KR20080034969A - Laminate with fluoropolymer film and film-forming fluoropolymer - Google Patents

Abstract

A functionalized fluoropolymer, preferably with phosphate functionality, can be coated on a metal oxide containing rubber substrate, which coating, after heating, results in a fluoropolymer-rubber substrate laminate without degradation of the rubber, and with good adhesion between the fluoropolymer and the rubber.

Description

LAMINATE WITH FLUOROPOLYMER FILM AND FILM-FORMING FLUOROPOLYMER}

The present invention relates to laminates and film-forming fluoropolymers having a fluoropolymer film having flexibility while maintaining heat resistance and non-tackiness. More specifically, the present invention relates to laminates with fluoropolymers and film-forming fluoropolymers suitable for rolls of copiers, printers and the like.

Rubber (elastomer) rollers have been used primarily in fusing systems, such as printers. The surface of such rubber rollers is coated with silicone or fluoropolymer paints, but durability is a problem.

In some cases, proper adhesion is not obtained or the elastomer decomposes at the temperature (firing temperature) necessary to form the film from fluoropolymers, such as conventional PFA in rubber substrates. Coating of rubber rollers with PFA tubes using silicone adhesives has been attempted, but problems have arisen due to the poor heat resistance of the silicone adhesives when used at high temperatures.

In US Pat. No. 6,177,196, fluoropolymers having units derived from phosphorus-containing fluorinated vinyl ethers and compositions comprising such fluoropolymers and non-functional fluoropolymers are satisfied by imparting adhesion to the fluoropolymers. It has been proposed as a means of forming a luxurious film.

In addition, US Pat. No. 5,780,552 proposes an adhesive fluoropolymer having a core / shell structure in which a shell of a fluorine substituted copolymer comprising copolymer units of functional monomers is formed on a fluoropolymer core.

However, it has been found that such fluoropolymers do not have satisfactory adhesive strength when used to coat rubber rolls, or because the elastomer does not withstand the required firing temperatures during application.

There is a need for fluoropolymer films that can adhere strongly to elastomeric substrates, reduce the firing temperature to a temperature that the substrate can withstand, and exhibit satisfactory heat resistance in use.

<Overview of invention>

The present invention relates to a laminate comprising a substrate comprising a metal oxide and a functional group-containing fluoropolymer coating layer formed thereon.

The present invention provides a copolymer of tetrafluoroethylene with at least one monomer selected from the group consisting of perfluoro (alkyl vinyl ether) and perfluoroalkyl vinyl, wherein the phosphate group-containing fluoropolymer is from about 30 to about 80% by weight, wherein the at least one monomer is about 3 to 15 mole percent of the tetrafluoroethylene copolymer.

The present invention relates to a fluoropolymer having flexibility while maintaining heat resistance and non-tackiness and suitable for forming films on substrates such as fuser rolls / belts and press rolls / belts, such as copiers, printers, and the like.

The present invention provides a film-forming fluoropolymer that maintains satisfactory heat resistance during use and adheres strongly to the substrate upon firing at a temperature that does not result in degradation of the elastomeric substrate.

The present invention relates to a laminate comprising a substrate comprising a metal oxide and a functional group-containing fluoropolymer coating layer formed thereon.

Preferred embodiments of the invention relate to laminates wherein the functional group containing fluoropolymer is a phosphate group containing fluoropolymer.

A preferred embodiment of the invention relates to a laminate wherein the functional group containing fluoropolymer is a tetrafluoroethylene / trifluorovinyl ether group containing dihydrogen phosphate ester compound / fluorine containing comonomer copolymer resin.

A preferred embodiment of the present invention relates to a laminate wherein the phosphate group containing fluoropolymer is a trifluorovinyl ether group containing dihydrogen phosphate ester compound copolymer resin represented by the following formula (1).

Preferred embodiments of the invention relate to laminates wherein the fluorine-containing comonomer is perfluoro (alkyl vinyl ether) or perfluoroalkyl vinyl.

A preferred embodiment of the invention relates to a laminate wherein the functional group containing fluoropolymer is a composition having a functional group containing fluoropolymer and a fluoropolymer having no functional group.

Preferred embodiments of the present invention are directed to laminates wherein the fluoropolymer having no functional groups is tetrafluoroethylene / perfluoro (alkyl vinyl ether) or perfluoroalkyl vinyl copolymer resin.

The invention also relates to a laminate in which a fluoropolymer layer is formed on the outer surface of the laminate described above.

In addition, the present invention is a phosphate group-containing fluoropolymer in the copolymer resin of perfluoro (alkyl vinyl ether) or perfluoroalkyl vinyl and tetrafluoroethylene, the content of 30 to 80% by weight relative to the copolymer resin And the copolymer resin comprises 3 to 15 mole percent perfluoro (alkyl vinyl ether) or perfluoroalkyl vinyl component.

Preferred embodiments of the film-forming fluoropolymer compositions of the present invention are those wherein the phosphate group-containing fluoropolymer is tetrafluoroethylene, perfluoro (alkyl vinyl ether) or perfluoroalkyl vinyl, and dihydrogen represented by A copolymer resin of a phosphate ester compound, wherein the resin relates to a fluoropolymer composition comprising a perfluoro (alkyl vinyl ether) or perfluoroalkyl vinyl component in an amount of 3 to 15 mole percent.

The fluoropolymer according to the invention is a polymer produced by polymerizing at least one monomer, at least one of which is a fluoromonomer. Fluoromonomers according to the invention are olefins including vinyl ethers comprising at least one fluorine atom bonded to a carbon atom. The fluorine is preferably bonded to a carbon atom that is part of an olefinic double bond. More than half of the monovalent atoms bonded to carbon in the fluoromonomer are more preferably fluorine atoms, more preferably at least 75% of the monovalent atoms bonded to carbon in the fluoromonomer are fluorine atoms, Most preferably, all monovalent atoms bonded to carbon in the low monomer are fluorine atoms. It is preferred that all of the monomers used to prepare the fluoropolymers according to the invention are fluoromonomers. It is more preferred that all monomers are perfluoromonomers, provided that the functional monomers need not be perfluorinated.

The present invention provides a film-forming fluoropolymer that adheres strongly to a substrate, is capable of coating at temperatures that the substrate can withstand, and maintains satisfactory heat resistance during use. Film-forming means that a fluoropolymer in powder or particle form or in the form of a dispersion, for example an aqueous dispersion, can be applied to a substrate, and upon heating it sufficiently fuses to form a film.

The present invention also relates to a fluoropolymer which is capable of forming a film at a temperature that can withstand the substrate when applied as a coating, adhere strongly to the substrate and maintain satisfactory heat resistance in use.

The present invention provides raw materials that enable the formation of fluoropolymer films on the surface of flexible substrates such as elastomers and confer both flexibility and chemical resistance and low frictional properties of the fluoropolymers.

The present invention relates to laminates with a film formed on a substrate and film-forming fluoropolymers which can be suitably used in fuser rolls / belts and press rolls / belts of copiers, printers and the like.

The present invention relates to a laminate obtained by further applying a fluoropolymer to an outer surface of a laminate comprising a substrate and a functional group-containing fluoropolymer coating layer formed on the substrate. Such laminates can be used at high temperatures and are therefore suitable as rollers for copiers and the like.

The present invention relates to a laminate comprising a substrate comprising a metal oxide and a functional group-containing fluoropolymer coating layer formed on the substrate.

The functional group-containing fluoropolymer according to the present invention will first be described.

Examples of functional groups include esters, alcohols, acids, salts and halides, cyanates, carbamates and nitriles and the like. Examples of acids include carboxylic acids, acids derived from phosphorus, acids derived from sulfur, and the like.

Functional group-containing fluoropolymers can be obtained, for example, by copolymerizing functional group-containing fluorinated monomers. Examples of functional group-containing fluorinated monomers include the functional group-containing fluorinated monomers cited in US Pat. No. 6,177,196 and US Pat. No. 5,780,552. In addition, functional group-containing fluoropolymers can be obtained by reacting a functional group-containing fluorinated monomer with the fluoropolymer, such as grafting.

Phosphorus acids, preferably phosphate groups, are preferred examples of such functional groups.

Trifluorovinyl ethers comprising a dihydrogen phosphate ester functional group represented by Formula 1 are preferred examples of fluorinated monomers having phosphate groups as functional groups:

CF ₂ = CF (OR) _m (CH ₂ ) OP (O) (OH) ₂

In the above formula, R is a C ₁ -C _{2 O} fluorinated hydrocarbon group, m is an integer from 1 to 10, when m is 2 or more, R may be the same or different.

In Formula 1, R is a C ₁ -C _{2 O} fluorinated hydrocarbon group, preferably a fluorinated alkylene group.

In Formula 1, a compound in which (OR) is (OCF ₂ CF (CF ₃ )) _x (O (CF ₂ CF ₂ ) _n (CH ₂ ) _r ) _y is a trifluorovinyl ether group-containing dihydrogen It is a preferable example of a phosphate ester compound.

In the above formula, x is an integer of 1 to 3, y is an integer of 0 to 3, n is an integer of 0 to 3, r is 0 to 3 is an integer. When y is 2 or more, n and r may be the same or different.

Specific examples of the compound represented by the formula (1) include 2,2,3,3,5,6,6,8,9,9-decafluoro-5-trifluoromethyl-4,7-dioxanona-8 -En-1-yl dihydrogen phosphate (EVE-P) and 2,2,3,3,4,4,6,7,7-nonafluoro-5-oxahepta-6-en-1-yl di Hydrogen phosphate and the like.

In the present invention, the fluoropolymer is a copolymer of tetrafluoroethylene (TFE) and one or more types of fluorine-substituted comonomers, which copolymers are conventional methods such as aqueous emulsion polymerization or fluorinated solvents. It is preferable to obtain by copolymerization by polymerization in a solvent. Examples of such fluorine substituted comonomers are perfluoro (alkyl vinyl ether) having 1 to 5 carbon atoms (PAVE), which may comprise one or more ether oxygens, and referred to herein as perfluoroalkyl vinyl And perfluoroolefins having 3 to 8 carbon atoms. Copolymer resins of TFE and perfluoro (alkyl vinyl ether) (PFA resin) and copolymer resins of TFE and perfluoroalkyl vinyl are preferred fluoropolymers.

Hexafluoropropylene (HFP), perfluoro (methyl vinyl ether) (PMVE), perfluoro (ethyl vinyl ether) (PEVE) and perfluoro (propyl vinyl ether) (PPVE) are fluorine substituted comonomers. proper. More preferred are perfluoro (ethyl vinyl ether) (PEVE) and perfluoro (propyl vinyl ether) (PPVE).

The functional group-containing fluoropolymer of the present invention is preferably obtained by copolymerizing a fluorinated monomer containing the aforementioned functional group units when producing the fluoropolymer by polymerization. It is preferred that the copolymer is obtained by copolymerizing the functional group-containing fluorinated monomer, TFE and at least one type of fluorine substituted comonomer described above by conventional methods.

The polymerization can be carried out by methods known in the art. Examples thereof include solution polymerization in which the solvent is fluorocarbon or fluorochlorocarbon. Aqueous dispersion polymerization as described in the examples herein is preferred. The concentration of the polymer in the aqueous medium is about 10-50% by weight, preferably about 20-40% by weight, more preferably about 25-35% by weight.

The abovementioned compounds can be given as examples of fluorine-substituted comonomers. Perfluoro (alkyl vinyl ether) and perfluoroalkyl vinyl are particularly preferred.

The melting point of the functional group-containing fluoropolymer of the present invention is preferably about 200 ° C to 300 ° C, more preferably about 220 ° C to 280 ° C.

When the functional group-containing fluoropolymer of the present invention is a copolymer of TFE, fluorine substituted comonomers and functional group-containing fluorinated monomers, perfluoro (alkyl vinyl ether) and perfluoroalkyl vinyl as fluorine substituted comonomers The content of is preferably about 3 to 15 mol%, more preferably about 5 to 12 mol% with respect to the copolymer. Having a content of perfluoro (alkyl vinyl ether) and perfluoroalkyl vinyl in the above-mentioned range is preferable because the melting point of the functional group-containing fluoropolymer can be maintained within the range of about 200 ° C to 300 ° C. To an embodiment.

The content of the fluorinated monomer unit having a functional group is preferably about 0.02 to 5 mol%, more preferably about 0.1 to 2.5 mol% with respect to the copolymer.

The functional group-containing fluoropolymer of the present invention may be a composition comprising the functional group-containing fluoropolymer described above and a fluoropolymer having no functional group.

Compositions comprising functional group-containing fluoropolymers and fluoropolymers having no functional groups can readily and optionally control the content of functional groups, thereby providing a preferred practice of the functional group-containing fluoropolymers of the present invention. It becomes an aspect.

In addition, the term "functional group-containing fluoropolymer of the present invention" is sometimes used herein as a meaning of a composition comprising a functional group-containing fluoropolymer and a fluoropolymer having no functional group.

When the functional group-containing fluoropolymer of the present invention is a mixture of the functional group-containing fluoropolymer as mentioned above and the fluoropolymer having no functional group, the melting point thereof is that the fluoropolymer film is subjected to heating. Is preferably about 200 ° C. to 300 ° C., more preferably about 220 ° C. to 28 ° C., so that when formed on the substrate, the firing temperature is not so high as to damage the substrate.

Fluoropolymers having no functional groups can be selected from the above-mentioned fluoropolymers as appropriate. Among them, TFE / perfluoro (alkyl vinyl ether) copolymer resin and TFE / perfluoroalkyl vinyl copolymer resin are preferable.

In order to achieve the desired melting point, the fluoropolymer is a TFE / perfluoro (alkyl vinyl ether) copolymer resin or a TFE / perfluoroalkyl vinyl copolymer resin, with the proportion of the alkyl vinyl ether or alkyl vinyl component being copolymer resin With respect to, it is preferable to use a copolymer which is 3 to 15 mol% when the fluoropolymer film is formed on the substrate, and preferably 5 to 12 mol% when the fluoropolymer film is formed on the substrate. Therefore, when the fluoropolymer film is formed on a substrate, the copolymer resin of perfluoro (alkyl vinyl ether) or perfluoroalkyl vinyl and TFE comprising 3 to 15 mol% of alkyl vinyl ether or alkyl vinyl component is It is a preferred embodiment of the fluoropolymers of the present invention.

When the functional group-containing fluoropolymer of the present invention is a composition comprising a functional group-containing fluoropolymer as described above and a fluoropolymer having no functional group, the functional group-containing fluoropolymer is the total of the composition. It is preferably mixed at a ratio of 10 to 100% by weight, preferably 30 to 80% by weight based on the weight. The fluoropolymer and functional group-containing fluoropolymer may be mixed by any conventional method such as by melt mixing using a kneader, an extruder or a roll mill. If the polymer is produced by aqueous emulsion or dispersion polymerization, the aqueous dispersion may be mixed before separating the polymer from the aqueous medium.

Separation of the polymer may not be necessary if it is desired to apply the polymer to the substrate by coating methods such as spraying and roll-coating. In such cases, the polymer dispersion (or solution in the case of solvent-polymerization, recognizing that the polymer may not be completely dissolved in the solvent) may be used directly or the addition of thickening agents and other agents to aid coating and The concentration can be adjusted.

In addition, mixtures of fluoropolymers and functional group-containing fluoropolymers can be achieved by forming particles with a core / shell structure as mentioned in US Pat. No. 5,780,552. When particles having a core / shell structure are formed, the shell comprises a functional group containing fluoropolymer, and the core is a fluoropolymer.

Particles with such a core / shell structure can be produced by a polymerization process that produces a fluoropolymer. More specifically, the fluoropolymer is produced as a core by copolymerizing tetrafluoroethylene (TFE) with perfluoro (alkyl vinyl ether), perfluoroalkyl vinyl, or another fluorine substituted comonomer, Polymer particles having a shell comprising a fluorinated monomer having a functional group can be produced by addition and further copolymerization of the aforementioned fluorinated monomer with a functional group in a step near the end of the copolymerization. Such copolymerization may be carried out by dispersion polymerization, emulsion polymerization or suspension polymerization.

In addition, particles having a core / shell structure obtained by this method are preferred embodiments of the functional group-containing fluoropolymers of the present invention. The content of the resulting fluoropolymer and functional group-containing fluoropolymer can be calculated from the content of polymerized monomers when particles having a core / shell structure are produced by polymerization.

The total composition and content of the particles with core / shell structure can be determined by ¹⁹ F-NMR, and the melting point can be measured by differential scanning calorimetry (DSC).

The functional group containing fluoropolymers of the present invention can be used as film-forming fluoropolymers.

Preferred film-forming fluoropolymers of the invention comprise perfluoro (alkyl vinyl ether) or perfluoroalkyl, comprising from about 3 to 15 mole percent perfluoro (alkyl vinyl ether) or perfluoroalkyl vinyl components. A functional group-containing fluoropolymer composition obtained by mixing a phosphate group-containing fluoropolymer in a copolymer resin of vinyl and TFE in an amount of about 30 to 80% by weight relative to the copolymer resin.

More preferred embodiments of the film-forming fluoropolymers of the present invention are those wherein the phosphate group-containing fluoropolymers in the film-forming fluoropolymers described above are TFE, perfluoro (alkyl vinyl ether) or perfluoroalkyl vinyl, and A copolymer resin of the dihydrogen phosphate ester compound represented by the following formula (1), wherein the resin is a fluoropolymer composition comprising about 3 to 15 mole percent perfluoro (alkyl vinyl ether) or perfluoroalkyl vinyl compound.

Using the film-forming fluoropolymers of the present invention can coat a substrate, such as an elastomer, with a fluoropolymer without damaging the substrate by overheating, and can form a film having adequate heat resistance during use.

If a primer coating is to be applied (see Examples 1 to 4 and Comparative Example 1), the thickness is as thin as about 1 to 10 μm (about 25 to 35 wt% functional group containing fluoropolymer aqueous dispersion or solution). Dry at about 100 ° C. to 150 ° C. for about 10 to 30 minutes. Thereafter, the secondary coating of the fluoropolymer having a composition similar to that of the functional group-containing fluoropolymer but without the functional group is about 25 to 35% by weight with a thickness of about 5 to 100 μm, preferably about 5 to 50 μm. From aqueous dispersions or solutions. It is dried at about 100-150 ° C. for about 10-30 minutes. The film is then obtained by heating to about 300 ° C. for about 30 minutes.

Although the properties of the substrate including the metal oxide on the surface of the substrate on which the film is formed by the functional group-containing fluoropolymer of the present invention are not particularly limited, conventional polymers are preferred for the substrate, and elastomers are particularly preferred. Do. By elastomer is meant an amorphous polymer, ie a non-crystalline polymer, having a glass transition temperature below its use temperature, preferably below room temperature (about 20 ° C. to 25 ° C.). Using a flexible substrate, the film-forming fluoropolymers of the present invention can form thin fluoropolymer coatings to form the fluoropolymer coating without adversely affecting the flexibility of the substrate.

The present invention can suitably be used on flexible substrates, preferably flexible elastomer substrates, since fluoropolymer films that impart flexibility while providing heat resistance and non-tackiness can be formed on the substrate. Examples of such elastomers are silicone rubbers.

In addition, there is no particular limitation on the shape of the substrate. If the substrate is a material constituting the roll, it may be of cylindrical shape or it may be a cylinder having a shape as part of the roller. When the substrate is a sheet, it may be a molded article molded into a specific shape.

The functional group-containing fluoropolymers of the present invention can be suitably used on rubber (elastomer) roller-shaped substrates comprising metal oxides.

Oxides of metals of Groups III to VIII of the Periodic Table of the Elements are preferred for metal oxides. Preferred examples of the metal oxides include aluminum oxide, titanium oxide, tin oxide, manganese oxide, bismuth oxide, molybdenum oxide, iron oxide, nickel oxide, and the like. Especially, titanium oxide and iron oxide are preferable. Iron oxide is an example of a particularly preferred metal oxide. Red iron oxide (Fe ₂ O ₃ ) is preferred among iron oxides.

The particle size range of the metal oxides according to the invention is about 0.01 to 50 μm, preferably about 0.1 to 10 μm.

The metal oxide content as the weight percent of the total amount of the elastomer and the metal oxide is about 1 to 50% by weight, preferably about 3 to 45% by weight, more preferably about 5 to 40% by weight, most preferably about 10 to 30 Weight percent.

Various commonly known methods can be used to form films from the functional group-containing fluoropolymers of the invention on substrates. For example, the fluoropolymer may be applied to any site on the surface as particles or particle aggregates in the form of sprays, dispersions or slurries. In this case, it can also be mixed with a binder or other powder or liquid for other purposes. Powder coating techniques such as electrostatic spray or fluidized bed coating can be used. The fluoropolymer film is generally formed in strong contact with the substrate by heating (generally pressurized) to a temperature higher than the melting point of the fluoropolymer particles.

Appropriate adhesive strength between the fluoropolymer and the substrate has been found to form in the present invention as a result of the functional group containing fluoropolymer interacting with the metal oxide.

The fluoropolymers of the present invention may be suitably applied to fuser rolls / belts, press rolls / belts, and other parts of printers, copiers, etc., wherein the application is flexible fluoro, while maintaining heat resistance and non-tackiness. This is because the polymer coating can be formed.

The second layer of fluoropolymer may be formed on the outer surface of the laminate having a functional group containing fluoropolymer formed as a film on the substrate to which the metal oxide is added by the present invention. In this case, the functional group-containing fluoropolymer on the substrate acts as a primer. The laminate formed in this way has good interlayer adhesion, since the functional group containing fluoropolymer is strongly adhered to the substrate and the second layer of the fluoropolymer is adhered to the functional group containing fluoropolymer. . A laminate in which a fluoropolymer layer is formed on a substrate having an embedded functional group-containing fluoropolymer film layer is a preferred embodiment of the present invention.

When the substrate is a roller, the laminate in which the fluoropolymer layer is formed on the roller with the inserted functional group-containing fluoropolymer film layer can be suitably used in a copier or the like because the roller can withstand high temperatures.

A method of forming a fluoropolymer layer on a roller with an embedded functional group-containing fluoropolymer film layer includes forming a functional group-containing fluoropolymer film on a roller and applying the roller to a fluoropolymer tube. Forming a functional group-containing fluoropolymer film on the inner surface of the fluoropolymer tube, applying a roller to the tube, and forming a functional group-containing fluoropolymer layer on the inner surface of the tube, the fluoropolymer tube It includes the method of coating the roller with a tube when produced by extrusion.

As noted above, functional group-containing fluoropolymers are suitable for fluoropolymer coatings because they provide affinity with the fluoropolymer and proper adhesion strength between the fluoropolymer and the substrate as a result of interaction with the metal oxide. Acts as a primer for.

From the foregoing disclosure, the present invention relates to film-forming fluoropolymers which exhibit adequate adhesion to rubber substrates comprising metal oxides, which can be applied at temperatures which the substrate withstands, and which maintain adequate heat resistance during use.

In addition, the present invention allows for the formation of fluoropolymer films that can be applied at temperatures that the substrate can withstand, exhibit adequate adhesive strength with the substrate, and exhibit adequate heat resistance during use.

In addition, the present invention makes it possible to provide a base material in which a fluoropolymer film that imparts both the flexibility and chemical resistance of the fluoropolymer and low frictional properties is formed on the surface of a flexible substrate such as an elastomer.

In addition, the present invention makes it possible to provide a laminate in which a fluoropolymer film, which imparts both the flexibility and chemical resistance of the fluoropolymer and low frictional properties, is formed on a substrate.

The present invention relates to excellent rubber rolls for copiers, printers, and other devices coated with flexible fluoropolymers while maintaining heat resistance and non-tackiness.

The present invention provides a laminate comprising a substrate comprising a metal oxide, a functional group-containing fluoropolymer coating layer formed thereon, and a fluoropolymer provided on an outer surface.

The invention is illustrated in detail by the following examples and comparative examples. However, the present invention is not limited by these examples in any way.

Examples 1 to 4 and Comparative Example 1

Preparation of Aqueous Dispersions of Functional Group-Containing Fluoropolymers

A clean 4 L stainless steel polymerization reactor equipped with horizontal stir blades was used. A 2.2 L capacity of pure water containing 4.9 g of added ammonium perfluorooctanoate is placed in the reactor and the temperature inside the synthesizer is stabilized at 85 ° C. after removing oxygen from the interior of the system. A pressure difference of 0.03 MPa occurred in the system with ethane. 104 g of perfluoro (ethyl vinyl ether) (PEVE) was then added as a precharge fraction and the pressure was increased to 2.06 MPa with tetrafluoroethylene (TFE). 69 mg ammonium persulfate (APS) initiator dissolved in water is then added. When the pressure was reduced to 0.03 MPa, the polymerization was carried out while continuously feeding APS and PEVE into the polymerization reactor and maintaining a pressure of 2.06 MPa with TEE. The polymerization is carried out at a uniform temperature of 85 ° C. and a pressure of 2.06 MPa. 2,2,3,3,5,6,6,8,9,9-decafluoro-5-trifluoromethyl-4,7-dioxanona-8-en-1-yl dihydrogen phosphate ( 5% by weight of an aqueous solution of EVE-P) is added at a rate of 26 ml / min over 10 minutes after 110 minutes have elapsed. When the addition of the aqueous solution of EVE-P was completed, stirring was stopped and the reaction was terminated. The content added during the reaction is 100 mg APS and 84 g PEVE. After removal of residual TFE from the polymerization reactor by vacuum, the reactor was opened and a cloudy dispersion of about 30% by weight solids was obtained.

The solid fraction contained in this cloudy dispersion is agglomerated by freezing, washed with water and acetone, and dried to obtain a white solid. ^{According to} the results of ¹⁹ F-NMR analysis, such solids included 12 wt% PEVE and 0.6 wt% EVE-P. According to DSC, the primary melting point is 269 ° C and the secondary melting point is 257 ° C.

Preparation of Elastomer (Rubber) Substrate Member

Raw material :

A: SE1700 Clear, manufactured by Toray Dow-Corning.

B: SE1700, manufactured by Toray Dow-Corning.

C: red iron oxide, 100 ED, 0.1-1 탆 particle size, manufactured by Dainichi Seika Color & Chemicals Manufacturing Company (Tokyo).

First, raw material C is uniformly mixed with A in the proportions shown in Table 1 below. Thereafter, B is mixed in the proportions shown in Table 1 below. The resulting mixture is placed between two sheets of FEP (fluorinated ethylene propylene, also known as TFE / HFP copolymer) film, which in turn is placed between two metal plates. After heating at 120 degreeC for 30 minutes and applying the pressure of about 0.5 kg / cm <2> (50 kPa), the rubber base member was obtained.

Preparation of the primer

The aforementioned fluoropolymer aqueous dispersion, surfactant [Triton® X-100] and methyl cellulose thickening agent of the present invention are uniformly mixed in the proportions given below, and the mixture is passed through a 300-mesh SUS screen. To produce a fluoropolymer aqueous primer for the rubber.

Weight ratio

Fluoropolymer Aqueous Dispersions of the Invention: 90.4 parts

Surfactant: Triton X-100 1.6 parts

Methyl cellulose aqueous solution (4.8% by weight of methyl cellulose) 8.0 parts

Manufacture of test plates

The primer prepared as described above is applied to a thickness of 3 to 5 μm and dried (125 ° C. for 20 minutes on the surface of the rubber base member produced as described above by a conventional application method (such as spray coating or dipping)). ) A fluoropolymer topcoat (40 wt% solids, composition set forth below) was applied and dried at 125 ° C. for 20 minutes to obtain a 25 μm thick coating. Thereafter, the coated substrate was heated at 300 ° C. for 30 minutes to obtain a film.

Composition of the fluoropolymer topcoat ingredient weight% 1) Tetrafluoroethylene / hexafluoropropylene (FEP) dispersion (55.5 wt.% Solids) 56.62 2) Triton X-100 0.57 3) glycerin 0.50 4) Film-forming acrylic polymer 16.49 5) diethylene glycol monobutyl ether 2.23 6) oleic acid 1.13 7) aromatic hydrocarbons 2.72 8) triethanol amine 4.22 9) aqueous methyl cellulose solution (4.8 wt% methyl cellulose) 2.70 10) cerium (III) 2-ethylhexanoate 0.54 11) Deionized Water 12.28 Components 2, 5, 6, 7, 8 and 10 are premixed. Then 1, 11, 3, 4 and 9 are mixed in order, and finally the premix is added.

Adhesion test

Each film obtained as described above was subjected to a test width of 10 mm by the peel test method described on page 239 of Section 5.5.4, Modern Fluoropolymer Coating Processing Technology (Epotech KK, Tokyo, published 1988) and A 90 ° peel test was conducted at a peel rate of about 50 mm / min. The separation of the rubber layer and the primer is judged as "fail". Separation or tearing in the rubber substrate is judged as "pass". The results are summarized in Table 1 together with peel strength and separation sites (peel sites).

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Substrate composition A: B 10: 1 10: 1 10: 1 10: 1 10: 1 (A + B): C 90:10 85:15 80:20 70:30 100: 0 Peel Strength (g / cm) 420 400 380 380 40 Peeling site Tearing rubber layer Tearing rubber layer Tearing rubber layer Tearing rubber layer Between primer and rubber layer Adhesion test pass pass pass pass fail

Example 5

Samples were generated as described in Example 1 above. Such films were evaluated based on the tape adhesion-checkerboard (shaded) described on page 236 of section 5.5.1, Modern Fluoropolymer Coating Processing Technology (cited above). No delamination, ie detachment, of the coating is found.

Example 6

A primer prepared as described in Example 1 above was applied and dried on a silicone rubber roll containing red iron oxide produced by the formulation presented in the preparation of the test plate. The rollers were covered with a heat shrinkable tube and the walls of the tube were made of a PFA polymer similar to Example 1 with a thickness of 50 μm. Heat is applied (330 ° C. for 10 minutes) to shrink the tube, bring the tube into intimate contact with the rubber roller to form a heat-settled coating, and provide excellent adhesion due to the interaction of metal oxides with functional groups in the rubber. To form. When a 10 mm cut is made in the coating and a simple peel test is conducted by slowly pulling the coating by hand, the rubber layer develops braking and shows good adhesion.

Claims (20)

A laminate comprising a substrate comprising a metal oxide and a functional group-containing fluoropolymer coating layer formed thereon. The laminate of claim 1, wherein the functional group containing fluoropolymer is a phosphate group containing fluoropolymer. The laminate according to claim 2, wherein the functional group-containing fluoropolymer is a tetrafluoroethylene / trifluorovinyl ether group-containing dihydrogen phosphate ester compound / fluorine-containing comonomer copolymer resin. The laminate of claim 3, wherein the fluorine-containing comonomer is perfluoro (alkyl vinyl ether) or perfluoroalkyl vinyl. The laminate according to claim 3, wherein the trifluorovinyl group-containing dihydrogen phosphate ester compound of formula (1) is a dihydrogen phosphate ester: <Formula 1> CH ₂ = CH (OR) _m (CH ₂ ) OP (O) (OH) ₂ In the above formula, R is a C ₁ -C ₂₀ fluorinated alkylene group, m is an integer of 1 to 10, when m is 2 or more, R may be the same or different. The laminate of claim 4 comprising about 3 to 15 mole percent perfluoro (alkyl vinyl ether) component or perfluoroalkyl vinyl component. The laminate of claim 1, wherein the functional group containing fluoropolymer is a composition comprising a functional group containing fluoropolymer and a fluoropolymer having no functional group. 8. The laminate of claim 7, wherein the composition is a core / shell polymer, the core is a fluoropolymer having no functional groups, and the shell is a functional group containing fluoropolymer. 8. The laminate of claim 7, wherein the functional group-containing fluoropolymer comprises from about 30 to 80 weight percent of the total copolymer. The laminate according to claim 7, wherein the fluoropolymer having no functional group is a copolymer of tetrafluoroethylene with at least one monomer selected from the group consisting of perfluoro (alkyl vinyl ether) and perfluoroalkyl vinyl. . 10. The laminate of claim 9, wherein the fluoropolymer having no functional group comprises 3 to 15 mole percent of said at least one monomer. The laminate of claim 10, wherein the melting point of the functional group-containing fluoropolymer is about 200 ° C. to 300 ° C. 12. The laminate of claim 1, wherein the substrate comprises an elastomer. The laminate of claim 13, wherein the elastomer is a silicone rubber. The laminate according to claim 1, wherein the metal oxide of claim 1 is iron oxide. The laminate according to claim 15, wherein the iron oxide is red iron oxide. The laminate according to claim 1, wherein the substrate is a roller. The laminate of claim 1, wherein a fluoropolymer is provided on the outer surface. The phosphate group-containing fluoropolymer is a copolymer of tetrafluoroethylene with at least one monomer selected from the group consisting of perfluoro (alkyl vinyl ether) and perfluoroalkyl vinyl, and about 30 to 80 weight based on the copolymer Film-forming fluoropolymer composition, wherein the at least one monomer is about 3-15 mole% of the copolymer of tetrafluoroethylene. 19. The copolymer of claim 18, wherein the phosphate group-containing fluoropolymer is a copolymer of one or more monomers, dihydrogen phosphate ester monomers and tetrafluoroethylene selected from the group consisting of perfluoro (alkyl vinyl ether) and perfluoroalkyl vinyl. Wherein said copolymer comprises about 3 to 15 mole percent of said at least one monomer.