WO2002046302A1

WO2002046302A1 - Dispersion composition of fusible fluororesin, method of coating with the same, and coated article

Info

Publication number: WO2002046302A1
Application number: PCT/JP2001/010658
Authority: WO
Inventors: Yasukazu Nakatani; Koichiro Ogita
Original assignee: Daikin Industries, Ltd.
Priority date: 2000-12-06
Filing date: 2001-12-06
Publication date: 2002-06-13
Also published as: JPWO2002046302A1

Abstract

A dispersion composition which comprises a liquid medium and, dispersed therein, fusible fluororesin particles having an average-particle diameter of 5 to 1,000 νm and a multi-segment fluoropolymer comprising an elastomeric fluoropolymer chain segment and a nonelastomeric fluoropolymer chain segment. From this composition, a coating film combining durability with flexibility can be obtained.

Description

Specification

Fluorine-containing molten resin dispersion composition, its coating method and coated article

Technical field

TECHNICAL FIELD The present invention relates to a fluorine-containing molten resin dispersion composition, a method for coating the same, and a coated article. More specifically, the present invention relates to a fluorine-containing molten resin dispersion composition capable of obtaining a film having both durability and flexibility, and silicone. The present invention relates to a method of coating a rubber, heat-resistant resin or metal product with such a fluorine-containing molten resin dispersion composition and a coated article.

Background art

In general, silicone rubber or metal is used as the base material for rolls (hereinafter simply referred to as “OA rolls”) used in office automation (OA) equipment (eg, copiers, printers, etc.). On the surface of such an OA roll, a coating film made of a general fluorine-containing molten resin dispersion paint is formed for the purpose of imparting durability and non-adhesiveness. The resin contained in such a fluorine-containing molten resin-dispersed coating material has a small particle size of about 0.2 to 0.6 μπι and cannot obtain a sufficient film thickness, and thus has satisfactory durability. Sex has not been obtained. In addition, in recent years, as the colorization of office automation equipment has progressed, the sharpness of images has been required, and accordingly, it has been required that office automation rolls have both durability and flexibility.

Rolls with excellent flexibility can increase the nip width, and images fixed with such rolls are generally known to have small character misalignment and high sharpness.

Even when a belt made of a heat-resistant resin or metal is used instead of a silicone rubber port or a metal port, a film made of a fluorine-containing molten resin-dispersed paint is formed on the belt surface. Achieving both durability and flexibility is required.

In addition, as the speed of office automation equipment increases, the paper transportability of rolls and belts also needs to be improved.

Disclosure of the invention An object of the present invention is to provide a fluorine-containing molten resin dispersion composition capable of forming a film having both high durability and flexibility and high paper transportability. Another object of the present invention is to provide a method for coating a fluorine-containing resin-dispersed composition on a silicone rubber, heat-resistant resin or metal article, and an article produced by the coating method.

The above purpose is

(1) Fluorine-containing molten resin powder having an average particle size of 5 to 1000 μm, and a fluorine-containing multi-segmented polymer having an elastomeric fluorine-containing polymer chain segment and a non-elastomer-containing fluorine-containing polymer chain segment A fluorine-containing molten resin dispersion composition obtained by dispersing

(2) a laminate comprising a substrate made of silicone rubber, a heat-resistant resin or a metal, and a film formed on the surface of the substrate from the fluorine-containing molten resin dispersion composition of (1) above;

(3) a substrate comprising silicone rubber, a heat-resistant resin or a metal; an elastic layer formed on the surface of the substrate; and the fluorine-containing molten resin dispersion composition of (1) above on the elastic layer. A laminate having a formed film,

(4) The fluorinated molten resin dispersion composition of (1) above is applied to at least a part of silicone rubber, heat-resistant resin or metal article via a primer, and the liquid medium is removed from the applied composition. A method for coating an article comprising firing the fluorine-containing molten resin powder and the fluorine-containing multi-segmented polymer,

(5) The fluorine-containing molten resin dispersion composition of (1) above is applied to at least a part of silicone rubber, heat-resistant resin or metal article via an elastic layer, and a liquid medium is formed from the applied composition. Removing, followed by baking the fluorinated molten resin powder and the fluorinated multi-segmented polymer,

(6) A silicone rubber article having at least a part of its surface coated with a fluorine-containing molten resin dispersion composition according to the coating method of (4) or (5) above.

(7) An article made of a heat-resistant resin whose surface is at least partially coated with the fluorinated molten resin dispersion composition by the coating method of (4).

and (8) A metal article whose surface is at least partially coated with the fluorinated molten resin dispersion composition by the coating method of (4) above.

Is achieved by

In order to impart further flexibility to the laminate, an elastic layer made of a fluororubber vulcanizing composition is formed as an intermediate layer between a film made of the composition of the present invention and a substrate. Is also good.

In a preferred embodiment, in the fluorinated multi-segmented polymer, the elastomeric fluorinated polymer single-chain segment A gives flexibility to the entire fluorinated multi-segmented polymer, and at least one of its constituent units. 9 0 molar ^_0/0 is par full O Roo reflex in units.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described specifically.

(A) Fluorine-containing molten resin powder and dispersion composition thereof

The fluorine-containing molten resin powder used in the present invention is a fluorine-containing molten resin powder having an average particle size of 5 to 100 μm, and the dispersion composition is prepared by using such a fluorine-containing molten resin powder in a liquid medium. It is a dispersed composition.

In the case of a solvent-based composition, a solvent selected from ketones, alcohols, esters, aliphatic hydrocarbons and aromatic hydrocarbons having a boiling point of 250 ° C or lower and a surfactant of 10% by weight or lower based on the solvent. Is used as a medium. Water (or aqueous medium) is preferably used as the liquid medium because aqueous compositions are desired from the viewpoint of solvent control and environmental problems in recent years. Therefore, the present invention will be described below by taking an aqueous composition as an example.

(a) Fluorine-containing molten lumber

The fluorinated molten resin contained in the composition of the present invention, 1 5 0-3 5 has a melting point of 0 ° C, melt viscosity at 5 0 ° C above the melting point is 1 0 ⁷ Boyes following Things are preferred.

Specific examples include tetrafluoroethylene-perfluoroalkylvinyl ether copolymer (PFA), tetrafluoroethylene-perfluoroalkylvinyl alcohol ether-hexafluoropropylene copolymer (EPA)-Tetrafluore Tetrafluoroethylene copolymers such as Tylene-ethylene copolymer (ETFE) and Tetrafluoroethylene-hexafluoropropylene copolymer (FEP); Polychloroethylene trifluoroethylene (PCTFE) Examples include chloroethylene-based copolymers such as polyethylene-ethylene copolymer (ECTFE); vinylidene fluoride-based copolymers such as polyvinylidene fluoride (PVdF); and the like. These fluorinated molten resins can be used alone or in combination of two or more. Among them, tetrafluoroethylene copolymers are preferable in terms of non-adhesiveness, and PFA is more preferable in terms of heat resistance.

The average particle size of the fluorinated molten resin powder is usually 5 to 100 m, preferably 10 to 300 m. If the average particle size is too small, cracks will occur in the coating film during firing, making it impossible to obtain a film having a sufficient film thickness.If the average particle size is too large, the powder will precipitate in the dispersion composition. The dispersion state is not stable, and uniform coating may be difficult.

The apparent density of the fluorinated molten resin powder is usually from 0.3 to: 1.5 g / ml, preferably from 0.5 to 1.0 g / ml. If the apparent density is too low, the dispersibility of the powder is reduced, and the inclusion of bubbles and poor leveling properties are likely to occur.If the apparent density is too high, the powder sediments and becomes soothing that the dispersion stability of the composition decreases. .

The compounding amount of the fluorinated molten resin powder is from 15 to 80% by weight, preferably from 20 to 75% by weight, based on the total weight of the yarn. If the amount of the fluorinated molten resin powder is too small, the viscosity of the dispersion liquid will be low, and even if it is applied to the surface of an article, dripping will occur immediately and a film having a sufficient film thickness may not be obtained. If the amount of the fluorine-containing molten resin powder is too large, the composition may not be fluid, and coating may not be possible. The specific compounding amount may be appropriately selected within the above range in consideration of the coating method and the adjustment of the film thickness, etc.In the case of spray coating, etc., the concentration is relatively low, while in the case of press coating, etc. It is preferable that the content be 50% by weight or more to be a paste.

(b) Fluorine-containing multi-segmented polymer

The fluorinated multi-segmented polymer contained in the fluorinated molten resin dispersion composition of the present invention has an elastomer-free fluorinated polymer chain segment A in one molecule (hereinafter, simply referred to as “elastomer-unique segment A”). And non-elastomeric fluorine-containing polymer This refers to a block formed by grafting or graft-linking of a limer chain segment B (hereinafter, simply referred to as “non-elastomeric segment B”).

The film obtained from the fluorine-containing molten resin dispersion composition containing such a fluorine-containing multi-segmented polymer has heat resistance, abrasion resistance and non-adhesion while maintaining sufficient flexibility. . On the other hand, a film made of a fluorinated molten resin dispersion composition in which a mere mixture of an elastomeric fluorinated polymer and a non-elastomeric fluorinated polymer is blended, the type of each polymer to be mixed, Although it differs depending on the mixing properties and compatibility, it is generally inferior in mechanical properties, abrasion resistance and flexibility.

Elastomeric segment A refers to a segment having a glass transition point of 25 ° C or less, and is generally amorphous.

Specific examples of the monomer which is a constituent unit of the elastomeric segment A include tetrafluoroethylene, propylene hexanoleo-ethylene, chlorotrinoleoethylene, perfluoroalkyl vinyl ether (the alkyl group has 1 carbon atom. ~ 6) and

Formula: CFz

q—Rf ¹

(In the formula, X ¹ is a fluorine atom or a trifluoromethyl group, ¹ is a parafluoroalkyl group having 1 to 6 carbon atoms, p and q are integers of 0 to 5, provided that p + q≥l.)

And perfluorovinyl ethers represented by the following formulas. Of these, combinations and compositions having strong elastomeric properties can be used.

In addition, polyamine vulcanization, polyol vulcanization, peroxide vulcanization and other monomers that provide a cure site for curing reaction and monomers containing functional groups that impart functions such as adhesion to other materials are used. 10 mol. It may be introduced at / ₀ or less.

In a preferred embodiment, the elastomeric segment A is an elastic polymer chain consisting of 50-85 mol ⁰ / o of tetrafluoroethylene and 15-50 mol% of perfluoroalkyl butyl ether.

The non-elastomeric segment B preferably has a crystal melting point of 150 ° C or more.

Among the monomers that can constitute the non-elastomeric segment B, Specific examples include tetrafluoroethylene, hexafluoropropylene, black trifluoroethylene, perfluoroalkylbier ether,

Formula: CF ₂ = CF (CF ₂ ) _r X ²

(Wherein, X ² represents a fluorine atom or a chlorine atom, and r represents an integer of 1 to 10), and perhaloolefins such as perfluoro-2-butene; vinylidene fluoride, bur Fluoride, trifluoroethylene, formula: CH ₂ = C (CF ₃ ) ₂ or

Formula: CH ₂ = CX ³ — (CF ₂ ) _s — X ⁴

(In the formula, X ³ and X ⁴ each represent a hydrogen atom or a fluorine atom, and s represents an integer of 1 to 10.)

And the like.

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

In the non-elastomeric one segment B is a preferred embodiment, up to 1 0 0 mole ^_0/0 exceed Tetorafuruo port ethylene 8 5 mole ^_0/0, and

Formula: CF ₂ = CF-R _f ² (I)

(Wherein, R _f ² is triflate Ruo b methyl or 0R _{_f} ^³ (R _f ³ is the number of carbon atoms:! ~ Is 5 Par Furuoroarukiru group represents a group represented by)..)

Is a polymer chain consisting of 0 mol% to less than 15 mol% of the compound represented by Further, in another preferred embodiment the non-elastomeric one segment B is Tetorafuru Oroechiren 8 5-9 9.7 mole ^_0/0, and compounds of formula (I) 0. 3~1 · 5 Mo consisting Le% polymer chains It is.

Among the above, the monomers used as the main components include fluorinated olefins alone, combinations of fluorinated olefins, combinations of ethylene and tetrafluoroethylene, and ethylene and chlorotrifluoroethylene from the viewpoint of heat resistance and abrasion resistance. A combination of ethylene is preferable, and a combination of perhaloolefin alone or a combination of perhaloolefins is particularly preferable.

Fluorine-containing multi-segmented polymer is placed at both ends of Mainly a polymer molecule (B-A-B) with non-elastomer segment B bonded and a polymer molecule (A-B) with non-elastomeric segment B bonded to one end of elastomer segment A It is. If there is a large number of polymer molecules of only the elastomeric segment A to which the non-elastomeric segment B is not bonded, the mechanical properties and abrasion resistance of the resulting film tend to decrease.

The proportion of the elastomeric segment A and the non-elastomeric segment B in the fluorine-containing multi-segmented polymer varies depending on the application, required characteristics, and the composition of each segment, but the elastomeric segment A versus the non-elastomeric The ratio (weight ratio) of the segment B is 5:95 to 98: 2, preferably 20:80 to 95: 5.

If the proportion of the elastomeric segment A is low, the flexibility may be insufficient.If the proportion of the non-elastomeric segment B is low, the heat resistance, wear resistance, and mechanical properties may be insufficient. May be.

The fluorine-containing multi-segmented polymer is preferably used in the form of an aqueous dispersion from the viewpoint of dispersibility.

The particle size of the fluorine-containing multi-segmented polymer is from 1 to 100 nm, and from the viewpoint of the stability of the aqueous dispersion, it is preferably from 50 to 500 nm.

The compounding amount of the fluorine-containing multi-segmented polymer in the fluorine-containing molten resin dispersion composition is from 0.001 to 30% by weight, preferably from 0.01 to 20% by weight, based on the solid content. And more preferably 0.1 to 10% by weight.

If the compounding amount of the fluorine-containing multi-segmented polymer is too small, the flexibility of the obtained film may be insufficient. If the amount of the fluorine-containing multi-segmented polymer is too large, a film having a sufficient film thickness may not be obtained, and the mechanical properties of the film may be insufficient.

(c) water-soluble solvent

When water is used as the medium, the composition of the present invention preferably contains a water-soluble solvent. The water-soluble solvent has a function of wetting the fluorinated molten resin, and those having a high boiling point serve as a drying retarder that connects the resins when drying the coating film and prevents the generation of cracks. Fluorine-containing melt if the blending amount is appropriate even in a high boiling point solvent. Since the fat volatilizes sufficiently at the baking temperature, the properties such as heat resistance and non-adhesion of the film are not reduced.

Specific examples of the water-soluble solvent include low-boiling organic solvents having a boiling point of up to 10 ° C, such as methanol, ethanol, isopropanol, sec-butanol, t-butanol, aceton, and methyl ethyl ketone; Toluene, xylene, methyl sorb, ethyl sorb, methyl isobutyl ketone, n-butanol, etc. as medium boiling organic solvents at 100 to 150 ° C; high boiling organic solvents with boiling points of 150 ° C or more N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, ketocin, ethylene glycol, propylene glycol, glycerin, dimethyl carbitol, butyl dicanolebitol, Solve, cyclohexanol, diisobutyl ketone, 1,4-butanediol, triethylene glycol, tetra Ethylene glycol and the like. As the high-boiling organic solvent, an alcohol solvent is preferable because it has good wettability with the fluorinated molten resin and is easy to handle.

The amount of the water-soluble solvent is 0.5 to 50 weight of the total water. / ₀ , preferably 1 to 30% by weight.

When the amount of the low-boiling organic solvent is too small, the inclusion of bubbles becomes easy to occur, and when the amount is too large, the entire composition becomes flammable and the advantages of the aqueous dispersion composition may be impaired. . If the amount of the medium-boiling organic solvent is too small, the fluorine-containing molten resin may return to powder when the coating film is dried and may not be calcined.If the amount is too large, it may remain in the film after baking. The film properties may be reduced. If the amount of the high-boiling organic solvent is too large, it may remain in the fired film and deteriorate the film characteristics.

(d) Surfactant

The surfactant may be any one that can uniformly disperse the fluorine-containing molten resin powder at 15 to 80% by weight in the composition. Anionic surfactant, cationic surfactant, nonionic surfactant Both surfactants and amphoteric surfactants can be used.

For example, sodium alkyl sulfate, sodium alkyl ether sulfate, triethanolamine alkyl sulfate, triethanolamine Anionic surfactants such as anoalkyl ether sulfate, ammonium quinolequinole sulfate, ammonium alkyl ether sulfate, sodium alkyl ether phosphate and sodium phenol alkyl carboxylate; alkyl ammonium salts, alkylbenzenes Cationic surfactants such as diammonium salt; polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ester, propylene glycol-propylene oxide copolymer, perfluoroalkyl Nonionic surfactants such as ethylene oxide adducts and 2-ethylhexanol ethylene oxide adducts; alkylamine betaine, alkylamide betaine, imidazolymine betaine And other amphoteric surfactants. Among them, anionic and nonionic surfactants are preferable, and a particularly preferable surfactant is a nonionic surfactant having an oxishilene chain having a small residual amount of thermal decomposition.

The amount of the surfactant is usually from 0.01 to 50% by weight, preferably from 0.1 to 30% by weight, particularly preferably from 0.2 to 20% by weight of the fluorinated molten resin powder. If the amount of the surfactant is too small, the fluorinated molten resin powder may not be uniformly dispersed and may partly float.If the amount is too large, a large amount of the surfactant decomposition residue remains in the film. In addition to coloring, properties such as heat resistance and non-adhesion of the film may decrease.

(e) Additive

Various additives can be added to the composition of the present invention depending on the use. Examples of the additives include fillers, stabilizers, pigments, thickeners, decomposition accelerators, fire retardants, and antifoaming agents.

The composition of the present invention can be prepared by uniformly dispersing the fluorine-containing molten resin powder and the fluorine-containing multi-segmented polymer in pure water, preferably in the presence of a water-soluble solvent and a surfactant. it can. In addition, a solvent-based dispersion composition using a solvent having a low surface tension may not require water and a surfactant.

—In general fluorine-containing molten resin dispersion coating, the resin particle size in the coating is as small as 0.2-0.6 μm, so the thickness of the film formed by one coating is 20 μππι If it exceeds, cracks are likely to occur. Even if multiple coats are applied to make the film thicker, cracks tend to occur in thicker films. However, in the composition of the present invention, cracks It is possible to easily obtain a film having a film thickness of about 100 jum without generating cracks.

(B) Fluorine rubber vulcanizing composition

By forming an elastic layer made of, for example, a fluororubber vulcanizing composition as an intermediate layer between the film made of the composition of the present invention and the substrate, the flexibility of the entire coating layer can be increased.

The coating composed of the fluororubber vulcanizing composition may be a single layer composed of one type of fluororubber vulcanizing composition, or two or more layers composed of the same or different fluororubber vulcanizing compositions. May be formed from multiple layers.

Fluororubber is usually supplied as an aqueous dispersion.

Aqueous fluororubber dispurgeon is a 10 to 75% by weight of fluororubber in the presence of a surfactant, such as polyoxyethylene alkynoleatenole, polyoxyethylene alkynolephenylatenole, or anolequinolenesolenate. It is dispersed in water at a concentration of.

Fluororubber is a fluorinated copolymer containing a repeating unit represented by —CH ₂ — in the main chain. A typical example is a fluorinated copolymer containing vinylidene fluoride, specifically, a copolymer whose main chain contains a repeating unit having the following structure:

— At least one repeating unit selected from — CF ₂ — CH ₂ —, one CH ₂ — CH ₂ — and one CH ₂ — CH (CH ₃ ) —, and

— CF ₂ — CF (CF ₃ ) —, — CF ₂ — CF ₂ — and — CF „— CF (OR f) — (where R f is a perfluoroalkyl group having 1 to 6 carbon atoms) At least one repeating unit selected from)).

More specifically, vinylidenefluoride hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, ethylene-hexafluoropropylene copolymer, tetrafluoroethylene For example, a propylene copolymer. Among them, vinylidene fluoride copolymers are preferred from the viewpoint of crosslinkability.

The amount of fluoro rubber contained in the fluoro rubber vulcanizing composition is based on 100 parts by weight of water. The amount is 1 to 500 parts by weight, preferably 5 to 300 parts by weight, more preferably 10 to 150 parts by weight.

The vulcanizing agent used in the fluororubber vulcanizing composition used in the present invention may be any of a conventionally known polyamine vulcanizing agent and a polyol vulcanizing agent. Is preferably a polyol vulcanizing agent.

Further, the fluororubber vulcanizing composition may contain a fluororesin and Z or a fluorine-containing multi-segmented polymer.

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

(FEP), tetrafluoroethylene-perfluoroalkylbutyl ether copolymer (PFA), polytetrafluoroethylene, and the like, and one or more of these can be used. The fluororesin is preferably used in the form of an aqueous dispersion from the viewpoint of dispersibility.

Specific examples of the fluorine-containing multi-segmented polymer are as described above.

The sum of the contents of the fluororesin and the fluorine-containing multi-segmented polymer is 20 to 80% by weight based on the total weight of the solid content.

Since the surface of a film formed from a fluororesin vulcanizing composition containing a fluororesin and Z or a fluorine-containing multi-segmented polymer becomes a fluororesin rich, a film comprising the composition of the present invention and a fluororubber vulcanizing composition Adhesion with the film consisting of is improved. In order to achieve both the adhesion between the composition of the present invention and the fluororubber vulcanizing composition and the flexibility of the entire coating layer, it is desirable to increase the blending ratio of the fluorine-containing multi-segmented polymer.

(C) Substrate

In the present invention, a silicone rubber, a heat-resistant resin or a metal article can be used as the base material, but such an article can be used only if the whole article is made of silicone rubber, heat-resistant resin or metal. The surface coated with the fluorine-containing molten resin dispersion composition of the present invention is formed from a layer of silicone rubber, a heat-resistant resin or a metal. Also include articles that are in use.

Specific examples of the heat-resistant resin used for the base material (or the primer containing the heat-resistant resin) include polyimide, polyetherimide, polyamide, polyamideimide, polyethersulfone, polyetherketone, polyetheretherketone, and polyetherketone. Examples include polyethylene terephthalate, polycarbonate, polyphenylene sulfide, polyparapanoic acid, polyparabenzobisimidazole, polyparabenzobisoxazole, polyparabenzobisthiazole, and the like, and a multilayer product of these.

Specific examples of the metal include, but are not limited to, nickel, aluminum, and stainless steel (SUS).

(D) Primer

Since the fluorine-containing molten resin and the fluorine-containing multi-segmented polymer have low adhesiveness to silicone rubber or a heat-resistant resin or metal, it is desirable to bond them using a primer.

As a primer for silicone rubber, a polymer composition comprising an alkoxysilane monomer (Japanese Patent Application Laid-Open Nos. Sho 51-32626, Japanese Patent Publication No. 1-377377, Japanese Patent Publication No. 5-13131) No. 3), a composition containing an alkoxysilane monomer and an organic titanate compound (Japanese Patent Application No. 11-94945), and a fluorine-containing ethylenic polymer particle containing a functional group. A dispersion composition (WO98 / 520229) is preferred.

Examples of primers for heat-resistant resins and metals include (1) a known composition containing a fluororesin and a heat-resistant resin, (2) a silane compound, and (3) a dispersion composition of a functional group-containing fluorine-containing ethylenic polymer (WO98 / 5) 0 229) are preferably used, and among them, (3) a dispersion composition of functional group-containing fluorine-containing ethylenic polymer particles is particularly preferable. When an intermediate layer composed of a fluororubber vulcanizing composition is introduced, a polymer composition composed of an alkoxysilane monomer, a polymer composition composed of an alkoxysilane monomer, and an organic titanate compound are used as primers for silicone rubber. Preferred are compositions containing the same. As a primer for a heat-resistant resin or a metal, a silane compound or the like is preferably used as necessary. Here, the functional group-containing fluorine-containing ethylenic polymer used as a primer will be briefly described.

The functional group of the functional group-containing fluorine-containing ethylenic polymer is at least one selected from a hydroxyl group, a carboxyl group, a carboxylate, a carboxyester group, and an epoxy group. It can provide adhesiveness with the adhesive. The type and combination of the functional groups are appropriately selected depending on the type, purpose and application of the surface of the substrate, but those having a hydroxyl group are most preferable in terms of heat resistance.

The functional group-containing fluorinated ethylenic monomer (a), which is one of the components constituting the functional group-containing fluorinated ethylenic polymer, has the formula (3):

CX ^ CX ¹ — R _f — Y (3)

(Wherein, Y is one CH ₂ OH, one COOH, a carboxylate, a carboxyester group or an epoxy group, X and X ¹ are the same or different and are a hydrogen atom or a fluorine atom, and R _f is a C 1-40 carbon atom. A divalent fluorinated alkylene group, a fluorinated oxyalkylene group having 1 to 40 carbon atoms, a fluorinated alkylene group having an ether bond having 1 to 40 carbon atoms, or a fluorinated alkylene group having an ether bond having 1 to 40 carbon atoms Represents a xyalkylene group.)

The functional group-containing fluorinated ethylenic monomer represented by is preferred.

As the functional group-containing fluorine-containing ethylenic monomer (a), preferably

CF ₂ = CFO CF ₂ CF ₂ CH ₂ OH, CF ₂ = CFO (CF ₂ ) ₃ C OOH,

CF ₂ = CFOCF ₂ CF ₂ COOCH ₃ ,

CF ₂ = CFOCF ₂ CFOCF ₂ CF ₂ CH ₂ OH

I

CF ₃ ,

CF ₂ = CFCF ₂ COOH, CF ₂ = CFCF. CH ₂ OH,

CF ₂ = CFCF ₂ CF, CH ₂ CH-CH ₂

\

O,

And the like.

As another example of the functional group-containing fluorine-containing ethylenic monomer (a),

CF ₂ = CFCF ₂ OCF ₂ CF ₂ CF ₂ COOH, CF ₂ = CFCF ₂ OCFCFCOOCH ₃

CF

And the like.

Further examples of the functional group-containing fluorine-containing ethylenic monomer (a) include:

CH ₂ = CFCF ₂ CF ₂ CH ₂ CH ₂ OH, CH ₂ = CFCF ₂ CF ₂ CO OH,

CH ₂ = CFCF ₂ CF „CH ₂ CH— CH.

\

O,

CH ₂ = CF (CF ₂ CF ₂ ) ₂ -COOH,

CH _? = CFCF, OCFCH _? OH, CH „= CFCF, 0 CF COOH

CF. CF.

CH ₂ = CFCF ₂ OCFCH ₂ OCH ₂ CH-CH ₂

CF. O

CH ₂ = CFCF ₂ OCFCF ₂ OCFCH ₂ OH

I. I

CF ₃ CF ₃ ,

And the like.

Further, as the functional group-containing fluorine-containing ethylenic monomer (a),

CH ₂ = CHCF ₂ CF ₂ CH ₂ CH ₂ COOH,

CH ₂ = CH— (CF ₂ ) ₄ _CH ₂ CH ₂ CH ₂ OH,

CH ₂ = CH— (CF ₂ ) ₆ — CH ₂ CH ₂ COOCH ₃

And the like.

Others

CF ₃

I

CH „= CHCH ₂ C— OH

I

CF ₃ ,

And the like.

Examples of the fluorinated ethylenic monomer (b) which does not contain a functional group and which constitutes the functional group-containing fluorinated ethylenic copolymer together with the functional group-containing fluorinated ethylenic monomer (a) include tetrafluoroethylene. Ethylene, formula (4): CF ₂ = CF-R _f ¹ (4)

(Wherein, Rf ¹ represents CF ₃ or OR _f ² (where 1 is a C 1-5 perfluoroalkyl group).)

CH ₂ = CF- (CF ₂ ) _n -X ² (5) or 'CH ₂ = CH- (CF ₂ ) _n -X ² (6)

(In the formula, X ² is a hydrogen atom, a chlorine atom or a fluorine atom, and n is an integer of 1 to 5.)

And the like.

Further, in addition to the fluorine-containing ethylenic monomer having a functional group (a) and the fluorine-containing ethylenic monomer having no functional group (b), a fluorine atom is added as long as heat resistance is not reduced. An ethylenic monomer having no ethylenic monomer may be copolymerized. In this case, the ethylenic monomer having no fluorine atom is preferably selected from ethylenic monomers having 5 or less carbon atoms so as not to lower the heat resistance. Specifically, ethylene, propylene,

1-butene, 2-butene and the like.

The content of the functional group-containing fluorinated ethylenic monomer (a) in the functional group-containing fluorinated ethylenic polymer used in the present invention is 0.1% of the total amount of the monomers in the polymer.

05-30 is the mole ^_0/0.

Preferred examples of the functional group-containing fluorinated ethylene polymer used in the present invention are as follows.

(I) a functional group-containing fluorine-containing ethylenic monomer (a) 0. 05~30 mol% and Te trough Ruo ii ethylene 70-99. Polymer of 95 mole ^_0/0.

This polymer is particularly excellent in heat resistance and chemical resistance.

(II) The functional group-containing fluorinated ethylenic monomer (al) is contained in an amount of 0.05 to 30 mol% based on the total amount of the monomers, and is contained in the total amount of the monomers excluding the monomer (a). On the other hand, tetrafluoroethylene 85 to 99.7 mol% and the monomer represented by the above formula (4)

Polymer of 0.3 to 15 mol ^_0/0. For example, a tetrafluoroethylene-perfluoro (alkyl biel ether) copolymer having a functional group or a tetrafluoroethylene-hexafluoropropylene polymer having a functional group.

This polymer has almost the same heat resistance and chemical resistance as the polymer of the above (I). It is excellent in that it can be melt-molded and can be smoothed by heat even when applied in the form of paint.

(III) a monomer containing the functional group-containing fluorine-containing ethylenic monomer (a) in an amount of 0.05 to 30 mol% based on the total amount of the monomer, and further excluding the monomer (a) Te face the whole amount, tetrafurfuryl O b ethylenically 4 0-8 0 mole ^_0/0, ethylene 2 0-6 0 mole ^_0/0, the weight of the other copolymerizable monomer 0-1 5 mol% Combined (ethylene-tetrafluoroethylene polymer having a functional group).

This polymer has excellent heat resistance and weather resistance, has excellent mechanical strength, is hard and tough, and has excellent melt fluidity, so it can be molded and processed with other substrates. It is excellent in that it can be easily combined (laminated, etc.).

(IV) a monomer containing the functional group-containing fluorine-containing ethylenic monomer (a) in an amount of 0.05 to 30 mol% based on the total amount of the monomer, and further excluding the monomer (a) based on the total amount of vinylidene fluoride 4 0-9 0 mole ^_0/0, tetrafurfuryl O b ethylene 0-3 0 mole ^_0/0, the hexa full O b propene 1 0-5 0 mole percent of the monomer mixture ,

Tetrafluoropropoxy O b ethylenically 4 0-7 0 mole ⁰ / o, propylene 3 0-6 0 mole ^_0/0, the other copolymerizable monomer 0-2 0 mol% of the monomer mixture, or

Tetrafluoropropoxy O b ethylenically 4 0-8 5 mol ^_0/0, par full O b vinylethers 1 5-6 0 mol% polymer of monomer mixture of.

This polymer is preferable because of its excellent heat resistance.

The base material of the OA roll is generally made of silicone rubber or metal, and its surface is composed of a fluororubber vulcanizing composition and a general fluorine-containing molten resin dispersion paint for the purpose of durability and non-adhesion. Although a coating is provided, its durability is not always sufficient. The same applies when a belt made of a heat-resistant resin or metal is used instead of the silicone rubber roll or metal roll.

However, the composition of the present invention can easily form a film having a film thickness that was impossible with a conventional composition by one coating, and the film has sufficient durability and non-adhesiveness. Have. Furthermore, since the composition of the present invention contains a fluorine-containing multi-segmented polymer having an elastomeric segment, sufficient flexibility is imparted to the film. Furthermore, since the film made of the composition of the present invention has a high dynamic friction coefficient, high paper transportability can be achieved. Further, since the composition of the present invention contains a perfluoro compound, the resulting film has high toner releasability.

By using a fluorine-containing molten resin, a fluorine-containing multi-segmented polymer, and a silicone rubber or a primer having high adhesiveness to any of heat-resistant resins and metals, the composition of the present invention and silicone can be used. It is possible to strongly bond rubber or heat resistant luster or metal.

When the substrate is extremely flexible such as silicone rubber, the composition of the present invention can be laminated to form a multilayer structure having a hardness gradient. That is, a highly flexible film (the composition ratio of the fluorine-containing multi-segmented polymer is large) is formed on the base material side, and the film (the composition ratio of the fluorine-containing multi-segmented polymer is gradually reduced) is formed. By sequentially laminating the layers, the adhesion between the layers can be ensured. A similar laminated structure can be formed even when the intermediate layer requires flexibility while the surface layer requires high hardness.

The film formed from the composition of the present invention requires heat resistance, non-adhesiveness, lubricity, solvent resistance, etc. by applying it to an article based on silicone rubber or a heat-resistant resin or metal. The main applications include mouth and belts for OA equipment such as copiers, printers, and facsimile machines (for example, fixing rolls, pressure holes, fixing belts, and conveyor belts). However, it can also be used for seats and belts; 0-rings, diaphragms, chemical resistant tubes, fuel hoses, valve seals, gaskets for chemical plants, engine gaskets, etc. Example

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

Reference example 1

Preparation of fluorinated multi-segmented polymer dispersion

The aqueous dispersion obtained by the procedure described in Example 1 of WO99 / 33891 was concentrated with a surfactant (20% by weight aqueous solution of TD-90 manufactured by Lion Corporation). The solid concentration was 50% by weight. This is called "fluorine-containing multi-segmented polymer display puryon." The composition of this fluorine-containing multi-segmented polymer is Last elastomer segment / Non-elastomer segment = 84/16 (weight ratio).

Reference example 2

Preparation of Fluoro Rubber Dispersion

A vinylidenefluoridonotetrafluoroethylene Z hexafluoropropylene copolymer (monomer composition: 65/18/17 (molar ratio)) is produced by emulsion polymerization, and the resulting aqueous dispersion is subjected to surface activity. (20% by weight aqueous solution of TD-90 manufactured by Lion Corporation) to a solid concentration of 60% by weight. This is referred to as "fluorine rubber dispense."

Reference example 3

Preparation of pigment paste

3 parts by weight of filler (Talox R- 516 L, manufactured by Titanium Industry Co., Ltd.) and 5 parts by weight of an acid acceptor (DHT-4A, manufactured by Kyowa Chemical Industry Co., Ltd.) A 20% by weight aqueous solution of 13) was dispersed in 46 parts by weight of pure water together with 2 parts by weight to prepare a paste. This is called "pigment paste". Reference example 4

Preparation of composition for vulcanization of fluoro rubber

38 parts by weight of a fluoro rubber disposable, 47 parts by weight of a fluorine-containing multi-segmented polymer disperse, and 12 parts by weight of a pigment paste were mixed and sufficiently dispersed. To 100 parts by weight of this aqueous dispersion, 7 parts by weight of a polyol-based vulcanizing agent (a 10% by weight aqueous solution of bisphenol AF ammonium salt) and 0.8 parts by weight of a vulcanization accelerator (U—CAT SA610-50 manufactured by Sanwa Pro Co., Ltd.) In addition, a fluororubber vulcanizing composition was prepared. This is referred to as a "fluorine rubber vulcanizing composition".

Preparation Example 1

Preparation of fluorinated molten resin dispersion composition A

4 parts by weight of isopropyl alcohol, 8 parts by weight of nonionic surfactant (DS-401 manufactured by Daikin Industries, Ltd.), 6 parts by weight of triethylene glycol, 4 parts by weight of ethylene glycol, 20 parts by weight of pure water, PFA resin powder ( (Average particle size 25 μπι; apparent density 0.8 g / ml) 26 parts by weight, fluorine-containing multi-segmented polymer disperser 4 parts by weight of John were mixed and dispersed to prepare a uniform dispersion composition. This is referred to as fluorinated molten resin dispersion composition A.

Preparation Example 2

Preparation of fluorinated molten resin dispersion composition B

4 parts by weight of isopropyl alcohol, 8 parts by weight of nonionic surfactant (DS-401 manufactured by Daikin Industries, Ltd.), 6 parts by weight of triethylene glycol, 4 parts by weight of ethylene glycol, 20 parts by weight of pure water, PFA resin powder 26 Parts by weight, 8 parts by weight of a fluorine-containing multi-segment polymerized polymer dispersion were mixed and dispersed to prepare a uniform dispersed yarn composition. This is called a fluorine-containing molten resin dispersion composition B.

Preparation Example 3

Preparation of fluorinated molten resin dispersion composition C

4 parts by weight of isopropyl alcohol, 8 parts by weight of nonionic surfactant (DS-401 manufactured by Daikin Industries, Ltd.), 6 parts by weight of triethylene glycol, 4 parts by weight of ethylene glycol, 20 parts by weight of pure water, PFA resin powder 26 Parts by weight, 20 parts by weight of a fluorine-containing multi-segment polymerized polymer dispersion were mixed and dispersed to prepare a uniform dispersion composition. This is a fluorine-containing molten resin dispersion composition. That.

Preparation Example 4

Preparation of fluorinated molten resin dispersion composition D

4 parts by weight of isopropyl alcohol, 8 parts by weight of nonionic surfactant (DS-401 manufactured by Daikin Industries, Ltd.), 6 parts by weight of triethylene glycol, 4 parts by weight of ethylene glycol, 20 parts by weight of pure water, PFA resin powder 26 The parts by weight were mixed and dispersed to prepare a uniform dispersion composition. This is referred to as a fluorine-containing molten resin dispersion composition D. Preparation Example 5

Preparation of dispersion composition of functional group-containing fluorine-containing ethylenic polymer particles

In a 3 liter glass-lined autoclave equipped with a stirrer, valve, pressure gauge and thermometer, put 1500 ml of pure water and 9.10 g of ammonium perfluorooctanoate, purge with nitrogen gas, and evacuate. , 20 m 1 of ethane gas was charged.

Then, the perfluoro (1,1,9,9-tetrahydro-2,5-bistriff) Fluoromethyl-1,6-dioxa-1-nonenol):

CH ₂ = CFCF ₂ OCFCF ₂ OCF CH ₂ OH (7)

CF ₃ CF ₃

Of 3. 8 g, Pafuruoro (propyl Bulle ether) (PPVE) 18 ^g: a pressed with nitrogen gas, the temperature of the system was maintained at 70 ° C.

While stirring, tetrafluoroethylene gas (TFE) was injected so that the internal pressure became 8.5 kgf Zcm ² G.

Then, a solution of 0.15 g of ammonium persulfate dissolved in 5.0 g of water was injected under pressure using nitrogen to start the reaction.

Since the pressure decreases with the progress of the polymerization reaction, when the pressure drops to 7.5 kgf Zcm ² G, repressurize it to 8.5 kg fZcm ² G with tetrafluoroethylene gas, and reduce the pressure and pressure. Repeated.

While continuing to supply tetrafluoroethylene, every time about 40 g of tetrafluoroethylene gas is consumed from the start of polymerization, 1.9 g of the hydroxyl group-containing fluorine-containing ethylenic monomer represented by the above formula (7) is measured. Press-in three times (5.7 g in total) to continue the polymerization, and when about 160 g of tetrafluoroethylene was consumed from the start of the polymerization, stop the supply and cool the autoclave to release the unreacted monomer. 1702 g of a bluish translucent aqueous dispersion were obtained. This is called a dispersion composition of functional group-containing fluorine-containing ethylenic polymer particles.

The concentration of the polymer in the obtained aqueous dispersion was 10.9%, and the particle diameter measured by a dynamic light scattering method was 70.7 nm.

Further, a part of the obtained aqueous dispersion was taken, subjected to freeze coagulation, and the precipitated polymer was washed and dried to obtain a white solid. The composition of the obtained copolymer was determined by ¹⁹ F-NMR analysis and IR analysis to be TFE / PPVE / a fluorine-containing ethylenic monomer having a hydroxyl group represented by the formula (7) = 97.7 / 1. 2/1. 1 (mole ^_0/0) der ivy.

In the infrared spectrum, characteristic absorption of 1 OH was observed at 3620 to 3400 cm- ¹ .

Melting point Tm by DSC analysis is 310 ° C, 1% pyrolysis by DTGA analysis The temperature Td was 368 ° C. The melt flow rate was measured at 1372 gZl Om in when the melt flow rate was measured at 372 ° C for 5 minutes with a load of 7 kgf Zcm ^{2 by} a high-grade flow tester using a 2 mm, 8 mm long nozzle. Met.

Example 1

The dispersion composition of the functional group-containing fluorine-containing ethylenic polymer particles was spray-coated as a primer on a silicone rubber roll, and dried at 80 ° C: 00 ° C for 15 minutes. The fluorine-containing molten resin dispersion composition A is spray-coated thereon, dried at 80 to 100 ° C for 15 minutes, and baked at 340 ° C for 30 minutes to obtain a fluorine-containing film having a thickness of about 30 m. A molten resin-coated roll was obtained.

The durability of the film was evaluated as follows.

Copy paper (recycled PPC paper manufactured by Fuji Xerox Co., Ltd.) is pressed against the surface of the fluorine-containing molten resin-coated roll heated to 200 ° C with a load of lkg, and the roll surface is rotated by rotating the roll at a rotation speed of 300 rpm. After abrasion, a standard solution of wetting index (31 dyne m) was dropped, and the time required for the contact angle to become 20 ° or less by a goniometer was measured, and the time was used as a measure of durability.

The surface of the fluorine-containing molten resin-coated roll was measured with an IRHD surface microhardness tester (ASTM D1415), and the measured surface microhardness was used as a measure of flexibility. Example 2

The procedure of Example 1 was repeated, except that the fluorine-containing molten resin dispersion composition B was used instead of the fluorine-containing molten resin dispersion composition A.

Example 3

The procedure of Example 1 was repeated, except that the fluorine-containing molten resin dispersion composition C was used instead of the fluorine-containing molten resin dispersion composition A.

Comparative Example 1

The procedure of Example 1 was repeated except that the fluorine-containing molten resin dispersion composition D was used instead of the fluorine-containing molten resin dispersion composition A.

Comparative Example 2

Instead of fluorinated molten resin dispersion composition A, use PF A disperse gillon (AD-2CR, manufactured by Daikin Industries, Ltd., average particle size 0.3 im, solid content concentration 50% by weight). Spray coating, drying at 80 to 100 ° C for 15 minutes, and baking at 34 ° C for 30 minutes to obtain a fluorine-containing molten resin coated roll having a film thickness of about 20 μπ Obtained. The durability and flexibility of the film were evaluated in the same manner as in Example 1.

Example 4

The same dispersion composition of functional group-containing fluorine-containing ethylenic polymer particles as used in Example 1 was spray-coated on a polyimide film, and dried at 80 to 100 ° C. for 15 minutes. . Spray-coated the fluorinated molten resin dispersion composition A thereon, dried at 80 to 100 ° C for 15 minutes, and baked at 34 ° C for 30 minutes to obtain about 30 μm A fluorine-containing molten resin-coated film having a film thickness of

The durability of the film was evaluated as follows.

The surface of the fluorine-containing molten resin-coated film heated to 200 ° C was abraded with copy paper (recycled PPC paper manufactured by Fuji Xerox Co., Ltd.) using a Taber abrasion tester at a load of l kg and a rotation speed of 6 O rpm. Then, a wetting index standard solution (31 dyne mm) was dropped, and the contact angle was 20 with a goniometer. The time until it became below was measured and used as a measure of its endurance. '

The flexibility of the film was evaluated by the same method as in Example 1.

Example 5

The procedure of Example 4 was repeated except that the fluorinated molten resin dispersion composition B was used instead of the fluorinated molten resin dispersion composition A.

Example 6

The procedure of Example 4 was repeated except that the fluorine-containing molten resin dispersion composition C was used instead of the fluorine-containing molten resin dispersion composition A.

Comparative Example 3

The procedure of Example 4 was repeated except that the fluorine-containing molten resin dispersion composition D was used instead of the fluorine-containing molten resin dispersion composition A.

Comparative Example 4

Instead of the fluorinated molten resin dispersion composition A, PFA dispersion (AD-2CR, manufactured by Daikin Industries, Ltd.) is spray-coated, dried at 80 to 100 ° C. for 15 minutes, and then dried. Baking at 30 ° C for 30 minutes to obtain a fluorine-containing molten A fat-coated film was obtained. The durability and flexibility of the film were evaluated in the same manner as in Example 4.

Example 7

A silicone rubber roll was spray-coated with a polymer thread composed of an alkoxysilane monomer (GLP-104 QR, manufactured by Daikin Industries, Ltd.), and 80-100

Dry at 0 ° C for 15 minutes. A fluororubber vulcanizing composition is spray-coated thereon and dried at 80 ° C: 100 ° C for 15 minutes, and then baked at 330 ° C for 15 minutes to form a film of about 20 m. An elastic layer having a thickness was formed. Furthermore, a fluorine-containing molten resin dispersion composition A is spray-coated thereon, dried at 80 to 100 ° C for 15 minutes, and then baked at 34 ° C for 30 minutes to obtain about 30 μm. Fluorine-containing molten resin-coated roll having a film thickness of The durability and flexibility of the film were evaluated in the same manner as in Example 1.

Example 8

The procedure of Example 7 was repeated except that the fluorine-containing molten resin dispersion composition B was used instead of the fluorine-containing molten resin dispersion composition A.

Example 9

The procedure of Example 7 was repeated except that the fluorine-containing molten resin dispersion composition C was used instead of the fluorine-containing molten resin dispersion composition A.

Comparative Example 5

The procedure of Example 7 was repeated except that the fluorine-containing molten resin dispersion composition D was used instead of the fluorine-containing molten resin dispersion composition A.

Comparative Example 6

Instead of the fluorine-containing molten resin dispersion composition A, PFA dispersion (AD-2CR, manufactured by Daikin Industries, Ltd.) is spray-coated and dried at 80 to 150 ° C. for 15 minutes. It was baked at 34 ° C. for 30 minutes to obtain a fluorine-containing molten resin-coated roll having a film thickness of about 20 μιη. The durability and flexibility of the film were evaluated in the same manner as in Example 1.

Example 10

The polyimide film is spray-coated with a fluororubber vulcanizing composition, dried at 80 to 100 ° C for 15 minutes, and then baked at 330 ° C for 15 minutes to obtain a film thickness of about 20. An elastic layer was formed. Further, the fluorine-containing molten resin dispersion composition A is spray-coated thereon, dried at 80 to 100 ° C for 15 minutes, and baked at 34 ° C for 30 minutes to obtain about 30 / A fluorine-containing molten resin-coated film having a thickness of ni was obtained. The durability and flexibility of the film were evaluated in the same manner as in Example 4.

Example 1 1

The procedure of Example 10 was repeated, except that the fluorinated molten resin dispersion composition B was used instead of the fluorinated molten resin dispersion composition A.

Example 1 2

The procedure of Example 10 was repeated, except that the fluorinated molten resin dispersion composition C was used instead of the fluorinated molten resin dispersion composition A.

Comparative Example 7

The procedure of Example 10 was repeated except that the fluorinated molten resin dispersion composition D was used instead of the fluorinated molten resin dispersion composition A.

Comparative Example 8

Instead of the fluorinated molten resin dispersion composition A, PFA dispersion (AD-2CR manufactured by Daikin Industries, Ltd.) is spray-coated and dried at 80 to 100 ° C. for 15 minutes. It was baked at 40 ° C. for 30 minutes to obtain a fluorine-containing molten resin-coated film having a thickness of about 20 / zm. The durability and flexibility of the film were evaluated in the same manner as in Example 4.

The above results are shown in Table 1 (when the elastic layer is not formed) and Table 2 (when the elastic layer is formed).

Base material Fluorine tree Fluorine-containing multi-sectioned rubber Durability Flexibility Particle size of fat-Weight (min) of all compositions (Small surface) / o Small hardness) Example 1 Silicone comb 25 2.9 370 38 Example 2 Silicone rubber 25 5.3 200 35 Example 3 Silicone rubber 25 11.4 40 30 Comparative example 1 Silicone rubber 25 0 660 45 Comparative example 2 Silicone rubber 0.3 90 35 Example 4 e. Reimi 25 2.9 300 52 Example 5 E. Reimi 25 5.3 250 48 Example 6 E. Reimide, 25 11.4 180 44 Comparative Example 3 Refine 25 0 370 57 Comparative Example 4 E. Reimito, '0.3 200 49

Substrate Fluorine tree Fluorine-containing multi-segment durability Durability Flexible particle size of fat

(jum) (% by weight relative to small hardness) Example 7 Silicone rubber 25 2.9 200 33 Example 8 Silicone rubber 25 5.3 160 31 Example 9 Silicone rubber 25 11.4 40 24 Comparative Example 5 Silicone rubber 25 0 220 38 Comparative Example 6 Silicone Comb 0.3 90 30 Example 10 Sample 25 2.9 170 46 Example 11 e. Reimito, 25 5.3 130 44 Example 12 For the sample 25 11.4 30 39 Comparative example 7 For the sample 25 0 180 52 Comparative example 8 Liimide 0.3 50 42 Example 13

Spray-coated the fluorine-containing molten resin dispersion composition A on an aluminum plate, dried at 80-100 ° C for 15 minutes, and then baked at 340 ° C for 30 minutes to obtain a fluorine-containing film with a film thickness of about 30 μm. A molten resin-coated plate was obtained. Using this fluorine-containing molten resin-coated plate, the dynamic friction coefficient, image evaluation and toner releasability were evaluated by the following methods. A HE I DON-14 type frictional resistance tester was used.

A flat indenter with a copy paper (recycled PPC paper made by Fuji Xerox Co., Ltd.) wrapped around the fixed fluorine-containing molten resin-coated board with a load of 1 kg was pressed to 6000 m The kinetic friction coefficient was measured by moving at a speed of mZm in.

Image evaluation and evaluation of toner release property

The fluorine-containing molten resin-coated plate was wound around a roll and fixed, and kept in a thermostat at 180 ° C. for 5 hours. Place the copy paper on which the unfixed image has been formed (recycled PPC paper manufactured by Fuji Xerox Co., Ltd.) in a thermostat at 180 ° C, and rotate the roll heated on the unfixed image at a moving speed of 150 mm / sec. Was. The state of the image fixed in this way and the state of the toner attached to the fluorine-containing molten resin-coated plate were observed. Example 14

The procedure of Example 13 was repeated, except that the fluorinated molten resin dispersion composition C was used instead of the fluorinated molten resin dispersion composition A.

Comparative Example 9

The procedure of Example 13 was repeated except that the fluorinated molten resin dispersion composition A was used instead of the fluorinated molten resin dispersion composition A.

Table 3 shows the above results.

Table 3

Dynamic friction coefficient Image evaluation Toner release property

Example 13 0.60 No character shift Good

Example 14 0.81 No character shift Good

Comparative Example 9 0.23 Character shift good

Claims

The scope of the claims

1. In a liquid medium, a fluorinated molten resin powder having an average particle size of 5 to 1000 / zm and a fluorinated multi-segmented polymer having an elastomeric fluorinated polymer chain segment and a non-elastomeric fluorinated polymer chain segment are placed in a liquid medium. A fluorine-containing molten resin dispersion composition obtained by dispersion.

2. The elastomeric 14 'fluorine-containing polymer chain segment gives flexibility to the whole fluorine-containing multi-segmented polymer, and at least 90 mol% of its constituent units are perfluoroolefin units. The fluorinated molten resin dispersion composition according to claim 1.

3. The elastomeric one fluorine-containing polymer chain segment, claims an elastic polymer chain comprising tetrafluoropropoxy O Roe Ji Ren 50-85 mole ^_0/0 and Par Full O b alkyl Biel ether 15-50 molar% 1 Or the fluorinated molten resin dispersion composition according to 2.

4. non Erasutoma one fluorine-containing polymer chain segment, up to 100 mole ^_0/0 exceed Tetorafuruoroe styrene 85 mole ^_0/0, and

Equation: CF ₂ = CF— R _f ¹

(In the formula, Rf ¹ 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.) The fluorine-containing molten resin dispersion composition according to claim 1, which is a polymer chain composed of 0 mol% to less than 15 mol% of the compound represented by the formula:

5. The non-elastomeric one fluorine-containing polymer chain segment, Tetorafuruoroe styrene from 85 to 99.7 mole ^_0/0, and,

Equation: CF ₂ = CF— R _f ¹

(In the formula, Rf ¹ 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.) The fluorine-containing molten resin dispersion composition according to claim 1, which is a polymer chain consisting of 0.3 to 15 mol% of the compound represented by the formula:

6. The fluorine-containing molten resin dispersion composition according to any one of claims 1 to 5, wherein the composition is an aqueous dispersion composition.

7. The composition, comprising a fluorine-containing molten resin powder having an average particle diameter of 5 to 100, an elastomeric fluorine-containing polymer single-chain segment and a non-elastomer 1′14 fluorine-containing polymer chain segment. It comprises a fluorine-containing multi-segmented polymer, water, a water-soluble solvent and a surfactant. The content of the fluorine-containing molten resin powder is 15 to 80% by weight based on the total composition weight, and the fluorine-containing multi-segment is used. The fluorinated molten resin dispersion composition according to any one of claims 1 to 6, wherein the content of the fluorinated polymer is 0.001 to 30% by weight of the total composition weight.

8. A laminate having a substrate made of silicone rubber, a heat-resistant resin or a metal, and a film formed on the surface of the substrate, from the fluorinated molten resin dispersion composition according to any one of claims 1 to 7.

9. A substrate made of silicone rubber, a heat-resistant resin or a metal, an elastic layer formed on the surface of the substrate, and a fluorinated molten resin dispersion composition according to any one of claims 1 to 7 on the elastic layer. A laminate having a film formed from an object.

10. The fluorine-containing molten resin dispersion composition according to any one of claims 1 to 7 is applied to at least a part of silicone rubber, a heat-resistant resin, or a metal article via a primer, and the applied composition is applied. A method of coating an article, comprising: removing a liquid medium from an object; and then calcining the fluorine-containing molten resin powder and the fluorine-containing multi-segmented polymer.

11. The article is a silicone rubber article, and the primer is a polymer composition comprising an alkoxysilane monomer, a composition comprising a polymer comprising an alkoxysilane monomer and an organic titanate compound, and a functional group-containing fluorine-containing ethylenic compound. The method for coating an article according to claim 10, wherein the primer is at least one kind of primer selected from the group consisting of a dispersion composition of polymer particles.

1 2. The article is a heat-resistant resin or metal article, and the primer is selected from the group consisting of a composition containing a fluororesin and a heat-resistant resin, a dispersion composition of a silane compound and a functional group-containing fluorine-containing ethylenic polymer particle. The method for coating an article according to claim 10, which is at least one selected primer.

13. The method for coating an article according to claim 11, wherein the primer is a dispersion composition of functional group-containing fluorine-containing ethylenic polymer particles.

14. The fluorine-containing molten resin dispersion composition according to any one of claims 1 to 7 was applied to at least a part of silicone rubber, a heat-resistant resin, or a metal article via an elastic layer, and was applied. A method of coating an article comprising removing a liquid medium from a composition and then calcining the fluorinated molten resin powder and the fluorinated multi-segmented polymer.

15. An article made of silicone rubber, at least a part of which is coated with the fluorinated molten resin dispersion composition by the coating method according to claim 10, 11, 13, or 14.

16. An article made of a heat-resistant resin, the surface of which is at least partially coated with the fluorinated molten resin dispersion composition by the coating method according to any one of claims 10 and 12 to L3.

17. A metal product having at least a part of its surface coated with a fluorinated molten resin dispersion composition by the coating method according to any one of claims 10 and 12 to I3.

P

PPo

18. The article according to claim 15 or 17, which is a roll for office automation equipment.

19. The article according to any one of claims 15 to 17, which is a belt for office automation equipment.