl, Z-chlorobenzimidazole-S- or -6 -carbonyl or -sulphony], 2-chloro-l-methylbenzimidazole-5- or -6- carbonyl or -sulphonyl, 2-chloro-4-methylthiazole- (l 3)-5-carbonyl or -4- or -5-sulphonyl radicals, and the N-oxide of the chloroor 4-nitroquinoline-5- carbonyl radical. Also mentioned are the 2,2,33- tetrafluorocyclobutanecarbonyll or -sulphonyll 2-fluoro-2-chloro-3 ,3-difluorocyclobutanel -carbonyl and B-(2,2,3,3-tetrafluorocyclobutyl-l )-acryloyl, ozor 4 stated aliphatic acylamino radicals. e.g. acrylic acid, propiolic acid, chloromaleic acid, chloroacrylic acid, a,B-dibromopropionic acid, ,B-chloropropionic acid, etc., particularly, however, the halides corresponding 5 to the heterocyclic reactive radicals.

Particularly preferred are such dyestuffs containing reactive heterocyclic groups with at least two hetero atoms such as halogentriazinyl radicals carrying phenoxy, alkoxy, alkoxy-alkoxy or arylamino radicals, 10 those containing heterocyclic radicals having sulphonyl groups splitting off, and those containing fluorinecontaining heterocycles, especially fluorine-containing pyrimidyl radicals as well as dyestuffs containing as reactive grouping halogenated C fatty acids.

Examples of such dyestuffs which can be used according to the invention are:

o a H l so Na ll l O NH N u-c c-cl ll va N -so a o ca ca o-so -oa B-bromoacryloyl and aor B-alkylor arylsulphonylacso ryloyl radicals. l-/ C1 3 The dyestuffs to be used according to the invention CH areknown in appreciable numbers. The dyestuffs can 3 be prpoduced by the usual methods, e.g. by acylation of dyestuffs containing primary or secondary amino groups, the dyeings being of the most diverse classes as HO S stated, especially, however, of the anthraquinone, 3 IN phthalocyanine, or azo series, using acylating agents N=N containing one or several reactive groups. Mentioned HO S i 7 I H as such acylating agents are, e.g. the anhydrides or chlorides of the acids corresponding to the above 3 9 I 4N HO S----- C I l 3 I Q so mi C N N C 1 x N fcu' N Nil-C -c-ct c N N c 3 H0.s i l 1 w I SOZNH 9 k 2 30 H OH Suitable heavy metals are manganese, iron, and, preferably, chromium. cobalt, nickel and. in particular, N PP l -C c-cl Such dyestuff complexes are derived preferably from 03 1:} 5 such azo dyestuffs which contain a group of the for- 0 Q mulkl C I Cl x Y as well as m N N SO- H a0 I ia-R m N=N l 15 wherein O and Y are each hydroxyl groups, carboxyl groups. 3 ammo groups, or alkylsulphonylamino groups. Also suitable, however, are dyestuffs of the phthalocyanine wherein R is a group of the formulae series.

"W 01 T Cl l N NH -CO l N Cl N}, \S 01/ l /N C1 C1 It is moreover possible to use fibre-reactive dyestuffs 4O Mentioned as examples of suitable fibre-reactive metal complexes containing sulphonic acid groups are having sulpho groups and which contain heavy metals complexes such as, e.g.:

in a complex bond.

no 5 on iio' c1 l 2-chromium complex 7 OH H N 1:1-chr0mium complex NH 7 a 2 Ji Cl fl fl C H CO NH B so H C1 -Cu-O 5.0 I so H 36 a s 3 c u -c1 SO ll 3 The mlxture of organic solvent used according to the 3 O CU Q invention consists of a chlorinated aliphatic hydrocar- NH-CO N\/Cl bon and a hydrophilic solvent. U As chlorinated aliphatic hydrocarbons are used car- OH S0 H bon tetrachloride, chloroform, methylene chloride, trichloroethane, tetrachloroethane, dibromoethylene and, in particular, trichloroethylene and perchloroeth- COCH ylene. I

' 1 :As hydrophilic solvents which are miscible with ().Cu water are used, e.g. aliphatic alcohols such as metha- O H nol,.ethanol, n-propanol, isopropanol, ketones such as 3 acetone, methyl ethyl ketone, cyclohexanone, ether and acetals such as diisopropyl ether, diphenylene ox- HO S-OCH -CH -SO N i ide, dioxane, tetrahydrofuran glycerinformal and glycolformal, as well as acetonitrile and pyridine, diace- 3 tone alcohol, also higher-boiling glycol derivatives such as ethylene glycol monomethyl, -ethyl and -butyl ether C1 c1 and diethylene glycol monomethyl or -ethyl ether and so H diethylene glycol monomethyl or -ethyl ether, thiodil- :P-NH O-Cu 0 3 glycol, ethylene carbonate, 'y-butyrolacton, and particl i ularly the group of the water-miscible aprotic hydro- N=N l philic solvents boiling above C such as N,N-dime- N H thylformamide, N,N-dimethylacetamide, N-hexame- 3 thylphosphoric acid triamide, N-methylpyrrolidone,

9 1,5-dimethylpyrrolidone. N,N-dimethylmethoxyacetamide, N,N,N,N'-tetramethylurea, tetramethyleneurea, tetramethylenesulphone (sulpholane 3- methylsulpholane and dimethylsulphoxide.

Preferred mixtures of these solvents contain 98 to 60, preferably 97 to 70, per cent by weight of halogenated aliphatic hydrocarbon, and 2 to 40, preferably 3 to 30, per cent by weight of hydrophilic components.

In especially preferred mixtures of solvents are used as chlorinated aliphatic hydrocarbons trichloroethylene or perchloroethylene in admixture with a hydrophilic solvent or the amide or lactam of a lower fatty acid, especially N.N-dimethylacetamide or N,N-dimethylformamide or phosphorous containing solvents such as N-hexamethylphosphoric acid triamide in admixture with a chlorinated aliphatic hydrocarbon. Efficient mixtures of solvents consist of perchloroethylene- /N,N-dimethylformamide; trichloroethylene/N,N- dimethylformamide, perchloroethylene/N,N- dimethylacetamide and perchloroethylene/N-hexamethylphosphoric acid triamide.

The present dyeing process is suitable for dyeing of textile material containing amino and amide groups, e.g. certain modacrylic fibres, such as polypropylenes modified with amines, modified polyester fibres containing amino groups, and, preferably, synthetic polyamides, especially poly(hexamethylene-adipic acid amide) or Nylon 6.6, (poly-(w-caprolactam) or Nylon 6, poly(hexamethylenesebacic acid amide) or Nylon 6.10 or poly( l l-aminoundecanoic acid) or Nylon 11 as well as natural polyamides such as wool.

In exhaust dyeing, the textile material to be dyed can be in the form of loose material, fleece, yarn, or as knitted goods or fabrics. It is dyed, in loose form or in a form achieved by mechanical means, in a stationary bath, especially in suitable dye-jigs, winch-vats, cheesedyeing machines, or similar dyeing-machines, depending on the nature of the material to be dyed.

The dyeing may be performed in dyeing apparatus or dyeing vessels which are linked with the outside atmosphere (if necessary via a reflux condenser), or in closed vessels, such as pressure vessels. with or without pressure.

Dyeing is performed at a temperature of about 40 to 130C, preferably at a temperature where the textile material is not injured, for example polyamide at about 105C. during 30 to 50 minutes.

After attainment of the desired depth of colour, the dyed material is removed from the dye-bath and then preferably aftertreated with a commercial cleansingintensifier dissolved in, e.g. perchloroethylene. For the removal of the solvent still adhering, the textile material is treated either with steam or with hot air stream.

A further advantage of the dyeing process according to the invention is the shortening of the dyeing time compared with the conventional dyeing processes.

In the following non-limitative examples, if not otherwise stated, the term parts denotes parts by weight.

percentages are percentages by weight, and temperatures are given in degrees Centigrade.

EXAMPLE 1 03 Parts of the dyestuff of the formula are dissolved in 16 parts of N,N-dimethylformamide, and diluted with 145 parts of perchloroethylene. In this dye liquor, 5 parts of polyamide knitted fabric are dyed for 40 minutes at and then removed from the dye bath. Of a commercial cleansing-intensifier, such as is used in chemical cleaning, 1 to 2 parts are dissolved in 160 parts of perchloroethylene, and the dyed knitted fabric is aftertreated for 10 minutes at 50 in this bath.

'The material is subsequently dried in a warm air stream. By this means is obtained an even red dyeing having excellent fastness properties.

EXAMPLE 2 0.8 Parts of the dyestuff of the formula C CH EXAMPLE 3 0.2 Parts of the dyestuff of the formula C 1 N W are dissolved in 19 parts of N.N-dimethylacetamide. and diluted with 288 parts of perchloroethylene. In this dye liquor, 10 parts of polyamide 66 knitted fabric are dyed for 45 minutes at 105 and then removed from the dye bath. 1 to 2 parts of a commercial cleansingintensifier, such as is used in dry cleaning, are dissolved in 320 parts of perchloroethylene, and the dyed knitted fabric is aftertreated for 10 minutes at 50 in this bath. The material is subsequently dried in a warm air stream. A level scarlet red dyeing having good fastness properties is obtained.

Nil-G NHCOCH CI are dissolved in 19 parts of N,N-dimethylformamide, and diluted with 288 parts of perchloroethylene. In this dye liquor, 10 parts of woollen fabric are dyed for 45 minutes at 90 and then removed from the dye bath. 1 to 2 parts ofa commercial cleansing-intensifier, such as is used in dry cleaning, are dissolved in 320 parts of perchloroethylene, and the dyed fabric is aftertreated for l minutes at 50 in this bath. The material is subsequently dried in a warm air stream. A level blue dyeing having good fastness properties is obtained.

If the 19 parts of N,N-dimethylformamide are replaced by 15 parts of N-hexamethyl-phosphoric acid triamide, and otherwise the procedure of Example 4 is follwed, dyed material is obtained with similarly good properties.

NH l 2 son EXAMPLE 5 0.2 Parts of the dyestuff of the formula H0 9 Cl I ff wl a W H038 \N/. N N/N I: H F I\ C/ are dissolved in 19 parts of N,N-dimethylformamide, and diluted with 288 parts of perchloroethylene. In this dye liquor, parts of polyamide 66 or woollen knitting yarn are dyed for 45 minutes at 121 and then rinsed in a new bath in pure perchloroethylene for l0 minutes at The dyed material is then dried in a warm air stream. A level blue dyeing having excellent fastness properties is obtained.

What we claim is:

1. A process for the dyeing of a textile material containing amino or amide groups, which consists essentially of performing the dyeing by exhaust dyeing in a homogeneous solution of one or several dyestuffs, each of said dyestuffs containing at least one free sulphonic acid group and at least one fiber-reactive group in a solvent mixture consisting essentially of 98 to percent by weight chlorinated aliphatic hydrocarbon, admixed with 2 to 50 percent by weight of a hydrophilic solvent.

2. A process according to claim 1 wherein the dyeing is performed at the boiling point of the organic solvent mixture.

3. A process according to claim 1 wherein the mixture of organic solvents contains 98 to 60 percent by weight of chlorinated aliphatic hydrocarbon and 2 to 40 percent by weight of a hydrophilic solvent.

4. A process according to claim 1 wherein perchloroethylene is used in admixture with a hydrophilic solvent.

5. A process according to claim 1 wherein the solvent mixture employed is the amide or lactam of a lower fatty acid, especially N,N-dimethylacetamide or N,N-dimethylformamide in admixture with a chlorinated aliphatic hydrocarbon.

6. A process according to claim 1 wherein the mixture of solvents used is: perchloroethylene/N,N-dimethylformamide, trichloroethylene/N,N-dimethylformamide, perchloroethylene/N,N-dimethylacetamide or perchloroethylene/N-hexamethylphosphoric acid triamide.

7. A process according to claim 1 wherein natural or synthetic polyamide materials are dyed.

8. A process according to claim 7 wherein wool is dyed.

9. A process according to claim 7 wherein synthetic polyamide material is dyed.

10. The dyed textile material obtained by the process of claim 1.

11. A process according to claim 3 wherein the mixture of organic solvents contains 97 to percent by weight of chlorinated aliphatic hydrocarbon and 3 to 30 percent by weight of a hydrophilic component.

12. A process according to claim 1 wherein the sulphonic acid groups containing dyestuffs contain as the fiber-reactive radical a radical of a halogenated C fatty acid.

13. A process according to claim 12 wherein the chlorinated aliphatic hydrocarbon is perchloroethylene and the hydrophilic solvent is N,N-dimethylformamide. l

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US3510243 *Dec 1, 1966May 5, 1970Geigy Ag J RProcess for the continuous dyeing and printing of fibre material from linear,high molecular esters of aromatic polycarboxylic acids with polyfunctional alcohols
US3556708 *Dec 17, 1965Jan 19, 1971Gaf CorpCellulose dyeing with dichloroacrylamide quaternized reactive dyes
US3663161 *Jun 30, 1969May 16, 1972Ciba LtdProcess for continuous dyeing polyacrylonitrile textile material for a hydrophobic solvent dyebath
US3738803 *Dec 12, 1971Jun 12, 1973Stx Grp Interet EconDyeing of textile fibers in a solvent medium
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4705523 *Jun 4, 1986Nov 10, 1987Burlington Industries, Inc.Process for improving the flame-retardant properties of printed shaped articles from aramid fibers
US4705527 *May 14, 1986Nov 10, 1987Burlington Industries, Inc.Process for the printing of shaped articles derived from aramid fibers
US4710200 *May 14, 1986Dec 1, 1987Burlington Industries, Inc.Process for the continuous dyeing of poly(m-phenylene-isophthalamide) fibers
US4749378 *Sep 12, 1986Jun 7, 1988Burlington Industries, Inc.Process for improving the flame-resistant properties of aramid fibers
US4759770 *Jun 4, 1986Jul 26, 1988Burlington Industries, Inc.Process for simultaneously dyeing and improving the flame-resistant properties of aramid fibers
US4828571 *May 9, 1986May 9, 1989Pensa Ildo ENon-aqueous process for the dyeing of dyable materials at an elevated temperature in a non-reactive environment and in a non-aqueous dye solvent
US5227478 *Jan 24, 1992Jul 13, 1993Sandoz Ltd.2-chloro-4-[4'-(4",8"-disulfonaphth-2"-ylazo)-2'-methoxy-5'-methylanilino]-6
Classifications
U.S. Classification8/543, 8/917, 8/549, 8/564, 8/584, 8/924, 8/475, 8/614, 8/586
International ClassificationD06P1/92, C09B62/00
Cooperative ClassificationC09B62/00, D06P1/928, Y10S8/924, Y10S8/917, D06P1/924
European ClassificationC09B62/00, D06P1/92B2, D06P1/92D