US2469409A - Treatment of textile materials - Google Patents
Treatment of textile materials Download PDFInfo
- Publication number
- US2469409A US2469409A US63228645A US2469409A US 2469409 A US2469409 A US 2469409A US 63228645 A US63228645 A US 63228645A US 2469409 A US2469409 A US 2469409A
- Authority
- US
- United States
- Prior art keywords
- fabric
- salt
- formaldehyde
- maleic anhydride
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- 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
- D06M13/10—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 oxygen
- D06M13/12—Aldehydes; Ketones
- D06M13/127—Mono-aldehydes, e.g. formaldehyde; Monoketones
-
- 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
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
- D06M15/233—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated aromatic, e.g. styrene
-
- 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
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
-
- 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
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
- Y10T442/2402—Coating or impregnation specified as a size
Definitions
- This invention relates to improved textile fln-' ishing materials and methods of treating yarns and fabrics therewith.
- a further object of the invention is to provide a method of finishing fabrics which involves applying the finishing agent to the warp yarns prior to weaving, whereby the weaving operation is facilitated and a suitably finished fabric is obtained without further treatment.
- the yarn or fabric is treated with an aqueous solution or dispersion of an ammonium or amine salt of copolymerized styrene maleic anhydride and formaldehyde, after which the yarn or fabric is heated.
- This causes the styrene maleic anhydride copolymer to react with the formaldehyde, thereby insolubilizing the copolymer so that most of it remains on the fabric after washing and provides a substantially permanent finish.
- water-soluble formaldehyde-yielding substances such as water-soluble polymers of formaldehyde which decompose on heating to yield formaldehyde, may be used, for example, trioxane, paraformaldehyde and the like.
- Suitable ammonium or amine salts of the copolymer include the salts of ammonia, guanidine, alkylamines, such as methyl, butyl and amyl amine, and quaternary ammonium hydroxides, such as phenyl trimethyl ammonium hydroxide,
- the solution or bath In treating the fabric in the manner described above, it is preferable to keep the solution or bath below 180 F. to avoid appreciable reaction taking place during the impregnation of the fabric. However, the bath may be kept at somewhat higher temperatures for short periods without harmful effect.
- the fabric Upon removal from the bath, the fabric is heated at an elevated temperature until it is dry. Preferably, the fabric is heated at 250 to 300 F., but satisfactory results may be obtained at temperatures as low as 200 F.
- concentration of the styrene maleic salt in the bath and the pick-up should be adjusted to deposit on the fabric from 2 to by weight of the styrene maleic salt, but preferably between about 4 and 7%.
- the formaldehyde or formaldehyde polymer is ordinarily added in amounts varying between 1 and on the weight of the styrene maleic salt.
- the yarn or fabric may be treated in any order or simultaneouslytherewith.
- the formaldehyde may be applied in the form of a gas. It is desirable to have the bath or solution, or the gas, at slightly elevated temperatures to insure uniform penetration, but good results may also be obtained at room temperatures.
- the copolymer of styrene and maleic anhydride used in accordance with this invention is a wellestablished product which may be prepared in several ways.
- One of the well-known methods is mass polymerization, which involves heating styrene and maleic anhydride at temperatures between about and 300 F. for several hours or more. Preferably, the materials are heated cautiously, as in a water bath.
- Another method which may be used is known as the solvent process which involves reacting the styrene and maleic anhydride at slightly elevated temperatures in the presence of a solvent which is capable of dissolving both the starting materials and the finished polymer, such as acetone.
- the copolymerization may be carried out in the presence of a catalyst, such as benzoyl peroxide.
- copolymer of styrene and maleic anhydride produced by either of the above or by any other well-known method of manufacture is soluble in acetone, but insoluble in alcohol or benzene, and forms water-soluble salts of ammonia or alkali metals.
- substituted styrenes such as methyl or butyl styrene, chlorstyrene or the like, may be used to prepare copolymers which are soluble in dilute aqueous solutions of alkali or ammonia.
- maleic anhydride partially such as the half ester esterified maleic anhydride, of isopropyl maleate, may be used.
- copolymers of styrene and maleic anhydride which havebeen copolymerized with relativeiy small amounts'of other unsaturated compounds, such as vinyl acetate, vinyl chloride, vinyl ethy1 ether, indene, vinyl-methyl ketone, acrylic esters and the like.
- Example I A solution of an ammonium salt of styrene maleic anhydride resin was prepared by mixing together 600 parts of styrene maleic anhydride, prepared by copolymerizing equimolecular quantities of styrene and maleic anhydride at about 200 F. in a water bath, 400 parts of 26% NHiOH' and 9000 parts of water. The resulting mixture was then heated to 200 to 212 F. with stirring, and maintained at this temperatureuntil a uniform, somewhat viscous transparent'solution resulted. This required about one hour. After cooling the solution to about 120 F., a quantity of 35% formalin was added to the extent of about 10% on the weight of the styrene maleic anhydride used.
- Heavy cotton sheeting was dipped in the bath prepared as described above, after which it was passed through a padder adjusted for 100% pick-up.
- the bath was maintained at about 120 F. during the treatment of the fabric to insure uniform penetration. then heated for'about two and a half minutes on a tenter frame using hot air at 300 F., at which time it was substantially dry.
- the dry sheeting was washed for one hour at the boil in a running suds, and was found to retain 95% of the deposited resin.
- Example [I A solution of an ammonium salt of styrene maleic anhydride resin, containing 10% by weight of 35% formalin was prepared as described-in Example I. The resulting solution was then poured into the size box of a slasher, after when 1 a warp of iii/single cotton yarn was passed though the solution and dried on dry cans in the usual manner, using 12 pounds of steam. Thetreated yarn was then rolled up on a beam and woven. Excellent weaving was obtained and the resulting fabric possessed a desirably stiffened finish which retained its stiffened character even after washing. Moreover, the fabric had an unusually smooth feel and did not dust out.
- Example 111 mixture was then heated to 200 to 212 F. with' stirring, 'and maintained at this temperature until a uniform, somewhat viscous transparent solution resulted, which required about one hour.
- trioxane was added to the extent of about 5% on the weight of the styrene maleic anhydride used.
- Spun viscose rayon fabric was dipped in the bath prepared as described above, after which it was passed through a padder adjusted for 100% pick-up.
- the bath was maintained at about 120 F. during the treatment of the fabric to insure uniform penetration.
- the treated fabric was then heated for about four minutes on a tenter frame using hot air at 250 F., at the endof which time it was substantially dry.
- the dry fabric was leached for one-half hour at 150 F. in tap water, and wasfound to retain about 95% of the deposited resin.
- Example IV Samples of acetate rayon, nylon and glass yarns were treated in the same manner as the cotton yarn in Example II. In each case a uniformly sized warp was obtained which was readily woven.
- the resulting fabric were smooth, full and somewhat stiffened and retained these characteristics after washing.
- aqueous solutions referred to in the appended claims are intended to include aqueous dispersions, as it is possible that the ammonium or amine salts in the solutionare actually present in the form of a colloidal dispersion.
- the method of finishing textile fabrics which comprises treating the fabric with an aqueous solution of a substance selected from the group consisting of formaldehyde and watersoluble polymers of formaldehyde and a salt of copolymerized styrene maleic anhydride selected from the group consisting of ammonium salts and amine salts, said salt being deposited on the fabric in amounts varying from 2 to 15% by weight, said substance being added in amounts varying between 1 and 20% on the weight of said salt, and then drying the fabric, whereby said treating agents react to form an isoluble resin on the fabric.
- a substance selected from the group consisting of formaldehyde and watersoluble polymers of formaldehyde and a salt of copolymerized styrene maleic anhydride selected from the group consisting of ammonium salts and amine salts
- the method of finishing textile fabrics which comprises treating the fabric with an aqueous solution of an amine salt of copolymerized styrene maleic anhydride and formaldehyde, said salt being deposited on the fabric in amounts varying from 2 to 15% by weight, said formaldehyde being added in amounts varying between 1 and 20% on the weight of said salt, and then drying the fabric, whereby said treating agents react to form an insoluble resin thereon.
- the method of finishing textile fabrics which comprises treating the fabric with an aqueous solution of an ammonium salt of copolymerized styrene maleic anhydride and formaldehyde, said salt being deposited on the fabric in amounts varying from 2 to 15% by weight, said formaldehyde being added in amounts varying between 1 and 20% on the weight of said salt, and then drying the fabric, whereby said treating agents react to form an insoluble resin thereon.
- the method of finishing textile fabrics which comprises treating the fabric with an aqueous solution of an ammonium salt of copolymerized styrene maleic anhydride and trioxane, said salt being deposited on the fabric in amounts varying from 2 to 15% by weight, said trioxane being added in amounts varying between 1 and 20% on the weight of said salt, and then drying the fabric, whereby said treating agents react to form an insoluble resin thereon.
- the method of finishing textile fabrics which comprises treating the fabric with an aqueous solution of an ammonium salt of copolymerized styrene maleic anhydride and paraformaldehyde, said salt being deposited on the fabric in amounts varying from 2 to 15% by weight, said paraformaldehyde being added in amounts varying between 1 and 20% on the weight of said salt, and then drying the fabric, whereby said treating agents react to form an insoluble resin thereon.
- the method of finishing textile fabrics which comprises treating the fabric with an aqueous solution of an ammonium salt of copolymerized styrene maleic anhydride and formaldehyde,
- said salt being deposited on the fabric in amounts varying from 2 to 15% by weight, said formaldehyde being added in amounts varying between 1 and 20% on the weight of said salt, and then drying the fabric, whereby said treating agents react to form an insoluble resin thereon.
- the method of preparing and finishing textile fabrics which comprises treating warp yarn with an aqueous solution of a substance selected from the group consisting of formaldehyde and water-soluble polymers of formaldehyde and a salt of copolymerized styrene maleic anhydride selected from the group consisting of ammonium salts and amine salts, said salt being deposited on the fabric in amounts varying from 2 to 15% by weight, said substance being added in amounts v ying between 1 and 20% on the weight of said salt, then drying the yarn, whereby said treating agents react to form an insoluble resin thereon, and weaving the resulting yarn into a fabric.
- a substance selected from the group consisting of formaldehyde and water-soluble polymers of formaldehyde and a salt of copolymerized styrene maleic anhydride selected from the group consisting of ammonium salts and amine salts
- the method of sizing textile warp yarns which comprises treating said yarns with an aqueous solution of a substance selected from the group consisting of formaldehyde and watersoluble polymers of formaldehyde and a salt of copolymerized styrene maleic anhydride selected from the group consisting of ammonium salts and amine salts, said salt being deposited on the fabric in amounts varying from 2 to 15% by weight, said substance being added in amounts varying between 1 and 20% on the weight of said salt. and then drying the yarn, whereby said treating agents react to form an insoluble resin thereon.
- a substance selected from the group consisting of formaldehyde and watersoluble polymers of formaldehyde and a salt of copolymerized styrene maleic anhydride selected from the group consisting of ammonium salts and amine salts
- the method of sizing or finishing textile materials which comprises treating said material with an aqueous solution of a substance selected from the group consisting of formaldehyde and water-soluble polymers of formaldehyde and a salt of a copolymer prepared by copolymerizing a substance selected from the group consisting of styrene and substituted styrenes with a substance selected from the group consisting of maleic anhydride and partial esters of maleic anhydride, said salt being selectedfrom the group consisting of ammonium salts and amine salts, and being deposited on the fabric in amounts varying from 2 to 15% by weight, said substance being added in amounts varying between 1 and 20% on the weight of said salt and then drying the treated material, whereby said treating agents react to form an insoluble resin thereon.
- a finishing composition for textile fibers, yarns or fabrics which comprises an aqueous solution of a substance selected from the group consisting of formaldehyde and water-soluble polymers of formaldehyde and a salt of copolymerized styrene maleic anhydride selected from the group consisting of ammonium salts and amine salts, said substance being present in an amount varying between 1 and 20% on the weight of said salt.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Reinforced Plastic Materials (AREA)
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US63228645 US2469409A (en) | 1945-12-01 | 1945-12-01 | Treatment of textile materials |
GB3341246A GB628754A (en) | 1945-12-01 | 1946-11-11 | Improvements in or relating to methods of sizing or finishing textile materials, fabrics or yarns, and the finishing composition therefor |
FR937469D FR937469A (fr) | 1945-12-01 | 1946-11-20 | Améliorations apportées aux procédés d'encollage ou d'apprêtage des matières textiles, des fils et des tissus, ainsi que les matières, fils et tissus perfectionnés obtenus par ces procédés et la composition d'apprêtage qu'ils emploient |
FR937467D FR937467A (fr) | 1945-12-01 | 1946-11-20 | Perfectionnements aux presses pour le moulage des matières plastiques |
BE469565D BE469565A (ru) | 1945-12-01 | 1946-11-30 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US63228645 US2469409A (en) | 1945-12-01 | 1945-12-01 | Treatment of textile materials |
Publications (1)
Publication Number | Publication Date |
---|---|
US2469409A true US2469409A (en) | 1949-05-10 |
Family
ID=24534892
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US63228645 Expired - Lifetime US2469409A (en) | 1945-12-01 | 1945-12-01 | Treatment of textile materials |
Country Status (4)
Country | Link |
---|---|
US (1) | US2469409A (ru) |
BE (1) | BE469565A (ru) |
FR (2) | FR937469A (ru) |
GB (1) | GB628754A (ru) |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2577624A (en) * | 1947-03-29 | 1951-12-04 | Monsanto Chemicals | Mineral-coated paper and process of producing same |
US2609350A (en) * | 1946-12-21 | 1952-09-02 | Gen Aniline & Film Corp | Textile finishing agent |
US2650172A (en) * | 1949-01-21 | 1953-08-25 | American Viscose Corp | Moistureproofing of nonfibrous cellulosic material |
US2651587A (en) * | 1947-06-02 | 1953-09-08 | Monsanto Chemicals | Treatment of textile materials |
DE906685C (de) * | 1950-08-16 | 1954-03-15 | Dynamit Nobel Ag | Verfahren zur Verbesserung der Eigenschaften von Textilien |
US2702241A (en) * | 1950-10-07 | 1955-02-15 | Hawley Products Co | Glass fiber material |
US2712003A (en) * | 1949-11-23 | 1955-06-28 | Monsanto Chemicals | Manufacture of water-soluble heteropolymers |
US2722488A (en) * | 1952-08-16 | 1955-11-01 | Gen Aniline & Film Corp | Process of coloring glass fabrics with a resinous coating dyed with a vat dye |
US2722489A (en) * | 1952-08-16 | 1955-11-01 | Gen Aniline & Film Corp | Process of coloring glass fabrics with vat dyes |
US2744835A (en) * | 1953-06-10 | 1956-05-08 | Owens Corning Fiberglass Corp | Method of treating fibers with a vinyl copolymer and a werner complex |
US2772157A (en) * | 1953-03-16 | 1956-11-27 | Raybestos Manhattan Inc | Production of mixed fibrous sheet material |
US2848357A (en) * | 1954-12-15 | 1958-08-19 | Monsanto Chemicals | Aqueous terpolymer sized nylon yarns |
US2859193A (en) * | 1956-07-30 | 1958-11-04 | Goodrich Co B F | Aqueous dispersion comprising carboxyl containing elastomer, vulcanizing agent, and formaldehyde |
US2874069A (en) * | 1954-03-12 | 1959-02-17 | Deering Milliken Res Corp | Method for reducing the pilling tendencies of fabrics |
US3236685A (en) * | 1962-06-20 | 1966-02-22 | Eastman Kodak Co | Process for treating textile fibers and other shaped products with coatings |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1923168A (en) * | 1931-02-05 | 1933-08-22 | United Shoe Machinery Corp | Method of making woven fabrics |
DE592233C (de) * | 1930-12-24 | 1934-02-03 | Ig Farbenindustrie Ag | Verfahren zur Herstellung polymerer Derivate |
US2047398A (en) * | 1930-06-26 | 1936-07-14 | Ig Farbenindustrie Ag | Artificial resins and process of making them |
US2282701A (en) * | 1938-12-08 | 1942-05-12 | Rohm & Haas | Process of waterproofing |
US2359038A (en) * | 1938-07-12 | 1944-09-26 | Gen Aniline & Film Corp | Interpolymerization products of diene synthesis products and compounds having an omega-methylene group and process of their production |
-
1945
- 1945-12-01 US US63228645 patent/US2469409A/en not_active Expired - Lifetime
-
1946
- 1946-11-11 GB GB3341246A patent/GB628754A/en not_active Expired
- 1946-11-20 FR FR937469D patent/FR937469A/fr not_active Expired
- 1946-11-20 FR FR937467D patent/FR937467A/fr not_active Expired
- 1946-11-30 BE BE469565D patent/BE469565A/xx unknown
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2047398A (en) * | 1930-06-26 | 1936-07-14 | Ig Farbenindustrie Ag | Artificial resins and process of making them |
DE592233C (de) * | 1930-12-24 | 1934-02-03 | Ig Farbenindustrie Ag | Verfahren zur Herstellung polymerer Derivate |
US1923168A (en) * | 1931-02-05 | 1933-08-22 | United Shoe Machinery Corp | Method of making woven fabrics |
US2359038A (en) * | 1938-07-12 | 1944-09-26 | Gen Aniline & Film Corp | Interpolymerization products of diene synthesis products and compounds having an omega-methylene group and process of their production |
US2282701A (en) * | 1938-12-08 | 1942-05-12 | Rohm & Haas | Process of waterproofing |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2609350A (en) * | 1946-12-21 | 1952-09-02 | Gen Aniline & Film Corp | Textile finishing agent |
US2577624A (en) * | 1947-03-29 | 1951-12-04 | Monsanto Chemicals | Mineral-coated paper and process of producing same |
US2651587A (en) * | 1947-06-02 | 1953-09-08 | Monsanto Chemicals | Treatment of textile materials |
US2650172A (en) * | 1949-01-21 | 1953-08-25 | American Viscose Corp | Moistureproofing of nonfibrous cellulosic material |
US2712003A (en) * | 1949-11-23 | 1955-06-28 | Monsanto Chemicals | Manufacture of water-soluble heteropolymers |
DE906685C (de) * | 1950-08-16 | 1954-03-15 | Dynamit Nobel Ag | Verfahren zur Verbesserung der Eigenschaften von Textilien |
US2702241A (en) * | 1950-10-07 | 1955-02-15 | Hawley Products Co | Glass fiber material |
US2722488A (en) * | 1952-08-16 | 1955-11-01 | Gen Aniline & Film Corp | Process of coloring glass fabrics with a resinous coating dyed with a vat dye |
US2722489A (en) * | 1952-08-16 | 1955-11-01 | Gen Aniline & Film Corp | Process of coloring glass fabrics with vat dyes |
US2772157A (en) * | 1953-03-16 | 1956-11-27 | Raybestos Manhattan Inc | Production of mixed fibrous sheet material |
US2744835A (en) * | 1953-06-10 | 1956-05-08 | Owens Corning Fiberglass Corp | Method of treating fibers with a vinyl copolymer and a werner complex |
US2874069A (en) * | 1954-03-12 | 1959-02-17 | Deering Milliken Res Corp | Method for reducing the pilling tendencies of fabrics |
US2848357A (en) * | 1954-12-15 | 1958-08-19 | Monsanto Chemicals | Aqueous terpolymer sized nylon yarns |
US2859193A (en) * | 1956-07-30 | 1958-11-04 | Goodrich Co B F | Aqueous dispersion comprising carboxyl containing elastomer, vulcanizing agent, and formaldehyde |
US3236685A (en) * | 1962-06-20 | 1966-02-22 | Eastman Kodak Co | Process for treating textile fibers and other shaped products with coatings |
Also Published As
Publication number | Publication date |
---|---|
BE469565A (ru) | 1946-12-31 |
FR937469A (fr) | 1948-08-18 |
FR937467A (fr) | 1948-08-18 |
GB628754A (en) | 1949-09-05 |
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