EP0249126B1 - Finissages hydrophobiques et oléophobiques - Google Patents

Finissages hydrophobiques et oléophobiques Download PDF

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Publication number
EP0249126B1
EP0249126B1 EP87107948A EP87107948A EP0249126B1 EP 0249126 B1 EP0249126 B1 EP 0249126B1 EP 87107948 A EP87107948 A EP 87107948A EP 87107948 A EP87107948 A EP 87107948A EP 0249126 B1 EP0249126 B1 EP 0249126B1
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EP
European Patent Office
Prior art keywords
component
contain
epichlorohydrin
textile
agents
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
Application number
EP87107948A
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German (de)
English (en)
Other versions
EP0249126A3 (en
EP0249126A2 (fr
Inventor
Wilfried Di. Kortmann
Wulf Dr. Von Bonin
Firedrich Dr. Reich
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Bayer AG
Original Assignee
Bayer AG
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Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Priority to AT87107948T priority Critical patent/ATE71676T1/de
Publication of EP0249126A2 publication Critical patent/EP0249126A2/fr
Publication of EP0249126A3 publication Critical patent/EP0249126A3/de
Application granted granted Critical
Publication of EP0249126B1 publication Critical patent/EP0249126B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • 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
    • 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
    • D06M13/46—Compounds containing quaternary nitrogen atoms
    • D06M13/463—Compounds containing quaternary nitrogen atoms derived from monoamines
    • 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
    • D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
    • 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
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/04—Vegetal fibres
    • D06M2101/06—Vegetal fibres cellulosic
    • 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
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/04—Vegetal fibres
    • D06M2101/06—Vegetal fibres cellulosic
    • D06M2101/08—Esters or ethers of cellulose
    • 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
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/10—Animal fibres
    • D06M2101/12—Keratin fibres or silk
    • 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
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/26—Polymers or copolymers of unsaturated carboxylic acids or derivatives thereof
    • D06M2101/28—Acrylonitrile; Methacrylonitrile
    • 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
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/32—Polyesters
    • 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
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/34—Polyamides
    • 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
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/11—Oleophobic properties
    • 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
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties

Definitions

  • both the carrier group and the polymer serve to convert the inert fluorocarbon residue as carrier of the phobicization function into a stable preparation, e.g. B. to be transferred in an aqueous medium or to bring about the adhesion and permanence of the fluorocarbon group on the substrate.
  • perfluoro compounds are perfluorocarboxylic acids or sulfonic acids or their salts and derivatives such as amides and (co) polymers of unsaturated compounds which contain the perfluoroalkyl radical mentioned, with optionally fluorine-free monomers, e.g. B. in the form of polymer dispersions or latices.
  • Suitable unsaturated compounds with a perfluoroalkyl radical are known, for example, from US Pat. No. 3,916,053.
  • Preferred compounds are acrylate (co) polymers with a fluorine content of 20-45, in particular 35-45% by weight.
  • Compounds of this type are described, for example, in US-A-3,356,628, 3,329,661, 3,752,783 and 4,296,224.
  • Preferred fatty acids are straight-chain or branched, saturated or unsaturated fatty acids with 12-22 carbon atoms or mixtures thereof, in particular those with melting points above 30 ° C.
  • Preferred polyamines are polyalkylene polyamines and in particular polyethylene-polyamine mixtures which are obtained when dihaloethane is reacted with ammonia.
  • these mixtures those which consist of polyethylene polyamines with at least 3 amino groups, in particular 3-7 amino groups, are again to be mentioned. They are obtained, for example, by distilling off the di- and triamine fraction from the reaction products of dichloroethane and ammonia mentioned above.
  • the basic amides are obtained from this by reacting 0.75-1.5, in particular 0.8-1.1, equivalents of fatty acid per primary amino group of the polyethylene polyamine.
  • Quaternized basic amides B. which are preferably prepared by quaternization in an aqueous medium, are described, for example, in GB-A-711 404, in DE-A-35 15 479 and 35 27 976.
  • Particularly preferred amides B. are known from EP-A-0 008 761 and DE-A-35 15 480. From these publications is the use of the amides reacted with epichlorohydrin in aqueous medium as paper sizing agents is known.
  • the agents according to the invention serve in particular as textile finishing agents. They are preferably in the form of aqueous dispersions.
  • the quantitative ratio of A: B is, for example, 2: 1 to 1:10, in particular 1: 1 to 1: 6, based on the solids content.
  • the aqueous dispersions preferably contain a total solids content of 0.5-50, preferably 5-25% by weight.
  • the dispersions are stable and can be marketed as such. You can add other ingredients such as other textile auxiliaries, e.g. B. synthetic resins. These further constituents are preferably nonionic or cationic.
  • the aqueous dispersions can be further diluted with water before use on the textile materials.
  • the ratio of aqueous dispersion to textile material is chosen so that a coating quantity of 0.5-15.0 g, preferably 0.5-5.0 g and in particular 0.5-1.5 g, total solids of the mixture according to the invention per kg Textile material is achieved.
  • natural and synthetic materials such as fibers, filaments, yarns, nonwovens, fabrics, knitted fabrics and knitted fabrics made in particular of cellulose and its derivatives but also of polyester, polyamide and polyacrylonitrile materials, wool or silk can be successfully finished.
  • the hydrophobized or oleophobicized textile structures are found, for. B. Use for the production of umbrella coverings, tents, water-repellent clothing or covers, balloon covers, awnings, textile floor coverings, packaging materials or footwear.
  • the finishing is carried out by known methods, preferably by the pull-out or padding method, for example between room temperature and 40 ° C., but also by splashing or spraying with a subsequent temperature treatment at 80-180, preferably 120-150 ° C.
  • the textile finishing agents according to the invention have no advantages with regard to a sizing effect on paper compared to the components B.
  • This behavior of the mixtures used according to the invention shows that the known action of the quaternized basic fatty acid amides used as paper sizes does not indicate their suitability as a component of the invention Phobitation formulations allow, although the paper sizing is an effect that appears to be comparable to a hydrophobing.
  • dispersion A an acrylate copolymer containing perfluoroalkane groups and having an F content of approx. 40% by weight in solids, used in the market for textile hydrophobization and present in approx. 15% aqueous dispersion, is used.
  • dispersion B An approximately 15% aqueous dispersion according to EP-A-0 008 761, size G, is used as dispersion B.
  • Dispersions A. and B. are now mixed in a weight ratio of 1: 2.
  • Phobianssflotten are made from these components, which contain different amounts of the components depending on the textile fiber substrate.
  • the grade for oil repellency corresponds to the highest numbered test liquid that does not wet the fiber material within 30 seconds: Grade 1 lowest value Grade 8 highest value.
  • a cotton gabardine fabric with a m2 weight of approx. 240 g was equipped with the following formulations on the foulard.
  • a b c d Synthetic resin A 60 60 60 60 60 g / l catalyst 4th 4th 4th 4th g / l Component V 20th 20th 20th 20th g / l Component II - 20th - - g / l Component III - - 20th - g / l Component IV - - - 10th g / l
  • component II and III claimed according to the invention give this increase of 3 g / l, based on the solid substance, while component IV, which is not according to the invention, is effective only when the amount used is 10 g / l.
  • Component IV does not improve the grip compared to textile goods treated only with Component V, but rather affects the character of the grip on the rougher, harder side.
  • Components II and III create a soft, smooth and flowing handle.
  • extenders in combination with fluorine-based phobing agents, increase the oil-repellent effect (for example, formulation d).
  • the increase in effect with component III represents an improvement that cannot be achieved with known extenders.
  • a colored polyester / cotton poplin fabric (67% PES / 33% cotton) with a weight of approx. 160 g m2 was equipped with the following formulations on the foulard: a b c Synthetic resin A 60 60 60 g / l catalyst 4th 4th 4th g / l Component V 20th 20th 20th g / l Component II - - 20th g / l Component IV - 10th - g / l
  • the finished samples were then washed 5 times at 40 ° C on a Miele washing machine type W 763 with the easy-care program with the addition of a household detergent and dried at 80 ° C in a Miele household dryer.
  • Component II claimed according to the invention improves the washing resistance of fluorine finishes in such a way that even after 5 machine washes, the phobic values are completely retained, while the finishes without extender or with component IV drop off significantly or are no longer present.
  • Example 2 The textile goods described in Example 2 were equipped with the following liquors using the same process and the same treatment.
  • component II claimed according to the invention is also used in the equipment fleet, optimum results are achieved Hydrophobic values achieved with half the amount of fluorine normally used.
  • component IV in the finishing bath still requires 75% of the amount of fluorine.
  • the material available for finishing is a polyacrylic awning fabric: 290 g / m2, spinneret-dyed, sold under the brand name DRALON (Bayer AG).
  • the equipment is applied as a pad.
  • the fleet intake is 75% of the weight of the goods.
  • the awning fabric is treated at 150 ° C for 4 minutes.
  • a polyamide taffeta fabric for umbrella covering (m2 - weight: 70 g) is equipped with the following liquor formulations on the foulard: a b c d Component V 10th 10th 10th 10th Component I - 10th - - Component IV - - 3rd 10th
  • the wet weight gain is approximately 62%.
  • the polyamide fabric is treated for 5 minutes at 150 ° C.
  • a b c d 1a beading time (minutes) 8th 10th 0 10th 1b) Beading off effect (grade 5-1) 3rd 5 3rd 5 1c) water absorption (%) 13 4th 12 16 1d) water penetration (cm3) 40 10th 50 40 3) Oil repellency (grade 1-8) 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6
  • component I does not change the oil repellency.
  • Textiles containing wool and wool require extremely high amounts of fluorine-containing products in order to achieve practical hydro- and oleophobic treatment compared to pure synthetic fiber materials.
  • a polyester wool blend fabric (45% wool and 55% polyester, weight: 311 g / m2) is padded as follows: a b c Component V 50 50 50 g / l Component II - 25th - g / l Component IV - - 15 g / l
  • Component IV achieves only a slight improvement over the textile goods that are only equipped with component V.
  • a wool fabric with a weight of 288 g / m2 is given the following formulations in the pull-out process: a b c Component V 2nd 2nd 2nd % of the weight of the goods Component I - 2nd - "" Component IV - - 2nd ""
  • the liquor ratio (product weight to liquor quantity) is 1: 30.
  • the liquors are adjusted to a pH of 6 using 60% acetic acid.
  • the treatment is first carried out at 18 ° C for 20 minutes. Then the liquor temperature is increased to 40 ° C and treated again for 20 minutes. The goods are moved evenly in the fleet throughout the period.
  • the wool samples are then centrifuged in a dewatering centrifuge to a residual moisture content of 30%, dried at 100 ° C and reheated at 140 ° C for 3 minutes.
  • Component V and the mixture V with IV do not give any hydrophobic effect. Only the use of component I with component V show very good water-repellent effects in the irrigation test. The oil repellency is increased by one or two notes compared to formula a or c.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Lubricants (AREA)
  • Fats And Perfumes (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Dental Preparations (AREA)
  • Materials For Medical Uses (AREA)

Claims (6)

  1. Produits hydrofugeants et oléofugeants qui contiennent :
    A. un composé à un groupe perfluoralkyle en C₂-C₂₀ qui peut être interrompu par l'oxygène et qui est relié à un groupe porteur réactif ou polaire ou à la chaîne d'un polymère, et
    B. des produits de quaternisation d'amides d'acides gras basiques obtenus par réaction d'acides gras à plus de 8 atomes de carbone, de polyamines et de 0,5 à 5 équivalents d'épichlorhydrine par rapport aux groupes amino de l'amide basique.
  2. Produits selon la revendication 1, contenant en tant que composant A un (co)polymère d'acrylate à une teneur en fluor de 20 à 45% en poids.
  3. Produits selon la revendication 1, contenant en tant que composant B un produit de réaction d'acides gras saturés ou insaturés en C₁₂-C₂₂, de polyalkylènepolyamines et de 0,5 à 5 équivalents d'épichlorhydrine.
  4. Produits selon la revendication 3, contenant en tant que composant B un produit de réaction dont le composant polyalkylènepolyamine est un mélange polyéthylènepolyamines obtenu par réaction du dichloréthane avec l'ammoniac et séparation des fractions de di- et le cas échéant de tri-amines.
  5. Produits selon la revendication 3, contenant en tant que composant B un produit de réaction de l'épichlorhydrine obtenu par quaternisation avec l'épichlorhydrine en milieu aqueux.
  6. Procédé pour l'apprêtage de matières textiles, caractérisé en ce que l'on utilise des produits selon les revendications 1 à 5.
EP87107948A 1986-06-13 1987-06-02 Finissages hydrophobiques et oléophobiques Expired - Lifetime EP0249126B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87107948T ATE71676T1 (de) 1986-06-13 1987-06-02 Hydrophobe und oleophobe ausruestungen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3620033 1986-06-13
DE19863620033 DE3620033A1 (de) 1986-06-13 1986-06-13 Hydrophobe und oleophobe ausruestungen

Publications (3)

Publication Number Publication Date
EP0249126A2 EP0249126A2 (fr) 1987-12-16
EP0249126A3 EP0249126A3 (en) 1990-07-04
EP0249126B1 true EP0249126B1 (fr) 1992-01-15

Family

ID=6302997

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87107948A Expired - Lifetime EP0249126B1 (fr) 1986-06-13 1987-06-02 Finissages hydrophobiques et oléophobiques

Country Status (10)

Country Link
US (1) US4833188A (fr)
EP (1) EP0249126B1 (fr)
JP (1) JPH0674410B2 (fr)
AT (1) ATE71676T1 (fr)
CA (1) CA1339998C (fr)
DE (2) DE3620033A1 (fr)
DK (1) DK171182B1 (fr)
ES (1) ES2044866T3 (fr)
FI (1) FI90791C (fr)
PT (1) PT85003B (fr)

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AU648738B3 (en) * 1992-06-19 1994-04-28 Kelvin Harold Arnold Vertical and roller blinds made of treated fabric
DE4228975C2 (de) * 1992-08-31 2002-01-31 Gore W L & Ass Gmbh Oleophob und/oder permanente hydrophob ausgerüstete Fasern, textile Materialien und Membranen, Verfahren zur Herstellung der Fasern, textilen Materialien und Membranen
US5380778A (en) * 1992-09-30 1995-01-10 Minnesota Mining And Manufacturing Company Fluorochemical aminoalcohols
JP3266031B2 (ja) * 1996-04-18 2002-03-18 株式会社村田製作所 圧電共振子およびそれを用いた電子部品
US6197378B1 (en) 1997-05-05 2001-03-06 3M Innovative Properties Company Treatment of fibrous substrates to impart repellency, stain resistance, and soil resistance
US6077468A (en) 1999-01-11 2000-06-20 3M Innovative Properties Company Process of drawing fibers
US6207088B1 (en) 1999-01-11 2001-03-27 3M Innovative Properties Company Process of drawing fibers through the use of a spin finish composition having a hydrocarbon sufactant, a repellent fluorochemical, and a fluorochemical compatibilizer
US6117353A (en) * 1999-01-11 2000-09-12 3M Innovative Properties Company High solids spin finish composition comprising a hydrocarbon surfactant and a fluorochemical emulsion
US6120695A (en) * 1999-01-11 2000-09-19 3M Innovative Properties Company High solids, shelf-stable spin finish composition
US6068805A (en) * 1999-01-11 2000-05-30 3M Innovative Properties Company Method for making a fiber containing a fluorochemical polymer melt additive and having a low melting, high solids spin finish
US6537662B1 (en) 1999-01-11 2003-03-25 3M Innovative Properties Company Soil-resistant spin finish compositions
US6355081B1 (en) 1999-06-01 2002-03-12 Usf Filtration And Separations Group, Inc. Oleophobic filter materials for filter venting applications
US6579342B2 (en) 2001-02-07 2003-06-17 Pall Corporation Oleophobic membrane materials by oligomer polymerization for filter venting applications
US6521012B2 (en) 2001-05-01 2003-02-18 Pall Corporation Oleophobic coated membranes
US6811696B2 (en) * 2002-04-12 2004-11-02 Pall Corporation Hydrophobic membrane materials for filter venting applications
JP2008202174A (ja) * 2007-02-21 2008-09-04 Ist Corp 撥水撥油性獣毛繊維製品

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US2937098A (en) * 1958-09-18 1960-05-17 Simoniz Co Liquid polishing composition driable to a bright coating
US3252932A (en) * 1959-08-10 1966-05-24 Minnesota Mining & Mfg Resin compositions comprising a segmented fluorine-containing copolymer and an aminoplast
US3441531A (en) * 1966-01-17 1969-04-29 Pennsalt Chemicals Corp Vinylidene fluoride polymer dispersions having low viscosity
US3462296A (en) * 1966-07-22 1969-08-19 Du Pont Fluorinated oil- and water-repellent copolymer and process for treating fibrous materials with said copolymer
FR2202144A1 (en) * 1972-10-11 1974-05-03 Asahi Glass Co Ltd Oil and water-repellent compsns - contg copolymers of fluoroalkyl gp-contg monomers, haloalkyl vinyl ethers and opt. other monomers
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DE3515480A1 (de) * 1985-04-30 1986-10-30 Bayer Ag, 5090 Leverkusen Kationische leimungsmittel
DE3515479A1 (de) * 1985-04-30 1986-10-30 Bayer Ag, 5090 Leverkusen Verfahren zur herstellung von papier oder papieraehnlichen materialien
DE3527976A1 (de) * 1985-08-03 1987-02-05 Bayer Ag Verfahren zur herstellung von papier oder papieraehnlichen materialien
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Also Published As

Publication number Publication date
PT85003A (en) 1987-07-01
ES2044866T3 (es) 1994-01-16
US4833188A (en) 1989-05-23
JPH0674410B2 (ja) 1994-09-21
DE3775995D1 (de) 1992-02-27
FI872607A0 (fi) 1987-06-11
EP0249126A3 (en) 1990-07-04
CA1339998C (fr) 1998-08-18
DK300587D0 (da) 1987-06-12
DK300587A (da) 1987-12-14
JPS633084A (ja) 1988-01-08
DK171182B1 (da) 1996-07-15
EP0249126A2 (fr) 1987-12-16
DE3620033A1 (de) 1987-12-17
ATE71676T1 (de) 1992-02-15
FI872607A (fi) 1987-12-14
FI90791C (fi) 1994-03-25
PT85003B (pt) 1990-03-08
FI90791B (fi) 1993-12-15

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