WO2002000782A1 - Water-based composition for fluororubber vulcanization and fluororubber-coated article - Google Patents

Abstract

A water-based composition for fluororubber vulcanization which comprises a fluororubber, a multi-segment fluoropolymer having at least one elastomeric fluoropolymer chain segment and at least one nonelastomeric fluoropolymer chain segment, a vulcanizing agent, and water. The composition gives a coating film having all of heat resistance, wearing resistance, and flexibility.

Description

 Specification

 Aqueous composition for fluorosulfur calo-sulfur and fluororubber coated article

 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. An article having a coating layer formed from Background art

 Aqueous compositions for vulcanization of fluororubber 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.

 Taking advantage of these features, 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.). . In recent years, OA equipment has been developed with high speed or color, and the conventional water-based composition for vulcanizing vulcanizates has been used to improve heat resistance and abrasion resistance. Is not enough.

 As a roll with excellent durability, a roll coated with a PFA (tetrafluoroethylene-perfluoroalkylalkyl vinyl ether copolymer) tube is known. Force This has a drawback of poor flexibility. It was difficult to sufficiently melt and develop color.

On the other hand, 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丽_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.).

However, 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.

 In addition, a 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.

 According to the present invention, the above-mentioned object is attained by:

 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,

 Vulcanizing agents, and

 water

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.

In a preferred embodiment, in the fluorinated multi-segmented polymer, 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.

 Hereinafter, each component contained in the composition of the present invention will be specifically described.

 (I) Fluorine rubber

 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.

One CF ₂ —CH ₂ —, one CH ₂ — CH ₂ —, and _CH ₂ —CH (CH ₃ ) —

At least one type of repeating unit selected from:

_CF ₂ — CF (CF ₃ ) —, —CF ₂ —CF ₂ —, and — CF ₂ — CF (0R _f ) _

(In the formula, R _f is a perfluoroalkyl group having 1 to 6 carbon atoms.)

At least one repeating unit selected from forces.

 More specifically, 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. Among them, 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.

0 parts by weight, preferably 5 to 300 parts by weight, more preferably 10 to 150 parts by weight.

 (Π) Caro sulfurizer and vulcanization accelerator

 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:

^{_{HsN- X 1 - C 3 H 6}} - S i - (OR x) y (CH 3) 3 one _y

(In 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丽over丽one, y is 2 or 3.)

An aminosilane compound represented by or a partial or complete hydrolyzate thereof, R,

HO— S i— O— S i— O— S i -OH

 I I I

OH OH OH

(In the formula, 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.)

And the like.

 Examples of the polyol-based vulcanizing agent 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. For example,

Phenol compounds such as formula:

(Where Y is a hydrogen atom, a halogen atom, R ⁵ , CH ₂ OR ⁵ or OR ⁵ , and Z is one C

— Or one CH, 〇CH. 1, R ⁵ is an alkyl group having 1 to 4 carbon atoms, and n is 0

Represents an integer of 0. ) And a salt of a phenol resin and a basic compound.

 Examples of the basic conjugate include an ammonium salt, a tertiary amine, a phosphonium salt, an alkali metal, and an alkaline earth metal.

 Specific examples of the ammonium salt include trimethinolbenzilammonium, triethylbenzinoleammonium, dimethinoledecylbenzinoleum, triethylbenzyme / reammonium, myristylbenzyldimethinoleammonium, and dodecyltrimethylammonium. Dimethyltetradecylbenzylammonium, trimethylenoletetradecylammonium, coconut trimethylammonium, stearyl trimethylammonium, distearyldimethylammonium, tetrabutylammonium, 1,4-phenylenedimethylenebistrimethane Noreammonium, 1,4-phenylenedimethylenebistrietinoleammonium, ethylenebistrietinoleammonium and the like.

Specific examples of 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-phenylpropyl) _1, 8-diaza-bicyclo [5.4.0] -ndecene-7, Trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, triisobutylamine, methylgetylamine, dimethylethynoleamine, dimethyl-n-propylamine, dimethyl-n-butylamine, dimethyl Isobutylamine, dimethyl / reisopropylamine, dimethyl-sec-butylamine, dimethyl-tert-butylamine, triallylamine, diarylmethylamine, aryldimethylamine, benzyldimethylamine, benzylgetylamine, N-arylpiperidine , N-ethylpiperidine, W-butylpyridine, N-methylpyrrolidine, N-cyclohexylpyrrolidine, N_n-butylpyrrolidine, N-ethylpyrrolidine, N-benzylopyrrolidine, 2,4,6-trimethylpyridine Is mentioned.

Specific examples of the phosphonium salt include benzyl / retrifoe- / lephosphonium, methionoletrifeninolephosphonium, 2,4-dichlorobenzinoletrifeninolephosphonium, 4-methylbenzinoletriphenylphosphonium, and 4-methylbenzinoletriphene Ninolefosphonium, m-trifluoromethylbenzyltriphenylphosphonium, 2-cyanobenzinoletriphenylphosphonium, α-force benzoethoxyretinophenylphosphonium phosphonium, diphenylmethyltriphenylphosphonium, 1-Naphthinolemethorinolephosphonium, uretethoxymethione / lethrifeninolephosphonium, methoxymethinolethrifenylphosphonium, aralkyl oximeinolethrifeninolephosphonium, 1-force Phenylenophosphonium, isobutynoletophenylphosphonium, 4-cyanobutinoletriphenylphosphonium, 2-pentyne / retrifenylphosphonium, arylphosphinolephosphonium, tetraphenylenophosphonium, methyltrioctylphosphonium Benzyltrioctylphosphonium, methoxhetoxetinoletriotatinolephosphonium, butyltrioctylphosphonium, _ra -trifluoromethylbenzyltrioctylphosphonium, 2,2,3,3-tetraphno 2,2-, 3,3,4,4,5,5-octafluoropentyltrioctylphosphonium, tetraoctylphosphonium, tetrabutylphosphonium, etc. No.

 Specific examples of the alkali metal include lithium, sodium, and potassium.

Specific examples of anorecali earth metals include beryllium, magnesium, canolecum, And the like.

Of these, 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.

 When a polyol vulcanizing agent is used, the following compounds can be blended as vulcanization accelerators, which are optional components.

 (a) Quaternary ammonium salt

Wherein: NR ⁶ ₄ X or _{^{R 6 3 NR 7 - NR 6}} 3 · 2Y

(Wherein 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, and Y represents an acid group or Represents a hydroxyl group.)

Quaternary gamma-pum salt indicated by.

 Specific examples of 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.

Specific examples of the quaternary ammonium salt 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 [5.4.0]- 7-indesenium chloride, 8-methinole-1,8-diaza-bisic mouth [5.4.0]-7-indene-dimethyalide, 8_methinole-1,8-diaza-bisix mouth [ 5.4.0]-7-Pindecenium hydroxide, 8-Methyl-1,8-diaza-bisic mouth [5.4.0] _7-Pindecenium-methinoresa / refate 8 main Chinore - 1, 8 Jiaza - Bishiku opening [5. 4.0] - 7-© down de Seni ©-time bromide, 8-Puropinore -

1,8-diaza-bisic mouth [5.4.0] _7-indesenimpromide, 8-dodecyl-1,8-diaza-bisic mouth [5.4.0]-7-indesenimuk Mouth Ride, 8-Dodecinole-1, 8-Diaza-Bixic Mouth [5.4.0]-7-ndesenium Hydroxide, 8-Eicosyl-1,8-Diaza-Bicyclo [ 5.4.0] -7-Pindece-mum chloride, 8-tetracosyl-1,8-diaza-bisic mouth [5.4.0] -7-Pindece-pumuclide, 8-benzyl-1,8 -Zaza-Bisik mouth [5.4.0]-7-Bendisenimuk mouth ride, 8 -Benzil-1,8-Zaza-Bishik mouth [5.4.0] -7-Pendesenium hydro Oxide, 8-Phenyl-1,8-diaza-vicide [5.4.0]-7-Pendesenimc-ride, 8- (3-phenylpropyl) -1,8-diaza-bisic Mouth [5. 4. 0] -7-Pinde-mum mouth ride, etc. Quaternary 1, 8- diaza- bicyclo [5. 4. 0]- 7-Pinde-Pum salt and the like.

 (b) quaternary salts of tertiary amines with inorganic or organic acids

Wherein: NR ⁶ ₃ or R ⁶ ₂ NR ⁷ - withdrawal ⁶ ₂

(Wherein, R ⁶ and R ⁷ are as defined above.)

Tertiary Amin indicated by.

 Specific examples of 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.

 Specific examples of inorganic or organic acids that form quaternary salts include:

Formula:

HC1, HBr, HF, (C 2 H 5) 3 NH + C1-, (C 2 H 5) 3 NH + N0 3 _{one, 2 (C 2 H 5)} 3 NH + S0 4 2 -, 2 (C 2 ^{_{H 5) 3 NH + C0 3}} 2 -, (C 2 H 5) 3 NH + R 8 0-, (C 2 H 5) 3 NH + R 8 CO0-, (C 4) 3 NH + C1-, ( C ₄ H ₉ ) ₃ NH ⁺ N 0 ₃ —, 2 (C ₄ ) ₃ NH ⁺ S 0/1, 2 (C ₄ H ₉ ) ₃ NH + C 0 ₃ ^2- , (C ₄ H ₉ ) ₃ NH + R ⁸ 0-, or (C ₄ H _{9) 3} thigh ⁺ R ⁸ C00 one

(In the formula, 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.)

And the like.

 Primary or secondary amines are not preferred because reactions other than polyol vulcanization occur.

 (c) Quaternary phosphonium salt

Wherein: PR ⁶ ₄ X or _{^{R 6 3 PR 7 - PR 6}} 3 '2Y

(Wherein, R ⁶ , R ⁷ and Y are as defined above.)

A quaternary phosphonium salt represented by the formula:

Specific examples of the 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, isoptinoletriphenylphosphonium chloride, Mupromide,

4-cyanobutinoletriphosphorum bromide, 2-pentyltriphosphophosphambromide, aryltriphosphophosphonium chloride, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenyl / lephosphonium bromide , Methyltrioctylphosphonium chloride, methyltrioctylphosphonium trafluoroporate, methyltrioctylphosphonium acetate, methyl trioctylphosphonium dimethinophosphate, benzinoletrioctyl / lephosphonium chloride, benzyl trioctyl Hoyu um bromide, main Tokisheto key Chez Chino Leto Rio Chi le phosphonyl © skeleton chloride, butyl trioctyl phosphonium - Umupuromaido, _m - triflate Ruo Lome Chino leveling down Jill tri O Chi le phosphonyl © Solid port Ride, 2,2,3,3_tetrafluoropropyltrioctylphosphorum chloride, 2,2,3,3,4,4,5,5 -Ottafluoropentinotritrioctinolephosphonide Examples include muchloride, tetraoctinolephosphonium bromide, tetraptinolephosphonium chloride, and tetrabutylphosphonium promide.

 (d) Organic acid

 In the present invention, an organic acid can be added to the composition for the purpose of further improving the storage stability. As the organic acid, 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. In the present invention, the organic acid is also included in the “vulcanization accelerator”. .

The mixing ratio of the components of the composition of the present invention, when the polyamine vulcanization system, relative to 100 parts by weight of fluorine rubber, an amine compound from 0.01 to ⁵ 0 parts by weight, preferably from 0.1 to ² 0 parts by weight It is. In the case of a polyol vulcanization system, 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. When 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. In addition, you may use together a polyamine type | system | group sulfuric acid agent and a polyol type | system | group sulfuric acid agent.

 (DI) Fluorine-containing multi-segmented polymer

 The fluorine-containing multi-segmented polymer contained in the composition of the present invention contains, in one molecule, an elastomer 1 ′ | · raw fluoropolymer chain segment A (hereinafter, simply referred to as “elastomer-soluble segment A”) and a non-elastomer. (5) 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.

 A film obtained from a fluororubber hydrosulfuric acid composition obtained by combining such a fluorine-containing multi-segmented polymer with heat resistance, abrasion resistance and non-adhesiveness while maintaining sufficient flexibility It is. In comparison with this, 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),

Formula: CF ₂ = CF0 (CF ₂ CFX ⁴⁰ ) _p _ (CF ₂ CF ₂ CF ₂₀ ) _q — R _f

(In the formula, 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!) + q≥1. And the like, and perfluorovinyl ethers represented by the following formulas. Of these, combinations and compositions having elastomer properties can be used. In addition, 10 moles of a monomer that provides a cure site for vulcanization of polyamine caro-sulfur and polyol—a monomer containing a functional group that imparts functions such as adhesion to other materials. /. It may be introduced below. In a preferred embodiment, 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. 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,

Formula: CF ₂ = CF (CF ₂ ) _p X ⁵

(Wherein p is an integer of 1 to 10 and X ⁵ represents a fluorine atom or a chlorine atom.) And perhaloolefins such as perfluoro-2-butene; vinylidene fluoride, vinylinolefin Ride, trifluoroethylene, formula: CH ₂ = C (CF ₃ ) ₂

Formula: CH ₂ = CX ⁶ — (CF ₂ ) _q _X ⁷

(In the formula, X ⁶ and X ⁷ are each a hydrogen atom or a fluorine atom, and q represents an integer of 1 to 10.)

And the like.

 In addition, monomers copolymerizable with these, for example, ethylene, propylene, vinylidene dendrite, vinyl ethers, vinyl carboxylate, and acrylics can also be used as the copolymerization component.

In one preferred embodiment, 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):

CF ₂ = CF-R _f ¹ (I)

(In the formula, 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.) A polymer chain consisting of 0 to less than 15 mol% of the compound represented by the formula: Further, in another preferred embodiment, 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.

 Among the above, 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. 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. When the number of polymer molecules of only the elastomeric segment A to which the non-elastomeric segment B is not bonded is large, the mechanical properties and abrasion resistance of the obtained film tend to decrease. 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. When 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.

 (IV) Fluororesin and terminally modified perfluorinated polyether

Heat resistance of the resulting film ゃ Further improve abrasion resistance or flexibility In order to adjust various physical properties of the composition, a fluororesin and Z or a terminal-modified perfluoropolyether may be added to the composition of the present invention.

 Specific examples of the fluororesin include polyvinylidene fluoride, ethylene-tetrafluoroethylene copolymer, polychlorinated trifluoroethylene, tetrafluoroethylene-hexafluoropropylene-perfluoroalkylbutyl ether copolymer. Polymer (EPA), tetrafluoroethylene-hexafluoropropylene copolymer

(FEP), tetrafluoroethylene-perfluoroalkynolevinyl ether copolymer (PFA), polytetrafluoroethylene, terminal-modified EPA, terminal-modified FEP, terminal-modified PFA, and the like. One or more of these can be used. Among them, a tetrafluoroethylene polymer is preferable in terms of non-adhesiveness. 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

― (CF ₂ CF ₂ CF ₂ 0)

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

Formula: One (CH ₂ ) _n —, One (CF ₂ ) _n —, One (CH ₂ 0) _n —, or One (CF ₂ 0) _n —

 (Where l≤n <100)

Via

 (V) Various additives

In addition to the above, 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.

 Examples of the filler include calcium carbonate, barium sulfate, and H-shaped fillers such as glass fiber, carbon fiber, asbestos | ¾ 锥, and potassium titanate »锥. Examples of the colorant include an inorganic pigment and a composite oxide pigment.

 Examples of the acid acceptor include double salts such as magnesium oxide, lead oxide, zinc oxide | &, lead carbonate, zinc carbonate, and hydrotalcite, and those having high activity such as calcium hydroxide gelate. Easy to wake up, not preferred. Further, a compound having a pKa smaller than that of the basic compound is preferable. If the pKa of the acid acceptor is large, the composition is liable to cause geli-dori. Usually, the acid acceptor can be blended in an amount of 1 to 40 parts by weight based on 100 parts by weight of the fluorine-containing copolymer depending on its activity.

 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.

 In the aqueous composition for fluororubber calosulfurization of the present invention, 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 | ¾ 锥 and synthetic il; and the like can be used.

 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 口 Belts (eg, fixing zippers, crimping zippers, fixing belts) and conveyor belts for OA equipment And gaskets for chemical plants and jets. Example

 Hereinafter, the present invention will be described specifically with reference to Examples.

 Example 1

 Preparation of fluoro rubber dispersion A:

An aqueous dispersion obtained by producing a vinylidene fluoride / tetrafluoroethylene / hexafluoropropylene copolymer (monomer composition: 65/18/17 (molar ratio)) by emulsion polymerization. .. 2 0 weight of a surfactant (manufactured by NOF Corp. EAD- _13/0 aqueous solution and 2 0 weight ./ company made EAD- 15 aqueous solution: both major component, C ₁₃ H ₂₇ -

0 (CH ₂ CH ₂ 0) _n H) to a solids concentration of 60% by weight. This is called "Fluorine Rubber Disposable A ".

 Preparation of Fluorinated Multi-Segmented Polymer Dispersion A:

 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".

 The composition of the non-elastomeric fluoropolymer chain segment in the fluorine-containing multi-segmented polymer contained in the aqueous dispersion is TFEZPFVE = 99.0 / 1.0 (molar ratio), The composition of the fluorinated polymer chain segment was TFEZPMVE = 6040 (molar ratio).

 Preparation of Pigment paste A:

 3 parts by weight of a filler (Talox R-516L manufactured by Titanium Industry Co., Ltd.) and 5 parts by weight of an acid acceptor (DHT-4A manufactured by Kyowa Chemical Industry Co., Ltd.) were added to a surfactant (20 parts by weight of a surfactant (EAD-13). Aqueous solution) was dispersed in 46 parts by weight of pure water together with 2 parts by weight to prepare a paste. This is called “Pigtnent Paste A”.

 Preparation of Paint A:

 38 parts by weight of a fluororubber dispurgeon A, 52 parts by weight of a fluorine-containing multi-segmented polymer disperseon A, and 12 parts by weight of a pigment paste A were mixed and dispersed in + minutes. To 100 parts by weight of this aqueous dispersion, 5 parts by weight of a polyamine vulcanizing agent (GLS-223B solution manufactured by Daikin Industries, Ltd.) was added to prepare a coating material. This is called “Paint A”.

 Preparation of film and measurement of tensile properties:

 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 2

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.

 Example 3

 Preparation of fluororesin dispersion A:

 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. This is referred to as “fluororesin dispersion A”.

 Preparation of Paint B:

 Mix and sufficiently disperse 8 parts by weight of fluoro rubber dispersion A, 26 parts by weight of fluorine-containing multi-segmented polymer monodispersion A, 26 parts by weight of fluororesin dispersion A, and 12 parts by weight of pigment paste A. Was. To 100 parts by weight of this aqueous dispersion was added 5 parts by weight of a polyamine-based U sulfurizing agent (GLS-223B solution) to prepare a coating material. This is called “Paint B”.

 Preparation of film and measurement of tensile properties:

 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 4

 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. Example 3 was repeated except that 8 parts by weight were used.

 Comparative Example 1

 Preparation of Paint C:

Fluororubber Disconnect purge Yung A 3 8 parts by weight, the fluorine榭脂disk purge Yung A 5 2 parts by weight, was thoroughly dispersed in a mixture of Pigment Paste A 1 ² parts by weight. To 100 parts by weight of the aqueous dispersion, 5 parts by weight of a polyamine-based vulcanizing agent (GLS-223B liquid) was added, A paint was prepared. This is called “Paint C”.

 Preparation of film and measurement of tensile properties:

 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.

 Comparative Example 2

 In the preparation of the paint, instead of the polyamine vulcanizing agent, 7 parts by weight of a polyolefin vulcanizing agent (a 10% by weight aqueous solution of bisphenol AF ammonium salt) and 0.8 parts by weight of a vulcanization accelerator (SA610-50) were used. Comparative Example 1 was repeated except that it was used.

 Comparative Example 3

 Preparation of Paint D:

 50 parts by weight of a fluorine-containing multi-segmented polymer dispersion A, 5 parts by weight of ethylene glycolone, and 1 part by weight of jetanolamine were mixed and sufficiently dispersed. This is called “Paint D”.

 Preparation of film and measurement of tensile properties:

 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.

 Tables 1 and 2 show the above results. Example 1 Example 2 Example 3 Example 4 Vulcanization system e. Riamin Ho. Rio "Le Ho. Liamin Ho. Rio-Le

Tensile properties

• 100% tensile stress (kgfZcm ² ) 37 29 44 36

'' Strength at break (kgf / cm ² ) 76 52 79 58

• Elongation at break (%) 270 420 220 380 Table 2

 Comparative Example 1 Comparative Example 2 Comparative Example 3 Vulcanized e. Riamin Ho. Rio

Tensile properties

-100 ° /. Tensile stress (kgfZcm ² ) 51 42 88

• Strength at break (kgf / cm ² ) 86 60 110

• Elongation at break (%) 220 370 150

Claims

The scope of the claims

 1. fluoro rubber,

 Elastomer '! ■ Fluorine-containing multi-segmented polymer having raw fluorine-containing polymer chain segment and non-elastic 1, mer-fluorinated polymer chain segment 1,

 Vulcanizing agents, and

 water

An aqueous composition for vulcanizing a fluororubber comprising:

2. elastomeric one fluorine-containing polymer chain segment, which can provide flexibility to the entire fluorine-containing multi-segment polymer, at least 9 0 mole _^0/0 of its constituent units par full O Roo reflex in units 2. The fluororubber vulcanizing aqueous composition according to claim 1.

3. The elastomeric one fluorine-containing polymer chain segment is a tetrafurfuryl O Roe Ji Ren 50-85 mole _^0/0 and Pafuruoro (alkyl Honoré vinyl ether) 1 5 elastic polymer strand consisting of 50 mole _^0/0 according Item 3. The aqueous composition for vulcanizing a fluororubber according to Item 1 or 2.

4. The non-elastomeric one fluorine-containing polymer chain segment, until Tetorafuruoroe styrene 85 Monore _^0/0 beyond 100 mole _^0/0, and of formula (I):

CF ₂ = CF-R _f ¹ (I)

(In the formula, Rf 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.) 3. The aqueous composition for vulcanizing a fluororubber according to claim 1, which is a polymer chain comprising less than 15 mol% of the compound represented by the formula (1).

. 5. non Erasutoma fluorine-containing polymer Ichikusari segment Tetorafuruoroe styrene 85 to 99 7 mol _^0/0, and of formula (I):

CF ₂ = CF-R _f ¹ (I)

(In the formula, represents 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.)) fluorine rubber vulcanization aqueous composition of claim 1 in a polymer chain composed of a compound from 0.3 to 15 mole _^0/0 indicated.

6. The aqueous composition for vulcanizing a fluororubber according to any one of claims 1 to 5, further comprising a fluororesin Z or a terminal-modified perfluoropolyether.

 7. The aqueous composition for vulcanizing a fluororubber according to any one of claims 1 to 6, wherein the vulcanizing agent is a polyol vulcanizing agent.

 8. An article, the surface of which is at least partially covered with a coating layer formed from the aqueous composition for vulcanizing a fluororubber according to any one of claims 1 to 7.

 9. The article according to claim 8, which is a mouthpiece or belt for office automation equipment.