EP0202471B1 - Dispersion aqueuse anionique - Google Patents

Dispersion aqueuse anionique Download PDF

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Publication number
EP0202471B1
EP0202471B1 EP86105191A EP86105191A EP0202471B1 EP 0202471 B1 EP0202471 B1 EP 0202471B1 EP 86105191 A EP86105191 A EP 86105191A EP 86105191 A EP86105191 A EP 86105191A EP 0202471 B1 EP0202471 B1 EP 0202471B1
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EP
European Patent Office
Prior art keywords
denotes
formula
ycf2
anionic dispersion
ch2ch2
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Expired - Lifetime
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EP86105191A
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German (de)
English (en)
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EP0202471A3 (en
EP0202471A2 (fr
Inventor
Karl Dr. Hintermeier
Heinrich Dr. Bathelt
Frank Dr. Wehowsky
Hans Wagener
Manfred Seidel
Manfred Müller
Klaus Kaschub
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Sanofi Aventis Deutschland GmbH
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Cassella AG
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Priority to AT86105191T priority Critical patent/ATE65809T1/de
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Publication of EP0202471A3 publication Critical patent/EP0202471A3/de
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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
    • 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
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/402—Amides imides, sulfamic acids
    • D06M13/425—Carbamic or thiocarbamic acids or derivatives thereof, e.g. urethanes
    • D06M13/428—Carbamic or thiocarbamic acids or derivatives thereof, e.g. urethanes containing fluorine atoms

Definitions

  • the present invention relates to an aqueous anionic dispersion which contains a bis- (2-perfluoroalkyl-ethoxy-carbonylamino) toluene, its preparation and its use for finishing textiles with oleophobic and hydrophobic agents, and the active ingredient contained in the dispersion.
  • a commercial product for textile finishing contains such fluorine-containing bisurethanes together with cationic dispersing agents in an aqueous dispersion.
  • a disadvantage of using this dispersion is that fibers or textiles treated with it attract dirt particles that are normally anionically charged. For this reason, the cationic dispersions of the fluorine-containing bisurethanes must contain a special antistatic additive if one does not want to be forced to subject the finished goods to additional antistatic treatment later.
  • the percentages given above represent percentages by weight.
  • the percentages for a, b, c and d are based on the total weight of the aqueous dispersion.
  • the perfluoroalkyl radicals or perfluoroalkyl compounds mentioned above and below can also have an H atom according to the above definitions in the ⁇ position for Y.
  • the compounds of the formulas II, III and IV can be used in the form of their technical mixtures, which generally contain several compounds of the type mentioned with different index numbers n, p, q and / or r.
  • the compounds of formula I are known.
  • the active ingredient A which is used according to the invention for the preparation of the aqueous anionic dispersion, is new.
  • A is used to produce the product specified under A.
  • Suitable tolylene di-isocyanates are, in particular, 2,4- and / or 2,6-tolylene di-isocyanate, in particular in the form of a commercial product which contains approximately 80% by weight of 2,4-tolylene di contains isocyanate and about 20% by weight of 2,6-tolylene di-isocyanate.
  • the reaction for the production of product A is generally carried out in such a way that the compound II or the mixture of the compounds II is melted and 2 to 5% by weight, preferably 2 to 3.5% by weight, of N-methyl pyrrolidone is admixed and then to 10 o C higher than the melting point temperature of the tolylene di-isocyanate at a approximately 5 or mixture of tolylene di-isocyanate is added dropwise with stirring.
  • the mixture is then heated to temperatures of approximately 130 ° C. in the course of an hour, the reaction proceeding slightly exothermic from temperatures of approximately 80 ° C.
  • the reaction is brought to a conclusion by an approximately three-hour reaction time at approximately 130 ° C.
  • the progress of the reaction is continuously checked by IR spectroscopy on the samples for the disappearance of the isocyanate bands. If the reaction occurs within the specified time has not yet been completed, the reaction time must be extended, for example to 6 hours.
  • N-methylpyrrolidone presumably forms by-products of still unknown structure, which act as excellent dispersion stabilizers in the inventive dispersion of the product.
  • a larger addition of N-methylpyrrolidone in the preparation of product A does not adversely affect the effect of dispersion stabilization, but unnecessarily reduces the yield of the active substance of the formula I.
  • the monovalent cation X in the compounds of the formula III generally represents an alkali metal cation, in particular the sodium or potassium cation or the ammonium cation.
  • the ammonium cation can optionally also be substituted by organic radicals, for example triethanolammonium.
  • emulsifiers of the formula IV are also commercially available, mostly in the form of their technical mixtures.
  • r is in particular approximately 6.
  • d is preferably a number from 10 to 25.
  • components A, B, C and D are dispersed in water, with the supply of a relatively large amount of energy.
  • the quantitative ratios for the components are chosen so that the specified composition for the dispersion is achieved after dispersion. It is essential to pre-dissolve product A in at least part of the amount of solvent or solvent mixture to be used, and it is expedient to divide the dispersion into two substeps and first to do a predispersion and then a fine dispersion.
  • the predispersion is expediently carried out by using high shear forces, for example by using a high-speed stirrer, such as, for example, in an Ultraturrax type dispersion machine, and the predispersion obtained is then subjected, for example, to an ultrasound treatment or a treatment in a high-pressure homogenizer. After this treatment has ended, the particle size in the dispersion is more than 80%, preferably more than 95%, at or below 1 ⁇ m.
  • Water-soluble solvents such as, for example, mono- or di-alcohols, lower ketones, polyglycol esters and polyglycol ethers, or mixtures of such solvents, are used for solvent component D.
  • Component D advantageously contains at least one high-boiling, water-soluble solvent, ie a solvent whose boiling point is above approximately 150 ° C.
  • a solvent mixture used can also contain one or more water-insoluble solvents, such as esters, ethers and / or higher ketones.
  • Low-boiling solvent fractions can optionally be removed again at a later time, for example distilled off.
  • Suitable water-soluble, high-boiling solvents are in particular the (C1-C4) monoalkyl and dialkyl ethers of diethylene glycol and / or dipropylene glycol.
  • a further advantage for the stability of the dispersion is the addition of isopropanol, glycol or glycerin, individually or in a mixture, preferably in an amount of 1 to 5% by weight, based on the final setting.
  • Such (meth) acrylic acid ester polymers or copolymers are advantageously added to the dispersions according to the invention in the form of a separately prepared aqueous anionic dispersion. It is also expedient to use the polymer or. Disperse copolymer dispersion using a compound of formula III or a mixture of such compounds.
  • the (meth) acrylic acid ester polymers or copolymers normally contain building blocks of esters of acrylic and / or methacrylic acid with C1 to C18 alcohols and can be prepared, for example, in a manner known per se.
  • Methacrylic ester copolymers are preferred, particularly when the monomer mixture used for their preparation contains at least 80% by weight of esters of C1 to C4 alcohols.
  • Copolymers of methyl and isobutyl methacrylate are particularly preferred, particularly when the methyl ester content predominates in the copolymer.
  • a copolymer made from methyl methacrylate and isobutyl ester in a weight ratio of 3: 1 is very particularly preferred.
  • the preparation of this copolymer and its dispersion are described in Example 3.
  • Other (meth) acrylic ester polymers and copolymers can be prepared and dispersed analogously.
  • the aqueous anionic dispersions according to the invention meet all practical requirements and in particular show excellent long-term stability at temperatures from -20 to +40 o C. Although they freeze at sub-zero temperatures, the dispersion remains after thawing, in contrast to the previously known dispersions.
  • the aqueous anionic dispersions according to the invention have an excellent oleophobic, hydrophobic, dirt-repellent and conductivity-improving effect in textile finishing. They can be used both for textile finishing alone, as well as in combination with other finishing agents, such as textile resins based on glyoxal or their derivatives, plasticizers, PVA and EVA or similar dispersions.
  • the aqueous anionic dispersions according to the invention are suitable for finishing textiles made from natural or synthetic fibers, in particular from polyamide, polyester, polyacrylonitrile and wool, or mixtures of these types of fibers.
  • the textile material can be in any form, e.g. as thread, fiber, yarn, flake, as fabric, knitted fabric, knitted fabric or fleece, but especially as a carpet.
  • the dispersions according to the invention can be applied to the textile material in the form in which they are produced. Normally, however, they will be diluted with water to a solids content of 1 to 10% by weight, preferably 1.5 to 5% by weight, for use.
  • the application to the textile material to be treated can be carried out in any suitable manner, for example by spraying, splashing, padding, etc.
  • the application amount is chosen so that 0.01 on the textile material up to 1% by weight of fluorine, preferably 0.05 to 0.2% by weight of fluorine. This corresponds approximately to an amount of 0.1 to 10, preferably 0.5 to 2% by weight solids content.
  • drying is carried out at temperatures of up to approximately 120 ° C., for example at 100 to 120 ° C., and then heat treatment is carried out at temperatures of approximately 130 to 190 ° C., preferably 140 to 180 ° C. , which normally takes about 4 minutes to about 30 seconds.
  • the high-boiling organic solvents preferably contained in the dispersion also have an important meaning in fixing the active ingredient of formula I on the fiber in the sense of a kind of carrier effect.
  • the progress of the reaction is IR-spectroscopically on the disappearance of the isocyanate bands on samples taken controlled.
  • the response time may be shortened or extended.
  • Example 1 is repeated without the addition of N-methyl-pyrrolidone. 1154 g of a pale yellowish melt are obtained which solidify on cooling to a hard, pale yellowish crystal cake. Mp: 116 to 120 o C. Average F content: 60.5%.
  • the polymerization reaction will then begin immediately, as can be seen from a rise in temperature to about 57 ° C. and a change in color (bluish fluorescent).
  • the dropwise addition of the monomer solution from the storage vessel and a separately prepared catalyst solution consisting of 0.2 g of sodium pyrosulfite (Na2S2O5) and 10 g of water are started.
  • the introduction of nitrogen can be stopped.
  • the monomer solution should be metered in after about 1 hour and the catalyst solution a little later.
  • the reaction temperature is 55 to 60 o C with an unchanged bath temperature of 55 o C.
  • the polymer emulsion is heated to 60 to 62 o C (65 o C bath temperature) and stirred for 1 h under these conditions, then on Cooled to room temperature and filtered through a PE sieve bag (105 ⁇ m). 270.4 g of an approximately 40% whitish, opaque dispersion are obtained.
  • Example 3 The procedure is as in Example 3, but the 30 g of the isopropanol solution of the emulsifier used there is replaced by 4 g of a commercially available alkane sulfonate used as a wash raw material (e.g. commercial product ®Warolat U from Bayer AG).
  • a commercially available alkane sulfonate used as a wash raw material (e.g. commercial product ®Warolat U from Bayer AG).
  • the crude dispersion obtained is then subjected to a final fine treatment, namely by sonication using an ultrasound machine (for example of the Sonifier type from Branson) until 90% of the particles have reached or fallen below a size of 1 ⁇ m. This usually takes 10 to 15 minutes.
  • the temperature is initially kept at 40 to 45 ° C by water cooling, towards the end by cooling with ice water to 20 lowered to 30 o C.
  • Example 5 is repeated, but product A produced according to example 1 is replaced by 11.8 g of the bisurethane prepared according to example 2.
  • the dispersion obtained is not stable in storage, since a clear sediment forms within 24 hours, which further increases over time.
  • a solution of 1.25 g of a compound of the formula VII is placed in a 200 ml three-necked flask in the form of a beaker CF3 (CF2) 5-CH2CH2-O-CO-NH-CH2CH2-SSO3Na (VII) in 48.75 ml of water and 20 g of the approx. 40% anionically dispersed methacrylic ester copolymer according to example 4 submitted.
  • This raw dispersion is then subjected to a final fine treatment, namely by sonication using an ultrasound machine (for example of the Sonifier type from Branson) until 90% of the particles have reached or fallen below an average size of 1 ⁇ m. This usually takes 10 to 15 minutes.
  • the temperature is first kept at 40 to 45 o C by water cooling, and finally reduced to 20 to 30 o C by cooling with ice water.
  • the dispersion according to the invention prepared according to Example 5 or 7 is diluted with water to a solids content of 2 to 4% by weight.
  • the web to be treated is passed through the liquor thus obtained and squeezed off on a foulard. A repetition of this process promotes the penetration of the substrate and increases the effectiveness of the product according to the invention.
  • the textile substrate is dried in a drying unit at temperatures up to 120 ° C. and then fixed in the same or another unit by heat treatment at temperatures from 150 to 180 ° C. for 3 minutes to 3 seconds.
  • the dispersion prepared according to Example 5 is diluted with water to a solids content of 3% and sprayed onto a PA tufted carpet.
  • the carpet is then dried at 110 ° C. and then subjected to a 3-minute heat treatment at 150 ° C.
  • the oil repellency is tested according to the 3M / AATCC 18-1966 method, the hydrophobization / spray according to the AATCC 22-1952 method and the dry soiling according to the following regulation:
  • the carpet sample is laid out in a cylindrical vessel that can be closed with a lid and is 20 cm long and 10 cm in diameter. Then 200 g of steel balls with a diameter of 3 mm and 20 g of sieved vacuum cleaner dirt are added, the vessel is closed and rolled on a trolley for 1 hour. Then the sample is taken, vacuumed with a vacuum cleaner and assessed.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Colloid Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
  • Paints Or Removers (AREA)

Claims (10)

  1. Dispersion anionique aqueuse contenant :
    A) a % d'un produit qui renferme au moins un bis-(fluoralkyl-2 éthoxy-carbonylamino)-toluène répondant à la formule I :
    Figure imgb0017
     dans laquelle n désigne un nombre de 5 à 15 et Y représente -H ou -F,
    et qui peut être préparé par réaction d'un perfluoralkyl-2 éthanol répondant à la formule II :



            YCF₂-(CF₂)n-CH₂CH₂OH   (II)



    dans laquelle n et Y ont les significations qui leur ont été données ci-dessus,
    avec un di-isocyanato-toluène, dans le rapport molaire(1,8 à 2):1, en présence de 2 à 5 % de N-méthyl-pyrrolidone par rapport au composé de formule II,
    B) b % d'au moins un émulsionnant répondant à la formule III :



            YCF₂(CF₂)p-CH₂CH₂O-CO-NH-CH₂CH₂-SSO₃X   (III)



    dans laquelle p désigne un nombre de 5 à 15, Y représente -H ou -F et X représente un cation univalent,
    C) c % d'au moins un émulsionnant non ionique répondant à la formule IV :



            YCF₂-(CF₂)q-CH₂CH₂-(OCH₂CH₂)r-OH   (IV

    )

    dans laquelle Y représente -H ou -F, q représente un nombre de 5 à 15 et r représente un nombre de 0 à 10, et
    D) d % d'un solvant ou d'un mélange de solvants,
    a désignant un nombre de 5 à 25, b un nombre de 1 à 14, c un nombre de 1 à 14 et d un nombre de 5 à 30, et les valeurs de b et de c étant choisies de telle façon que la somme (b + c) soit égale à un nombre de 2 à 15.
  2. Dispersion anionique aqueuse selon la revendication 1, caractérisée en ce que b désigne un nombre de 1 à 9 et c un nombre de 1 à 9 et sont choisis de telle façon que la somme (b + c) soit égale à un nombre de 2 à 12, et/ou d désigne un nombre de 10 à 25.
  3. Dispersion anionique aqueuse selon la revendication 1 et/ou la revendication 2, contenant un produit qui renferme au moins un bis-(fluoralkyl-2 éthoxycarbonylamino)-toluène répondant à la formule I :
    Figure imgb0018
     dans laquelle n désigne un nombre de 5 à 15 et Y représente -H ou -F,
    et qui peut être préparé par réaction d'un perfluoralkyl-2 éthanol répondant à la formule II :



            YCF₂-(CF₂)n-CH₂CH₂OH   (II)



    dans laquelle n et Y ont les significations qui leur ont été données ci-dessus,
    avec un di-isocyanato-toluène, dans le rapport molaire (1,8 à 2):1, en présence de 2 à 3,5 % en poids de N-méthyl-pyrrolidone par rapport au composé II.
  4. Dispersion anionique aqueuse selon une ou plusieurs des revendications 1 à 3, caractérisée en ce que, dans les composés de formules I, II, III et/ou IV, Y représente -F et en ce que, dans les composés de formule I, n désigne un nombre de 5 à 11, de préférence de 7 à 11, dans les composés de formule III p désigne un nombre de 5 à 11, de préférence de 7 à 11, et/ou dans les composés de formule IV q désigne un nombre de 5 à 11, de préférence de 7 à 11, et r un nombre de 4 à 8.
  5. Dispersion anionique aqueuse selon une ou plusieurs des revendications 1 à 4, caractérisée en ce que la dispersion contient au moins un éther mono-alkylique ou di-alkylique à alkyle en C₁-C₄ du diéthylène-glycol ou du dipropylène-glycol et/ou de 1 à 5 % en poids d'isopropanol, de glycol et/ou de glycérol.
  6. Dispersion anionique aqueuse selon une ou plusieurs des revendications 1 à 5, caractérisée en ce qu'elle contient en outre de 5 à 25 % en poids d'au moins une dispersion anionique d'un polymère ou d'un copolymère d'un ester acrylique ou méthacrylique, de préférence d'un copolymère du méthacrylate de méthyle et du méthacrylate d'isobutyle.
  7. Dispersion anionique aqueuse selon la revendication 6, caractérisée en ce que la dispersion anionique du polymère de l'ester acrylique ou méthacrylique contient, comme émulsionnant, un composé répondant à la formule III :



            YCF₂(CF₂)q-CH₂CH₂O-CO-NH-CH₂CH₂-SSO₃X   (III)



    dans laquelle Y représent -H ou -F, q désigne un nombre de 5 à 15 et X représente un cation.
  8. Produit contenant au moins un bis-(fluoralkyl-2 éthoxy-carbonylamino)-toluène répondant à la formule I :
    Figure imgb0019
     dans laquelle n désigne un nombre de 5 à 15 et Y représente -H ou -F, produit qui peut être préparé par réaction d'un perfluoralkyl-2 éthanol répondant à la fomule II :



            YCF₂-(CF₂)n-CH₂CH₂OH   (II)



    dans laquelle n et Y ont les significations qui leur ont été données ci-dessus, avec un di-isocyanato-toluène, dans le rapport molaire (1,8 à 2):1, en présence de 2 à 5 %, de préférence de 2 à 3,5 %, de N-méthyl-pyrrolidone par rapport au composé de formule II.
  9. Procédé pour préparer des dispersions anioniques aqueuses selon une ou plusieurs des revendications 1 à 7, procédé caractérisé en ce que :
    A) un produit qui renferme au moins un bis-(fluoralkyl-2 éthoxy-carbonylamino)-toluène répondant à la formule I :
    Figure imgb0020
     dans laquelle n désigne un nombre de 5 à 15 et Y représente -H ou -F, qui peut être préparé par réaction d'un perfluoralkyl-2 éthanol répondant à la formule II :



            YCF₂-(CF₂)n-CH₂CH₂OH   (II)



    dans laquelle n et Y ont les significations qui leur ont été données ci-dessus, avec un di-isocyanato-toluène, dans le rapport molaire (1,8 à 2):1, en présence de 2 à 5 %, de préférence de 2 à 3,5 %, d'une N-méthyl-pyrrolidone par rapport au composé de formule II, et qui est dissous dans un solvant organique ou un mélange de solvants organiques, est dispersé dans de l'eau avec
    B) au moins un émulsionnant répondant à la formule III :



            YCF₂(CF₂)p-CH₂CH₂O-CO-NH-CH₂CH₂-SSO₃X   (III)



    dans laquelle p désigne un nombre de 5 à 15, Y représente -H ou -F et X représente un cation univalent, et
    C) au moins un émulsionnant non ionique répondant à la formule IV :



            YCF₂-(CF₂)q-CH₂CH₂-(OCH₂CH₂)r-OH   (IV)



    dans laquelle Y représente -H ou -F, q désigne un nombre de 5 à 15 et r désigne un nombre de 0 à 10,
    et éventuellement avec un quantité supplémentaire d'un solvant organique, les rapports entre les quantités étant choisis de telle façon qu'il se forme des dispersions selon une ou plusieurs des revendications 1 à 7.
  10. Application de la dispersion anionique aqueuse selon une ou plusieurs des revendications 1 à 7 pour l'ennoblissement oléophobe et hydrophobe de textiles.
EP86105191A 1985-04-20 1986-04-15 Dispersion aqueuse anionique Expired - Lifetime EP0202471B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT86105191T ATE65809T1 (de) 1985-04-20 1986-04-15 Waessrige anionische dispersion.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19853514373 DE3514373A1 (de) 1985-04-20 1985-04-20 Waessrige anionische dispersion
DE3514373 1985-04-20

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EP0202471A2 EP0202471A2 (fr) 1986-11-26
EP0202471A3 EP0202471A3 (en) 1988-10-12
EP0202471B1 true EP0202471B1 (fr) 1991-07-31

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US (1) US4775488A (fr)
EP (1) EP0202471B1 (fr)
JP (1) JPH06104192B2 (fr)
KR (1) KR860008334A (fr)
AT (1) ATE65809T1 (fr)
AU (1) AU582229B2 (fr)
BR (1) BR8601773A (fr)
DD (1) DD248383A5 (fr)
DE (2) DE3514373A1 (fr)
ES (1) ES8802404A1 (fr)
NZ (1) NZ215882A (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0213580B1 (fr) * 1985-08-30 1990-07-18 Hoechst Aktiengesellschaft Uréthanes contenant des groupements perfluoralcoyle et épichlorhydrine, leur dispersion aqueuse et leur application
US5242487A (en) * 1988-11-11 1993-09-07 Daikin Industries Ltd. Water- and oil-repellant composition
KR20200058622A (ko) 2018-11-19 2020-05-28 삼성디스플레이 주식회사 다결정 실리콘층의 제조 방법, 표시 장치 및 표시 장치의 제조 방법

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3171861A (en) * 1957-06-11 1965-03-02 Minnesota Mining & Mfg Fluorinated aliphatic alcohols
US3993380A (en) * 1976-01-21 1976-11-23 Lawrence Peska Associates, Inc. Combined extension cord and grounding device
CA1185731A (fr) * 1979-02-16 1985-04-16 John E. Bacino Compositions au fluorocarbure, et methode d'enduction par projection
JPS5994621A (ja) * 1982-11-12 1984-05-31 Unitika Ltd 防汚性繊維の製造法

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BR8601773A (pt) 1986-12-23
DE3514373A1 (de) 1986-10-23
US4775488A (en) 1988-10-04
NZ215882A (en) 1988-09-29
JPS61249538A (ja) 1986-11-06
ATE65809T1 (de) 1991-08-15
AU582229B2 (en) 1989-03-16
ES8802404A1 (es) 1988-05-16
DD248383A5 (de) 1987-08-05
AU5638986A (en) 1986-10-23
DE3680580D1 (de) 1991-09-05
ES554146A0 (es) 1988-05-16
KR860008334A (ko) 1986-11-14
EP0202471A3 (en) 1988-10-12
EP0202471A2 (fr) 1986-11-26
JPH06104192B2 (ja) 1994-12-21

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