Classifications

• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
  • D06P1/02—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using azo dyes
  • D06P1/12—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using azo dyes prepared in situ
  • D06P1/127—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using azo dyes prepared in situ using a stabilised diazo component, e.g. diazoamino, anti-diazotate or nitrosamine R-N=N-OK, diazosulfonate, hydrazinesulfonate, R-N=N-N-CN
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
  • Y10S8/913—Amphoteric emulsifiers for dyeing
  • Y10S8/914—Amino carboxylic acids
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
  • Y10S8/916—Natural fiber dyeing
  • Y10S8/917—Wool or silk
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
  • Y10S8/916—Natural fiber dyeing
  • Y10S8/918—Cellulose textile
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
  • Y10S8/92—Synthetic fiber dyeing
  • Y10S8/921—Cellulose ester or ether
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
  • Y10S8/92—Synthetic fiber dyeing
  • Y10S8/927—Polyacrylonitrile fiber

Definitions

• United States Patent U.S. Cl. 8-46 2 Claims ABSTRACT OF THE DISCLOSURE Process for the production of water-insoluble azo dye stuffs on textile material comprising treating the textile material in an alkaline bath containing a coupling component and a compound of the formula wherein R is a radical of an aromatic or heterocyclic amine, Me is an alkali metal or alkaline earth metal and n is 1 or 2, a Wetting or dispersing agent and, optionally, an inorganic salt, and producing the dyestuff by treatment with acid agents below 40 C.
• water-insoluble azo dyestuffs can be produced on textile material comprising cellulose or protein fibers by treating the textile material in an alkaline bath containing a coupling component and a diazoamino or tetrazoamino compound of the formula in which R represents the radical of an aromatic or heterocyclic amine, Me represents an alkali metal or alkaline earth metal and It stands for one of the integers 1 and 2, a wetting or dispersing agent and, if desired, an inorganic salt, and producing the dyestuff by treatment with acid agents below 40 C.
• the process of the invention is carried out by treating the textile material in the form of yarn in hanks, wound bodies, combed or loose material in an alkaline bath which contains a coupling component having a high substantivity and a diazoamino or tetrazoamino compound of the above formula, a wetting or dispersing agent and, if desired, an inorganic salt, for example sodium chloride, sodium phosphate or sodium sulfate.
• the treatment is carried out for at least minutes so that the coupling component can be sufiiciently and uniformly fixed on the textile material. In general. the treatment is carried out at room temperature or at moderately elevated temperature, preferably below 35 C.
• an organic acid is added to the bath, for example formic acid, acetic acid, tartaric acid, citric acid, lactic acid or glycolic acid or a mixture of said acids or a mixture of an inorganic acid, for example hydrochloric acid or sulfuric acid, with an organic acid, in an amount such that the total quantity of alkali in the bath and on the textile material is neutralized and a pH value beween about 4 and 7 is attained, the temperature being below 40 C.
• the dyestuff is produced on 3,441,364 Patented Apr. 29, 1969 the textile material.
• the treated material is then Washed in a neutral or acid bath, if desired in the presence of dispersing agents and the dyeing is finished in the usual manner. Dyeings which possess an excellent fastness to rubbing are obtained.
• Piece goods can be dyed by impregnating the goods on :1 padding machine having two or more rollers with a mixture of the coupling component and an excess of diazoamino or tetrazoamino compound, rolling them together, and after 30 minutes for example, coupling is effected by passing the treated goods through an organic acid, a mixture of organic acids or a mixture of organic and inorganic acids at a temperature below 40 C.
• This process can also be performed by passing the material through a compartment of a roller vat or by several passages on a jig or on a Winch vat, in which process additions of inorganic salts and dispersing agents sometimes show an excellent effect in the impregnating and developing stage.
• compounds can be used which are distinguished by a high substantivity for the textile material, i.e. coupling components which at a goods-to-liquor ratio of 1:20, a dyeing period of 30 minutes at 30 C., a concentration of 1 gram per liter of water without the addition of salts and an excess of 4.5 grams of sodium hydroxide per liter of bath, possess such a high substantivity that at least 9 grams are absorbed by 1 kilogram of cotton.
• a high substantivity for the textile material i.e. coupling components which at a goods-to-liquor ratio of 1:20, a dyeing period of 30 minutes at 30 C., a concentration of 1 gram per liter of water without the addition of salts and an excess of 4.5 grams of sodium hydroxide per liter of bath, possess such a high substantivity that at least 9 grams are absorbed by 1 kilogram of cotton.
• Suitable compounds are, for example: 2,3-hydroxynaphthoylamino-benzenes such as 1-(2',3-hydroxynaphthoylamino)-2,5-dimethoxy-4-chlorobenzene or 1-(2',3-hydroxynaphthoylamino) 2 methoxy-4-chloro-5-methylbenzene; 6-bromoor 6-methoxy-2,3-hydroxynaphthoic acid aryl amides such as l-(6'-bromo-2',3-hydroxynaphthoylamino)-2-methoxybenzene; condensation products of 2,3-hydroxynaphthoic acid and polynuclear isocyclic or heterocyclic amines such as 2-(Z',3-hydroxynaphthoylamino)-naphthalene, 2-(2,3'-hydroxynaphthoylarnino) -carbazole, 2-(2'
• the compounds commonly used in the ice-colour technique enter into consideration, for example condensation products of high molecular weight fatty acids and protein degradation products, condensation products of high molecular weight fatty acids and aminoalkyl-sulfonic acids, condensation products of formaldehyde with naphthalene-sulfonic acids or purified sulfite cellulose waste liquor.
• the process of the present invention can be carried out on textile material of natural or regenerated cellulose, cyano-ethylated cellulose, wool, natural silk, regenerated protein fibers or on mixtures of natural or regenerated cellulose with copolymers of acrylonitrile, vinylidene chloride and N-vinylpyrrolidone.
• the process of the present invention provides an essential simplification.
• the dyebath is discharged after impregnation with the coupling component, the fabric is centrifuged, filtered with suction or subjected to an intermediate rinsing, and the dyestuff is developed in a second bath with a diazonium compound.
• the process of the present invention includes the impregnation and developing stage in one bath, and after a period necessary for fixing the coupling component coupling takes place without any intervening operation so that the duration of such a dyeing process is essentially reduced.
• German Patent 1,057,061 teaches a process for producing water-insoluble azo dyestuffs on vegetable fibers by treating the said fibers at a long goods-to-liquor ratio in a bath containing a coupling component and a diazoor tetrazoamino compound without solubilizing groups and developing the azo dyestufi by treatment in an acid bath.
• the process according to the invention which is carried out with the use of substantive coupling components and diazoaminoor tetrazoamino compounds from diazotized aromatic monoor diamines and cyanamide, is distinguished in that the dyestuffs can be developed at low temperatures and an elevation of the temperature after the addition of acid is not necessary.
• a further advantage of the present process resides in the fact that the diazoamino or tetrazoamino compounds with cyanamide are present as stabilizers in the alkaline bath in the form of dissolved alkali metal salts whereby a complete penetration of the material to be dyed is achieved resulting in a quantitative coupling, whereas with the use of water-insoluble diazoamino compounds the latter are superficially deposited on the material to be dyed, which may result in an incomplete penetration of the dyestutf.
• a re-coupling of the diazonium compound with the cyanamide cannot take place because on splitting neutral salts and urea are formed in addition to the diazonium compound. In this manner the dyestufi components used are fully utilized.
• EXAMPLE 1 A cross-wound bobbin of 500 grams of cotton yarn was treated in a dyeing machine having a content of about 6 liters for 30 minutes with a solution of 20 C, (circulation towards the outside) containing in about 5.8 liters of water 8.1 grams of the diazonium compound of diazotized l-amino-Z,S-dichlorobenzene and sodium cyanamide and 3 grams of the sodium salt of ethylene diaminetetracetic acid with dc-aeration of the core of the bobbin.
• the bath was discharged after about 30 minutes, the yarn was thoroughly rinsed and soaped for 15 minutes at 60 C. with 16.5 grams of a mixture of 63% of perchloroethylene, 17% of a reaction product of about 10 mols of ethylene oxide with 1 mol of nonyl phenol and 20% of isopropyl alcohol and 13 grams of a solution of 25% strength of sodium nitrilotriacetate in 6 liters of water.
• the bath was discharged, the yarn was rinsed and soaped for 15 minutes at the boil with 13 grams of a reaction product of about 10 mols of ethylene oxide with 1 mol of nonyl phenol and 13 grams of a solution of 25% strength of sodium nitrilotriacetate in 6 liters of water, the yarn was rinsed again and dried. A dark violet dyeing was obtained which was very fast to rubbing.
• EXAMPLE 2 In the manner described in Example 1, a cross-wound bobbin of 500 grams of cotton yarn was de-aerated at 20 C. in a dyeing machine having a capacity of 6 liters with a solution of 9.6 grams of the diazoamino compound of diazotized 1-amino-2-methoxy-5-chlorobenzene and sodium cyanamide and 6 grams of sodium ethylene diamine tetraacetate in 6 liters of water.
• the yarn was further treated for 30 minutes with change of the bath direction, 120 grams of sodium chloride were added and treatment was continued for 20 minutes at 20 C. 6 cc. of a reaction product of about 20 mols of ethylene oxide with cresyl camphane, 51.3 cc. of hydrochloric acid of 20 B. and 36 cc. of acetic acid of 50% strength were added, whereby the pH was reduced to about 4.5 and coupling occurred. After a further 20 minutes the yarn was aftertreated as described in Example 1, rinsed and dried. A dark red dyeing was obtained which was fast to rubbing.
• Cotton yarn was treated at 20 C. at a goods-to-liquor ratio of 1:20 in an aqueous solution containing per liter of water 1.1 grams of 2-(2',3-hydroxynaphthoyl amino)-3-methoxy-diphenylene oxide, 3 grams of a dis persing agent containing 16% of a condensation product of partially decomposed casein and palm-kernel fatty acid and 8% of a condensation product of a-ethylhexylchlorocarbonic acid ester and sodium a-ethylhexyltaurate, 5 cc.
• Cotton yarn was treated at 20 C. at a goods-to-liquor ratio of 1:20 in an aqueous solution containing per liter of water 1.1 grams of 2-(2',3-hydroxynaphthoylamino)- 3-methoxy-diphenylene oxide, 3 grams of a dispersing agent containing 16% of a condensation product of partially decomposed casein and palm-kernel fatty acid and 8% of a condensation product of a-ethylhexylchlorocarbonic acid ester and sodium a-ethylhexyltaurate, 5 cc.
• EXAMPLE 5 A cross-wound bobbin of 500 grams of cotton yarn was treated for de-aeration in a goods-to-liquor ratio of 1:12 at 20 C. with the aqueous solution of 5 grams of the diazoamino compound of diazotized 1-amino-2- methoxy-benzene-5-carboxylic acid amide and sodium cyanamide, 3 grams of sodium ethylene diamine acetate, 24 grams of a dispersing agent containing 16% of a condensation product of partially decomposed casein and palm-kernel fatty acid and 8% of a condensation product of u-ethylhexyl-chlorocarbonic acid ester and sodium ozethylhexyltaurate, and grams of sodium chloride with circulation of the bath towards the outside.
• EXAMPLE 6 A cross-wound bobbin of 500 grams of cotton yarn was treated at a goods-to-liquor ratio of 1:12 at 20 C. with the aqueous solution of 13.6 grams of the diazoamino compound of diazotized 1-amino-2-methyl-3-chlorobenzene and sodium cyanamide, 3 grams of the sodium salt of ethylene diamine tetraacetic acid, 60 grams of sodium chloride and 24 grams of a dispersing agent containing 16% of a condensation product of partially decomposed casein and palm-kernel fatty acid and 8% of a condensation product of a-ethylhexyl-chlorocarbonic acid ester and sodium a-ethylhexyl taurate.
• EXAMPLE 7 A cross-wound bobbin of 500 grams of cotton yarn was treated in a dyeing machine having a capacity of about 6 liters, for minutes with circulation of the bath towards the outside with a solution of C. containing 9.8 grams of the diazoamino compound of diazotized l-amino-2,5-dichlorobenzene and sodium cyanamide and 6 grams of sodium ethylene diamine tetraacetate.
• EXAMPLE 8 A cross-wound bobbin of 500 grams of cotton yarn was treated in a dyeing machine having a capacity of 6 liters, with circulation towards the outside, with a solution of 20 C. containing 8.4 grams of the diazoamino compound of diazotized l-amino-2-methoxy-5-nitrobenzene and sodium cyanamide and 6 grams of sodium ethylene diamine tetraacetate.
• the yarn was rinsed, treated with 16.5 grams of a mixture of 63% of perchloroethylene, 17% of a reaction product of about 10 mols of ethylene oxide with 1 mol of nonyl phenol and 20% of isopropyl alcohol and 12 grams of a solution of 25% strength of sodium nitrilotriacetate in 6 liters of water for 15 minutes at C., rinsed and treated for 15 minute-s at boiling temperature with 12 grams of a reaction product of about 10 mols of ethylen oxide with 1 mole of nonyl phenol and 12 grams of a solution of 25% strength of sodium nitrilotriacetate in 6 liters of water, rinsed again and dried. A brownish-yellow dyeing of a very good fastness to rubbing was obtained.
• EXAMPLE 9 A cross-wound bobbin of 500 grams of cotton yarn was treated in a dyeing machine having a capacity of 6 liters, with circulation of the bath towards the outside, at 20 C., with a bath containing 10.8 grams of the diazoamino compound of diazotized l-amino-2-methoxy-5- nitrobenzene and sodium cyanamide, 60 grams of sodium chloride and 6 grams of sodium ethylene diamine tetra acetate.
• the bath was discharged, the yarn was rinsed and treated for about 15 minutes at 60 C. with 16.5 grams of a mixture of 63% of perchloroethylene, 17% of a reaction product of about 10 mols of ethylene oxide with 1 mol of nonyl phenol and 20% of isopropyl alcohol, and 12 grams of a solution of 25% strength of sodium nitrilotriacetate in 6 liters of water, rinsed in the hot and treated for about 15 minutes at boiling temperature with 12 grams of a reaction product of about 10 mols of ethylene oxide with 1 mol of nonyl phenol, 6 grams of calcined sodium carbonate and 12 grams of a solution of 25 strength of sodium nitrilotriacetate in 6 liters of water, thoroughly rinsed in the hot and cold and dried. A red dyeing of good fastness to rubbing was obtained.
• the bath was discharged, the fabric was thoroughly rinsed and soaped at 60 C. and at boiling temperature each time for 20 minutes with 4.8 kilograms of Castile soap, 0.8 kilogram of sodium nitrilotriacetate and 0.8 kilogram of a condensation product of oleic acid and methyltaurine in 1600 liters of water, rinsed and dried. An even black dyeing fast to rubbing was obtained.
• EXAMPLE 11 1 kilogram of natural silk was treated at 25 C. at a goods-to-liquor ratio of 1:20 with an aqueous solution containing per liter of water 1.5 grams of 2(2',3-hydroxy-naphthoylamino)-naphthalene, 2.1 grams of the diazoamino compound of diazotized 1-amino-2-methyl- 3-chlorobenzene and sodium cyanamide, 0.5 gram of a condensation product of oleic acid and N-methyltaurine, 2 grams of a dispersing agent containing 16% of a condensation product of partially decomposed casein and palm-kernel fatty acid and 8% of a condensation product of a-ethylhexyl-chlorocarbonic acid ester and sodium ethylhexyltaurate, 1.6 grams of sodium hydroxide and 23 grams of sodium chloride.
• the aftertreatment was carried out with 1 gram of a condensation product of oleic acid and methyltaurine and 0.5 gram of sodium nitrilotriacetate per liter of water at 60 C. to avoid a damage of the wool fiber.
• EXAMPLE 12 A cross-wound bobbin of 500 grams of cotton yarn was thoroughly wetted in a dyeing machine and treated at about 30 C. with a bath prepared in the following manner:
• Solutions (a) and (b) were introduced successively into a bath of about 27 C. containing in about 5400 cc. of water 29.5 cc. of sodium hydroxide solution of 38 Be., 50.4 grams of trisodium phosphate and 6.5
• Solutions (a) and (b) were introduced into a bath containing in 19 liters of water 20 grams of a condensation product of oleic acid and methyltaurine, 148 cc. of sodium hydroxide solution of the 38 B., 600 grams of sodium chloride and 10 grams of sodium ethylene diamine tetraacetate. After 45 minutes 97 cc. of acetic acid of 50% strength and 138 cc. of hydrochloric acid of 20 B. were added over a period of 3-5 minutes and the material was treated for about 30 minutes at a pH of about 4.8. It was then thoroughly rinsed, first at 30-40 C. and then in the cold, and treated, each time for 15 minutes, at 60 C.
• EXAMPLE 14 1 kilogram of a mixed fiber yarn of 50 parts of cotton and 50 parts of a copolymer of acrylonitrile, vinylidene chloride and N-vinyl-Z-pyrrolidone was treated at 30 C. in a goods-to-liquor ratio of 1:20 with an aqueous solution containing per liter of water 1.6 grams of 2-(2',3'- hydroxynaphthoylamino)-napthalene, 2.2 grams of the iazoamino compound of diazotized l-amino-Z-methyl-S- chlorobenzene and sodium cyanamide, 0.5 gram of a condensation product of oleic acid and N-methyltaurine, 1.6 grams of sodium hydroxide and 33 grams of sodium chloride.
• the yarn was treated for 1 hour and over a period of 3-5 minutes 7 cc. of acetic acid of 50% strength were added.
• the yarn was treated for 30 minutes at a pH of about 5.5, thoroughly rinsed hot and cold and soaped for 30 minutes at the boil with 2 grams of a condensation product of oleic acid and methyltaurine and 0.5 gram of sodium nitrilotriacetate per liter of water, rinsed hot and cold and dried.
• a red dyeing having a very good covering capacity for both fibers was obtained.
• Solutions (a) and (b) were introduced with stirring into a solution of 1 gram of a condensation product of oleic acid and methyltaurine, 3 cc. of sodium hydroxide solution of 38 B. and 20 grams of sodium chloride in 920 cc. of water of 30 C.
• the material was treated for 30 minutes, 8 cc. of acetic acid of 50% strength were slowly added and treatment was continued at a pH of about 5.5 for a further 30 minutes.
• the material was rinsed at a moderate temperature and in the cold and soaped, each time for 15 minutes at 60 C. and at boiling temperature, with 1 gram of a condensation product of oleic acid and methyltaurine and 0.5 gram of sodium nitrilotriacetate per liter of water, rinsed and dried. A fast black dyeing was obtained.
• TAB LE Diazoamino compound of sodium Goods-to pH value cyanamide and diazoliquor during tized Gram/liter ratio coupling Tint 1-amino-2-phenoxy-5- 1. 49 1:20 4. Red.
• a process for the production of water-insoluble azo dyestuflis on textile material comprising fibers selected from the group consisting of cellulose fibers, protein fibers and fiber mixtures of cellulose and a copolymer of acrylonitrile, vinylidene chloride and N-vinyl pyrrolidone, which comprises treating the textile material in an alkaline bath which contains a coupling component highly substantive for the material to be dyed selected from the group consisting of arylamides of aromatic ortho-hydroxy carboxylic acids, arylamides of heterocyclic ortho-hydroxy carboxylic acids and arylamides of acylacetic acids and which furthermore contains a compound of the forin which R represents a radical of the group consisting of aromatic and heterocyclic amines, Me represents a member selected from the group consisting of an alkali metal atom and an alkaline earth metal atom and n stands for one of the integers 1 and 2, and a dispersing agent, and then treating the goods without intermediate drying with acid agents selected from

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• 1963
  • 1963-10-19 DE DE1963F0041036 patent/DE1262957C2/de not_active Expired
• 1964
  • 1964-10-07 NO NO155058A patent/NO119985B/no unknown
  • 1964-10-16 DK DK512864AA patent/DK109031C/da active
  • 1964-10-16 US US404503A patent/US3441364A/en not_active Expired - Lifetime
  • 1964-10-16 SE SE12457/64A patent/SE305194B/xx unknown
  • 1964-10-16 AT AT881264A patent/AT253458B/de active
  • 1964-10-16 CH CH1347564A patent/CH467900A/de unknown
  • 1964-10-19 JP JP39059190A patent/JPS5017588B1/ja active Pending
  • 1964-10-19 NL NL6412146A patent/NL6412146A/xx unknown
  • 1964-10-19 GB GB42550/64A patent/GB1077777A/en not_active Expired
  • 1964-10-19 BE BE654559A patent/BE654559A/xx unknown

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