WO2002000782A1 - Composition a base d'eau pour vulcanisation de caoutchouc fluore et article revetu de caoutchouc fluore - Google Patents

Composition a base d'eau pour vulcanisation de caoutchouc fluore et article revetu de caoutchouc fluore Download PDF

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WO2002000782A1
WO2002000782A1 PCT/JP2001/005492 JP0105492W WO0200782A1 WO 2002000782 A1 WO2002000782 A1 WO 2002000782A1 JP 0105492 W JP0105492 W JP 0105492W WO 0200782 A1 WO0200782 A1 WO 0200782A1
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Prior art keywords
fluororubber
fluorine
vulcanizing
formula
aqueous composition
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PCT/JP2001/005492
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English (en)
Japanese (ja)
Inventor
Nobuyuki Tomihashi
Koichiro Ogita
Kiyotaro Terasaka
Yasukazu Nakatani
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Daikin Industries, Ltd.
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Publication of WO2002000782A1 publication Critical patent/WO2002000782A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to an aqueous composition for vulcanization of fluororubber and an article coated with fluororubber, and more particularly, to an aqueous composition for fluororubber carosulfurization containing a specific fluorine-containing multi-segmented polymer.
  • Aqueous compositions for vulcanization of fluorororubber use the excellent flexibility, heat resistance, weather resistance, oil resistance, solvent resistance and chemical resistance of fluororubber, for example, textiles, fibers, metals, plastics, and rubber. It is widely used as an industrial material by being coated or impregnated on various other substrates.
  • the water-based yarn for vulcanizing fluororubber is often used as a surface coating material for rolls used in office automation (OA) equipment (eg, copiers, printers, etc.).
  • OA office automation
  • the conventional water-based composition for vulcanizing vulcanizates has been used to improve heat resistance and abrasion resistance. Is not enough.
  • fluorine Gomukaro vulcanization durability of the coating film formed from the aqueous composition to improve, to impart non-stick properties on the surface a fluorine resin or the terminal-modified per full O b polyether (end groups one ⁇ 2, is a functional group capable of reacting with fluorine rubbers such as one CH 2 0H Pafuruo port polyether compound) to be blended, etc. has been proposed (e.g., JP-5 7 - 1 3 5 8 7 1 JP, Japanese Unexamined Patent Publication No. 6-26401, etc.).
  • the heat resistance and abrasion resistance of the fluororubber itself are higher than that of the fluororesin, etc., and the fluororesin is used to improve the heat resistance and abrasion resistance of the entire composition. If a large amount of is blended, the flexibility is impaired.
  • composition in which terminally modified perfluoro-mouth polyether or the like is blended with fluororubber has good non-adhesiveness, but it cannot be said that heat resistance / abrasion resistance is sufficiently improved. Disclosure of the invention
  • An object of the present invention is to provide an aqueous composition for vulcanizing a fluororubber in which the obtained film has both heat resistance, abrasion resistance and flexibility.
  • Another object of the present invention is to provide an article having a film formed from a conventional aqueous composition for vulcanizing a fluororubber, and a fluororubber-coated article which has solved the above-mentioned disadvantages of the conventional OA equipment mouthpiece. To provide.
  • a fluorine-containing multi-segmented polymer having an elastomeric fluorine-containing polymer chain segment A and a non-elastomeric fluorine-containing polymer chain segment B,
  • An aqueous composition for vulcanization of fluororubber comprising: and an article of which at least a part of the surface is covered by a coating layer formed from the aqueous composition for vulcanization of fluororubber.
  • the elastomeric raw fluorinated polymer chain segment A is capable of imparting flexibility to the entire fluorinated multi-segmented polymer, and at least 9 0 molar 0/0 is par full O Roo reflex in units.
  • Fluororubber is usually supplied as a water dispersion.
  • Aqueous fluororubber dispergyl is a fluororubber that is prepared by adding a fluororubber in the presence of a surfactant such as polyoxyethylene alkyl ether, polyoxyethylene anolequinolefe-norethene, or anolequinolenoslephonate. It is dispersed in water at a concentration of 0 to 75% by weight.
  • Fluororubber is a fluorinated copolymer containing a repeating unit represented by —CH 2 — in the main chain.
  • a typical example thereof is an elastic fluorine-containing copolymer containing vinylidene fluoride, and specifically, a copolymer whose main chain contains a repeating unit having the following structure.
  • At least one type of repeating unit selected from:
  • R f is a perfluoroalkyl group having 1 to 6 carbon atoms.
  • At least one repeating unit selected from forces.
  • a copolymer of biurydene fluoride and hexafluoropropylene a copolymer of biurydene fluoride, tetrafluoroethylene and hexafluoropropylene, ethylene and hexafluoropropylene And a copolymer of tetrafluoroethylene and propylene.
  • vinylidene fluoride copolymers are preferred from the viewpoint of crosslinkability.
  • the amount of the fluororubber contained in the composition of the present invention is 1 to 50 parts by weight per 100 parts by weight of water.
  • the carosulfurizing agent used in the fluororubber aqueous composition for carbosulfurization of the present invention may be any of a conventionally known polyamine-based vulcanizing agent and a polyol-based vulcanizing agent [I sulfurating agent. Is preferably a polyol vulcanizing agent.
  • the polyamine-based caro sulfurizer has the formula:
  • R 1 represents a methyl group or Echiru group
  • X 1 is a single bond, one C 2 H 4 NH-, One C0NH-, or a single C 2 thigh one C 2 H 4 ⁇ over ⁇ one, y is 2 or 3.
  • R 2 , R 3 and R 4 are the same or different, and a hydrogen atom, an alkynole group having 1 to 6 carbon atoms, an amino group, a polyamino group, or at least one hydrogen atom is an amino group or a polyamino group Represents an alkyl group having 1 to 6 carbon atoms substituted with an amino group, provided that at least two of R 2 , R 3 and R 4 have an amino group, or at least one of R 2 , R 3 and R 4 One has a polyamino group.
  • polyol-based vulcanizing agent examples include a compound having at least two hydroxyl groups, particularly a phenolic hydroxyl group in a molecule, and a high-molecular compound having a U-vulcanizing property.
  • a compound having at least two hydroxyl groups particularly a phenolic hydroxyl group in a molecule
  • a high-molecular compound having a U-vulcanizing property for example,
  • Phenol compounds such as formula:
  • R 5 is an alkyl group having 1 to 4 carbon atoms, and n is 0
  • Examples of the basic conjugate include an ammonium salt, a tertiary amine, a phosphonium salt, an alkali metal, and an alkaline earth metal.
  • ammonium salt examples include trimethinolbenzilammonium, triethylbenzinoleammonium, dimethinoledecylbenzinoleum, triethylbenzyme / reammonium, myristylbenzyldimethinoleammonium, and dodecyltrimethylammonium.
  • tertiary amines include 1,8-diaza-bisic mouth [5.4.0] -ndecene_7, 8-methyl-1,8-diaza-bisic mouth [5.4.0] -ndecene -7, 8-Propyl-1,8-diaza-bisic mouth [5.4.0] -Pindecene-7, 8-Dodecyl-1,8-diaza-bisic mouth [5.4.0] -Pindecene -7,8-Eicosyl-1,8-diaza-bisic mouth [5.4.0] -Indecene-7,8-Tetracosyl-1,8-diaza-bisic mouth [5.4.0] -Indecene- 7,8-Benzyl-1,8-diaza-vicine mouth [5.4.0] -Pindecene-7,8-Phenethyl-1,8-diaza-vicine mouth [5.4.0] -Pindecene -7, 8- (3-
  • the phosphonium salt include benzyl / retrifoe- / lephosphonium, methionoletrifeninolephosphonium, 2,4-dichlorobenzinoletrifeninolephosphonium, 4-methylbenzinoletriphenylphosphonium, and 4-methylbenzinoletriphene Ninolefosphonium, m-trifluoromethylbenzyltriphenylphosphonium, 2-cyanobenzinoletriphenylphosphonium, ⁇ -force benzoethoxyretinophenylphosphonium phosphonium, diphenylmethyltriphenylphosphonium, 1-Naphthinolemethorinolephosphonium, uretethoxymethione / lethrifeninolephosphonium, methoxymethinolethrifenylphosphonium, aralkyl oximeinolethrifeninolephosphonium, 1-force Phenyl
  • alkali metal examples include lithium, sodium, and potassium.
  • anorecali earth metals include beryllium, magnesium, canolecum, And the like.
  • salts of hydroquinone, bisphenol A, bisphenol AF, and phenolic phenolic resin with gammo or tertiary amine are preferred in terms of film properties! / ,.
  • Hydroquinone, Bisufueno one Honoré A, Bisufueno one Honoré AF, Rezonore type phenol resin is particularly excellent vulcanization properties, also Anmoyuumu salt Ya tertiary Amin is Chikarari metal and Al force Li earth metals with different coating in Do not leave decomposition residues.
  • vulcanization accelerators When a polyol vulcanizing agent is used, the following compounds can be blended as vulcanization accelerators, which are optional components.
  • R 6 represents the same or different alkyl groups having 1 to 20 carbon atoms, halogenated alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, and two or more R 6 may together form a carbocyclic or heterocyclic ring
  • R 7 represents an alkylene group having 2 to 21 carbon atoms or a phenylenedialkylene group having 8 to 12 carbon atoms
  • Y represents an acid group or Represents a hydroxyl group.
  • the acid group include halide, sulfate, sulfate, bisulfite, thiosulfate, cysulfide, posizolefide, hydrogen sulfide, thiosinate, carbonate, bicarbonate, nitrate, carboxylate, porate, and phosphate.
  • Biphosphate, phosphite park mouth rate, bifluoride, arsenate, ferricyanide, ferrocyanide, molybdate, selenate, selenite, peranate, tungstate.
  • quaternary ammonium salt examples include trimethylbenzium ammonium chloride, triethylbenzylammonium chloride, dimethyldecylbenzyl realmonium chloride, triethynolebenmonoleammonium chloride, millidium chloride, Dimethyltetradecylbenzylammonium chloride, trimethinoletetradecammonium chloride, coconut trimethinoleammonium chloride Muchloride, stearyltrimethylammonium chloride, distearyldimethinoleammonium chloride, tetrabutylammonium hydroxide, 1,4-phenylenedimethylenebistrimethylammoniumdichloride, 1,4-phenylenedimethylene Alkyl and aralkyl quaternary ammonium salts such as bistriethynoleammonium dichloride and ethylenebistriethylammonium dimide, 8-methyl-1,8-diaza-bicyclo [
  • tertiary amines include trimethylamine, triethylamine, and trimethylamine.
  • -n-propylamine tri_n-butylamine, triisobutylamine, methylethylamine, dimethylethylamine, dimethyl-n-propylamine, dimethyl-n-butylamine, dimethylisobutylamine, dimethylisopropylamine, dimethyl-sec -Butylamine, dimethyl-tert-butylamine, triarylamine, di- Arylmethylamine, aryldimethylamine, benzyldimethylamine, benzyldiethylamine, N-arynolepiperidine, N-ethylpiperidine, N-butylpyperidine, N-methylpyrrolidine, N-cyclohexylpyrrolidine, N -n-butylpyrrolidin, N-ethylpyrrolidine, N-benzylpyrrolidine, 2,4,6-trimethylpyridine and the like.
  • inorganic or organic acids that form quaternary salts include:
  • R 8 represents an alkyl group having 1 to 20 carbon atoms or an Alker group, or an aryl group having 6 to 20 carbon atoms.
  • Primary or secondary amines are not preferred because reactions other than polyol vulcanization occur.
  • quaternary phosphonium salts include benzyltriphenylphosphonium chloride, benzinoletrifeninolephosphonium bromide, methinoletriphenyl phenol phosphomethine methanephosphonate, and bis (benzinoresulfene chloride).
  • Nolephosphine) lipodium chloride 2,4-diethyl benzotriphenylphosphonium chloride, 4-methinobenzoyl benzoyl chloride, 4-methylbenzoyltriphenylphosphonium chloride, 4-chlorobenzoyltriphenylphosphonium chloride , Tn-trifluoromethylbenzyltriphenylphosphonium chloride, 2-cyanobenzyltriphenylphosphonium bromide, QJ-force benzoylbenzotriole phenol dinolephosphonium bromide, diphenylenolemethinole trifle Enylphosphonium chloride , 1_naphthylmethyltriphenyl / lephosphoium chloride, Mubromide, methoxymethyltriphenylphosphoium chloride, aryloxy / triphenylphosphonium chloride, 1-force benzoquinone rife refine quinolephosphonium chloride, isoptinoletriphenyl
  • an organic acid can be added to the composition for the purpose of further improving the storage stability.
  • an organic acid having 1 to 12 carbon atoms preferably an organic acid having 1 to 4 carbon atoms is used.
  • Organic acids having more than 12 carbon atoms are not preferred because they may remain in the film.
  • More preferred organic acids are monocarboxylic acids such as formic acid, acetic acid and propionic acid, and dicarboxylic acids such as oxalic acid, malonic acid and succinic acid.
  • the organic acid suppresses polyol vulcanization of the fluorinated copolymer contained in the composition during storage. When the composition is applied, dried, and fired, the organic acid is evaporated or thermally decomposed, and the basic compound promotes the carosulfurization reaction.
  • the organic acid is also included in the “vulcanization accelerator”. .
  • 100 parts by weight of fluoro rubber Aonole vulcanizing agent 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, vulcanization accelerator 0 to 10 parts by weight, preferably 0.01 to 5 parts by weight.
  • the amount of the vulcanization accelerator is less than the above lower limit, carosulfurization is difficult to occur, while when the amount exceeds the upper limit, carosulfur control may be difficult.
  • the fluorine-containing multi-segmented polymer contained in the composition of the present invention contains, in one molecule, an elastomer 1 ′
  • elastomer-soluble segment A raw fluoropolymer chain segment A
  • non-elastomer-soluble segment B A raw fluoropolymer chain segment B (hereinafter, simply referred to as “non-elastomer-soluble segment B”) that is linked in a block or graph form.
  • the coating consisting of the fluororubber aqueous composition for calosulfuration which contains a mere mixture of an elastomeric fluorine-containing polymer and a non-elastomer fluorine-containing polymer, is based on the type of each polymer to be mixed. Although it depends on the mixing properties and compatibility, it is generally inferior in mechanical properties, abrasion resistance and flexibility.
  • Elastomeric segment A indicates a segment having a glass transition point of 25 ° C or lower, and is generally amorphous.
  • Specific examples of the monomer which is a constituent unit of the elastomer segment A include tetraphlorenoloethylene, hexafluoropropylene, ethylene chlorotrifinoleo, ethylene, perphnoleoloanolequinolebininoleatehenole (anolequinole group) Has 1 to 6 carbon atoms),
  • CF 2 CF0 (CF 2 CFX 40 ) p _ (CF 2 CF 2 CF 20 ) q — R f
  • X 4 is a fluorine atom or CF 3
  • R f is a perfluoroalkyl group having 1 to 6 carbon atoms
  • p is an integer of 0 to 5
  • q is an integer of 0 to 5, however
  • perfluorovinyl ethers represented by the following formulas.
  • combinations and compositions having elastomer properties can be used.
  • elastomeric one segment A is an elastomeric polymer chain comprising tetrafluoropropoxy O Roe Ji Ren 5 0-8 5 mol 0/0 Oyopi Pafuruoro (alkyl Biel ether Honoré) 1 5-5 0 mole 0/0 It is.
  • the elastomeric segment A can be obtained by an iodine transfer polymerization method known as a method for producing a fluororubber.
  • a method for producing a fluororubber for example, a method in which emulsion polymerization is carried out in an aqueous medium under substantially oxygen-free conditions in the presence of an iodine compound, preferably a iodine compound and a radical initiator.
  • the non-elastomer segment B preferably has a crystal melting point of 150 ° C or higher.
  • Specific examples of the fluorine-containing monomer among the monomers that can constitute the non-elastomeric segment B include tetrafluoroethylene, hexafluoropropylene, chlorotrinoleoethylene, and perphnoleroanole. Quinolebi-Noreetenore,
  • X 6 and X 7 are each a hydrogen atom or a fluorine atom, and q represents an integer of 1 to 10.
  • monomers copolymerizable with these for example, ethylene, propylene, vinylidene dendrite, vinyl ethers, vinyl carboxylate, and acrylics can also be used as the copolymerization component.
  • the non-elastomeric one segment B until Tetorafuru Oroechiren 8 5 mole 0/0 beyond 1 0 0 mole 0/0 and of formula (I):
  • R f 1 is a trifluoromethyl group or a group represented by the formula: OR f 2 (where R f 2 is a perfluoroalkyl group having 1 to 5 carbon atoms.)
  • R f 2 is a perfluoroalkyl group having 1 to 5 carbon atoms.
  • the non-elastomeric one segment B consists of tetra Furuoroechiren 8 5-9 9.7 mole 0/0, and compounds of formula (I) 0. 3 ⁇ 1 5 mole 0/0 Polymer chains.
  • the monomers used as the main components include fluorinated olefins alone, a combination of fluorinated olefins, a combination of ethylene and tetrafluoroethylene, and a combination of ethylene and ethylene oxide, from the viewpoint of heat resistance and abrasion resistance.
  • fluorinated olefins alone, a combination of fluorinated olefins, a combination of ethylene and tetrafluoroethylene, and a combination of ethylene and ethylene oxide, from the viewpoint of heat resistance and abrasion resistance.
  • Preferred is a combination of trifluoroethylene, and particularly preferred is a combination of perhaloolefins alone or a combination of perhaloolefins.
  • Blocking or grafting of the non-elastomeric segment B can be achieved by emulsion polymerization of the non-elastomeric segment A and then polymerizing the above monomer into the non-elastomeric segment B.
  • the fluorinated multi-segmented polymer thus obtained is composed of a polymer molecule (B—A—B) having a non-elastomeric segment B bonded to both ends of the elastomeric segment A and a non-elastomeric polymer at one end of the elastomeric segment A. It is mainly composed of polymer molecules (A-B) to which segment B is bonded.
  • A-B polymer molecules to which segment B is bonded.
  • the content ratio of the elastomeric segment A and the non-elastomeric segment B in the fluorine-containing multi-segmented polymer of the present invention varies depending on the use, required properties and the composition of each segment.
  • Segment B (weight ratio) "is 5Z95-98 / 2, preferably 20 / 80-95Z5.
  • the proportion of the elastomeric segment A is low, the flexibility may be insufficient, and when the proportion of the non-elastomeric segment B is low, the heat resistance, wear resistance, and mechanical properties may be insufficient. There is.
  • the fluorine-containing multi-segmented polymer is preferably used in the form of a 7K dispersion from the viewpoint of dispersibility, and is blended in an amount of 5 to 900 parts by weight to 100 parts by weight of the fluororubber.
  • a fluororesin and Z or a terminal-modified perfluoropolyether may be added to the composition of the present invention.
  • fluororesin examples include polyvinylidene fluoride, ethylene-tetrafluoroethylene copolymer, polychlorinated trifluoroethylene, tetrafluoroethylene-hexafluoropropylene-perfluoroalkylbutyl ether copolymer.
  • Polymer (EPA) tetrafluoroethylene-hexafluoropropylene copolymer
  • FEP tetrafluoroethylene-perfluoroalkynolevinyl ether copolymer
  • PFA tetrafluoroethylene-perfluoroalkynolevinyl ether copolymer
  • polytetrafluoroethylene terminal-modified EPA, terminal-modified FEP, terminal-modified PFA, and the like.
  • EPA tetrafluoroethylene-perfluoroalkynolevinyl ether copolymer
  • PFA tetrafluoroethylene-perfluoroalkynolevinyl ether copolymer
  • polytetrafluoroethylene polytetrafluoroethylene
  • terminal-modified EPA terminal-modified FEP
  • PFA terminal-modified PFA
  • the fluororesin is preferably used in the form of an aqueous dispersion from the viewpoint of dispersibility.
  • the terminally modified perfluorinated polyether used in the present invention has, in the main chain thereof, a compound represented by the following formula: — (CF (CF 3 ) CF 20 )-,-(CF 20 )-,-(CF 2 CF 20 ) One and
  • At least one type of repeating unit selected from the group consisting of repeating units represented by the formula: wherein the sum of the repeating units is in the range of 1 to 100.
  • Functional groups that modify the molecular terminals of the perfluoropolyether include Cl, Br, I, and NR 9 R lfl (wherein R 9 and R w are independently a hydrogen atom, an aryl group, or an alkyl group of. or a cycloalkyl group.), SH, NC0, N0 2, C00H, P0 2 H, S0 3 H, 0H, may be mentioned grayed Rishijiru or hydroxy-phenylene Le group. These functional groups may be located at either terminal of the main chain or side chain of the perfluoroalkyl group. These functional groups are directly bonded to the main chain composed of repeating units of the perfluoropolyether represented by the above formula, or
  • the composition of the present invention has a conductivity-imparting agent that is compatible with fluororubber compositions.
  • Various additives commonly added for example, a filler, a colorant, an acid acceptor, and the like can be added.
  • Examples of the conductivity-imparting agent include carbon blacks (Ketjen, acetylene, etc.); carbons such as PAN-based carbon fibers, pitch-based carbon fibers, and expanded graphite powder; and fluorines obtained by completely or partially fluorinating these carbons.
  • carbon acids Ag, Ni, Cu, brass, silver plated copper, Zn, Al, metal such as stainless steal (powder, deflection over click-like, etc. fibrous) s; Sn0 2 (Sb-doped), ln 2 0 Fine-particle metal oxides such as 3 (Sn-doped) and ZnO (A1 doped); ferrites; and high dielectric materials such as barium titanate.
  • the amount of the conductivity-imparting agent to be added is appropriately selected according to the type or the intended surface resistance value or volume resistance value, but it is 0 based on 100 parts by weight of the fluororubber vulcanizing aqueous composition. 440 parts by weight.
  • filler examples include calcium carbonate, barium sulfate, and H-shaped fillers such as glass fiber, carbon fiber, asbestos
  • the colorant examples include an inorganic pigment and a composite oxide pigment.
  • the acid acceptor examples include double salts such as magnesium oxide, lead oxide, zinc oxide
  • the composition of the present invention can be applied in the same manner as a conventional composition for vulcanizing a fluorine-containing copolymer, and can be vulcanized. That is, depending on the properties of the composition, the composition is applied to the object by brush coating, spray coating, immersion coating, flow coating, dispenser coating, screen coating, or the like, and after sufficiently drying, is subjected to 150 to 300. Bake at 0 ° C for 10 to 120 minutes.
  • the resulting film can have both heat resistance, abrasion resistance and flexibility.
  • a surface layer may be further formed on the coating layer formed from the composition of the present invention.
  • the surface layer is made of the above-mentioned fluorine-containing multi-segmented polymer, fluororesin, It can be formed in a conventional manner from one or more monofluoropolyethers. It is preferable that the surface of the article substrate (substrate) be sufficiently degreased and washed before applying the composition. In order to improve the adhesiveness between the article substrate and the composition, it is desirable to form a primer layer on the surface of the article to be coated with a silane-based primer or a silicone-based primer.
  • Examples of the article substrate coated with the composition of the present invention include metals such as iron, stainless steel, copper, aluminum, and brass; glass plates, glass products such as glass fiber woven and nonwoven fabrics; polypropylene, Molded products and coatings of general-purpose and heat-resistant resins such as polyoxymethylene, polyimide, polyamideimide, polysulfone, polyethersulfone, and polyetheretherketone; general-purpose rubbers such as SBR, butyl rubber, NBR, EPDM, and silicone rubber Molded articles and coatings of heat-resistant rubbers such as fluororubbers and the like; woven and nonwoven fabrics of natural
  • metals such as iron, stainless steel, copper, aluminum, and brass
  • glass plates such as glass fiber woven and nonwoven fabrics
  • the coating formed from the composition of the present invention can be used in fields where heat resistance, solvent resistance, lubricity, and non-adhesiveness are required. Specific applications include copying machines, printers, and facsimiles. Seat and belt; O-rings, diaphragms, chemical resistant tubes, fuel hoses, valve seals for OA equipment ⁇ Belts (eg, fixing zippers, crimping zippers, fixing belts) and conveyor belts for OA equipment And gaskets for chemical plants and jets.
  • Example 1 e. fixing zippers, crimping zippers, fixing belts
  • the translucent aqueous dispersion obtained by the procedure described in Example 3 of W099 / 33891 was treated with a surfactant (20% by weight of EAD-13 / .aqueous solution and 20% by weight of EAD-15 / .aqueous solution). It was concentrated to a solid concentration of 45% by weight. This is called "fluorine-containing multi-segmented polymer disparge A”.
  • Paint A was spray coated on aluminum foil, dried thoroughly at 80-100 ° C, and baked at 330 ° C for 15 minutes.
  • the aluminum foil was dissolved with hydrochloric acid, and the obtained film was punched into a JIS No. 4 dumbbell shape, and a tensile test was performed at a tensile speed of 50 OmmZmin.
  • Example 1 In the preparation of paint, 7 parts by weight of a polyol vulcanizing agent (10% by weight of 7% solution of bisphenol AFT ammonium salt) and a vulcanization accelerator in place of the polyamine vulcanizing agent (Sanapro Co., Ltd. SA610-50) The procedure of Example 1 was repeated except that 0.8 parts by weight was used.
  • a tetrafluoroethylene / perfluoroalkylbutyl ether copolymer (monomer composition: 95/5 (weight ratio)) is produced by emulsion polymerization, and the obtained aqueous dispersion is treated with a surfactant (EAD- (20% by weight of 13 // 7K solution and 20% by weight aqueous solution of EAD-15) to give a solid concentration of 48% by weight.
  • EAD- 20% by weight of 13 // 7K solution and 20% by weight aqueous solution of EAD-15
  • Paint B was spray coated on aluminum foil, dried thoroughly at 80-100 ° C, and baked at 330 ° C for 15 minutes.
  • the aluminum foil was dissolved with hydrochloric acid, and the obtained film was punched into a JIS No. 4 dumbbell shape, and a tensile test was performed at a tensile speed of 500 psi / min.
  • Example 3 In the preparation of the paint, 7 parts by weight of a polyol-based caro-sulfuric acid (10 wt./. Aqueous solution of bisphenol AF ammonium salt) and a vulcanization accelerator (SA610-50) were used instead of the polyamine-based caro-sulfuric agent.
  • SA610-50 a vulcanization accelerator
  • Paint C was spray-coated on aluminum foil, thoroughly dried at 80-100 ° C, and baked at 330 ° C for 15 minutes.
  • the aluminum foil was dissolved with hydrochloric acid, and the obtained film was punched into a JIS No. 4 dumbbell shape, and a tensile test was performed at a tensile speed of 50 O ram / min.
  • Paint D was spray coated on aluminum foil, dried thoroughly at 80-100 ° C, and baked at 330 ° C for 15 minutes.
  • the aluminum foil was dissolved with hydrochloric acid, and the obtained film was punched into a JIS No. 4 dumbbell shape, and a tensile test was performed at a tensile speed of 50 Omra / min.
  • Example 1 Example 2
  • Example 3 Vulcanization system e. Riamin Ho. Rio "Le Ho. Liamin Ho. Rio-Le
  • Comparative Example 1 Comparative Example 2 Comparative Example 3 Vulcanized e. Riamin Ho. Rio

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Abstract

L'invention concerne une composition à base d'eau destinée à la vulcanisation de caoutchouc fluoré. Cette composition renferme un caoutchouc fluoré, un fluoropolymère à segments multiples comprenant au moins un segment en chaîne de fluoropolymère élastomère et au moins un segment en chaîne de fluoropolymère non élastomère, un agent de vulcanisation et de l'eau. Ladite composition permet d'obtenir une pellicule protectrice présentant une résistance à la chaleur, une résistance à l'usure et une souplesse élevées.
PCT/JP2001/005492 2000-06-28 2001-06-27 Composition a base d'eau pour vulcanisation de caoutchouc fluore et article revetu de caoutchouc fluore WO2002000782A1 (fr)

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JP2000194642A JP2002012725A (ja) 2000-06-28 2000-06-28 フッ素ゴム加硫用水性組成物およびフッ素ゴム被覆物品
JP2000-194642 2000-06-28

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WO2002000782A1 true WO2002000782A1 (fr) 2002-01-03

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PCT/JP2001/005492 WO2002000782A1 (fr) 2000-06-28 2001-06-27 Composition a base d'eau pour vulcanisation de caoutchouc fluore et article revetu de caoutchouc fluore

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WO (1) WO2002000782A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002046302A1 (fr) * 2000-12-06 2002-06-13 Daikin Industries, Ltd. Composition de dispersion a base de fluororesine fusible, procede d'utilisation de cette composition comme revetement et article ainsi revetu

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5968363A (ja) * 1982-09-28 1984-04-18 Daikin Ind Ltd 改良されたフツ素ゴム組成物
JP2000351882A (ja) * 1999-06-14 2000-12-19 Daikin Ind Ltd フッ素ゴム加硫用水性組成物および被覆物品
WO2001000697A1 (fr) * 1999-06-30 2001-01-04 Daikin Industries, Ltd. Materiau compose fluore souple, resistant a la chaleur et non collant

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5741855A (en) * 1996-06-10 1998-04-21 Raychem Corporation Compatibilized fluoroplastic blends

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5968363A (ja) * 1982-09-28 1984-04-18 Daikin Ind Ltd 改良されたフツ素ゴム組成物
JP2000351882A (ja) * 1999-06-14 2000-12-19 Daikin Ind Ltd フッ素ゴム加硫用水性組成物および被覆物品
WO2001000697A1 (fr) * 1999-06-30 2001-01-04 Daikin Industries, Ltd. Materiau compose fluore souple, resistant a la chaleur et non collant

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JP2002012725A (ja) 2002-01-15

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