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WO2020171196A1 - Coating composition and coated article - Google Patents

Coating composition and coated article Download PDF

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Publication number
WO2020171196A1
WO2020171196A1 PCT/JP2020/006986 JP2020006986W WO2020171196A1 WO 2020171196 A1 WO2020171196 A1 WO 2020171196A1 JP 2020006986 W JP2020006986 W JP 2020006986W WO 2020171196 A1 WO2020171196 A1 WO 2020171196A1
Authority
WO
WIPO (PCT)
Prior art keywords
coating composition
solid lubricant
fluororubber
coating
present disclosure
Prior art date
Application number
PCT/JP2020/006986
Other languages
French (fr)
Japanese (ja)
Inventor
大輔 三瓶
智洋 城丸
中谷　安利
Original Assignee
ダイキン工業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ダイキン工業株式会社 filed Critical ダイキン工業株式会社
Priority to JP2021502171A priority Critical patent/JP7381938B2/en
Priority to CN202080014704.8A priority patent/CN113474161A/en
Priority to KR1020217029594A priority patent/KR20210126710A/en
Publication of WO2020171196A1 publication Critical patent/WO2020171196A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/082—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising vinyl resins; comprising acrylic resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D115/00—Coating compositions based on rubber derivatives
    • C09D115/02—Rubber derivatives containing halogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular

Definitions

  • the present disclosure relates to coating compositions and coated articles.
  • Patent Document 1 discloses a non-adhesive treatment layer formed from a non-adhesive treatment coating composition containing a fluororesin (solid lubricant), fluororubber, an amino group-containing silane coupling agent and water on a fluororubber layer. Is provided.
  • the present disclosure includes a fluororubber, a vulcanizing agent, a solid lubricant and an organic solvent,
  • the solid lubricant includes a solid lubricant (A) and a solid lubricant (B) different from the solid lubricant (A), and relates to a coating composition.
  • the solid lubricant (A) is preferably a fluororesin.
  • the solid lubricant (B) is preferably at least one selected from the group consisting of graphite, molybdenum disulfide, tungsten disulfide, graphite fluoride and boron nitride.
  • the mass ratio of the fluororubber to the solid lubricant is preferably 20/80 to 80/20.
  • the mass ratio of the solid lubricant (A) and the solid lubricant (B) is preferably 50/50 to 90/10.
  • the coating composition is preferably a non-adhesive treatment coating composition.
  • the coating composition is preferably a coating composition for non-stick treatment of an elastomer layer.
  • the present disclosure includes a metal plate, An elastomer layer provided on one side or both sides of the metal plate, It also relates to a coated article having a coating film formed from the coating composition of the present disclosure, which is provided on the elastomer layer.
  • the elastomer layer is preferably a fluororubber layer.
  • the coated article is preferably a fluororubber coated gasket material.
  • a coating composition that gives a coating film excellent in non-adhesiveness and scratch resistance, and a coated article provided with such a coating film.
  • the present disclosure includes a fluororubber, a vulcanizing agent, a solid lubricant and an organic solvent, and the solid lubricant is a solid lubricant (A) and a solid lubricant (B) different from the solid lubricant (A).
  • a coating composition comprising: Since the coating composition of the present disclosure contains the above-mentioned components, it can provide a coating film having excellent non-adhesiveness and scratch resistance. Examples of the non-adhesiveness include, for example, non-adhesiveness between the coating films during production or storage of the coating film formed from the coating composition of the present disclosure, and a coating film formed from the coating composition of the present disclosure. The non-adhesiveness to other materials (press dies etc.) that come into contact with the surface of the coating film at the time of production or use of.
  • the coating composition of the present disclosure is also excellent in coating stability.
  • fluororubber examples include vinylidene fluoride [VdF] fluorororubber, tetrafluoroethylene [TFE]/propylene [Pr] fluorororubber, TFE/Pr/VdF fluororubber, ethylene [Et]/hexafluoropropylene [HFP]. ] Fluorine rubber, Et/HFP/VdF type fluorinated rubber, Et/HFP/TFE type fluorinated rubber, fluorosilicone type fluorinated rubber, fluorophosphazene type fluorinated rubber and the like. Of these, VdF fluororubber is preferable.
  • the fluororubber may be used alone or in combination of two or more.
  • VdF fluororubber examples include VdF/HFP copolymer, VdF/TFE/HFP copolymer, VdF/chlorotrifluoroethylene [CTFE] copolymer, VdF/CTFE/TFE copolymer, VdF/perfluoro.
  • CTFE chlorotrifluoroethylene
  • vulcanizing agent examples include amine vulcanizing agents, polyol vulcanizing agents (polyhydroxy aromatic compounds, peroxide vulcanizing agents, etc., among which polyol vulcanizing agents are preferable.
  • polyol vulcanizing agent a vulcanizing agent usually used for polyol vulcanizing fluorororubber can be used.
  • examples of the above-mentioned polyol vulcanizing agent include compounds having at least two hydroxyl groups, particularly phenolic hydroxyl groups, in the molecule and having vulcanization performance, and this compound may be a polymer compound.
  • polyol vulcanizing agent among others, phenol derivatives such as bisphenol A, bisphenol AF, hydroquinone and salts thereof; polyhydroxy compounds having two or more enol type hydroxyl groups in the molecule such as phenol resin and salts thereof; A compound represented by the formula: R f 1 (CH 2 OH) 2 (R f 1 represents a perfluoroalkyl polyether group) and the like are preferable.
  • phenol derivatives such as bisphenol A, bisphenol AF, hydroquinone and salts thereof
  • polyhydroxy compounds having two or more enol type hydroxyl groups in the molecule such as phenol resin and salts thereof
  • a compound represented by the formula: R f 1 (CH 2 OH) 2 (R f 1 represents a perfluoroalkyl polyether group) and the like are preferable.
  • any commercially available polyol-based vulcanizing agent for fluororubber can be used.
  • the polyol vulcanizing agent may be used alone or in
  • a vulcanization aid may be used to accelerate vulcanization.
  • the vulcanization aid include alkyl and aralkyl quaternary ammonium salts; quaternary ammonium salts such as quaternary 1,8-diaza-bicyclo[5.4.0]-7-undecenium salt; tertiary amines.
  • a quaternary phosphonium salt and the like can be mentioned.
  • the addition amounts of the vulcanizing agent and the vulcanization aid can be appropriately selected according to the type and amount of the fluororubber used, and are not particularly limited. Also, two or more of the above may be used in combination.
  • the coating composition of the present disclosure includes, as the solid lubricant, a solid lubricant (A) and a solid lubricant (B) different from the solid lubricant (A).
  • solid lubricants examples include fluororesin, graphite, molybdenum disulfide, tungsten disulfide, graphite fluoride, and boron nitride. Can be used in combination.
  • the solid lubricant (A) is preferably a fluororesin.
  • fluororesin examples include polytetrafluoroethylene [PTFE], tetrafluoroethylene [TFE]/hexafluoropropylene [HFP] copolymer [FEP], TFE/perfluoro(alkyl vinyl ether) [PAVE] copolymer.
  • PFA polytetrafluoroethylene
  • TFE tetrafluoroethylene
  • HFP hexafluoropropylene
  • FEP TFE/perfluoro(alkyl vinyl ether)
  • PAVE perfluoro(alkyl vinyl ether) copolymer.
  • PFA polychlorotrifluoroethylene
  • PCTFE polychlorotrifluoroethylene
  • CTFE chlorotrifluoroethylene
  • ETFE Polyvinylidene fluoride
  • PVDF Polyvinylidene fluoride
  • the solid lubricant (B) is preferably at least one selected from the group consisting of graphite, molybdenum disulfide, tungsten disulfide, graphite fluoride and boron nitride, and from the group consisting of graphite and molybdenum disulfide. More preferably, it is at least one selected, and it is even more preferably graphite.
  • the mass ratio (A/B) of the solid lubricant (A) to the solid lubricant (B) is preferably 50/50 to 90/10, and 55/45 to 85/15. It is more preferably 60/40 to 80/20, still more preferably 65/45 to 80/20.
  • the solid lubricant preferably has an average particle diameter of 0.1 to 10 ⁇ m, more preferably has a lower limit of 0.15 ⁇ m, and more preferably has an upper limit of 5 ⁇ m in order to stably retain the solid lubricant in the coating film.
  • the average particle size is a value measured by CAPA700 (centrifugal sedimentation type particle size distribution measuring device) manufactured by Horiba Ltd.
  • the mass ratio of the fluororubber to the solid lubricant is preferably 20/80 to 80/20, more preferably 25/75 to 75/25, and 30 It is more preferably /70 to 70/30.
  • the organic solvent is not particularly limited, and examples thereof include ketones such as methyl ethyl ketone [MEK], methyl isobutyl ketone [MIBK], diisobutyl ketone [DIBK], diacetone alcohol, cyclohexanone, and isophorone, and esters such as butyl acetate and isopentyl acetate. It is possible to use ethers such as diethylene glycol dimethyl ether, hydrocarbons such as toluene and xylene, and amides such as N,N-dimethylacetamide and N-methyl-2-pyrrolidone.
  • the coating composition of the present disclosure may use only one type of the above organic solvent, or may use two or more types of organic solvents. The blending amount of the organic solvent can be appropriately adjusted according to the type of fluororubber blended in the coating composition.
  • the coating composition of the present disclosure contains the above organic solvent, it can be a solvent-based coating composition. Therefore, unlike a water-based paint using water as a solvent, it is not necessary to use a surfactant as a dispersant, and it is possible to prevent deterioration of coating film physical properties due to the surfactant remaining in the coating film. .. Further, it is superior in paint stability as compared with water-based paint.
  • the coating composition of the present disclosure may include a stabilizer in addition to the above-mentioned fluororubber, vulcanizing agent, solid lubricant and organic solvent.
  • a stabilizer include orthoformate ester, orthocarbonate ester, cyclic orthoester, lactone acetal, trimethyl orthoformate ester, triethyl orthoformate ester, trimethyl orthoacetate ester, triethyl orthoacetate ester, trimethyl orthocarbonate ester, and triethyl orthocarbonate ester.
  • Orthoesters such as tetramethyl orthocarbonate, tetraethyl orthocarbonate; organic acids such as monocarboxylic acids (formic acid, acetic acid, propionic acid, etc.) and dicarboxylic acids (oxalic acid, malonic acid, succinic acid, etc.), etc. be able to.
  • the coating composition of the present disclosure may use only one of the above stabilizers, or may use two or more types of stabilizers.
  • various additives such as a filler, a colorant, a defoaming agent, and a surface conditioner can be added to the coating composition of the present disclosure.
  • the filler include carbon black, white carbon, calcium carbonate, barium sulfate, talc, calcium silicate and the like. Of these, carbon black is preferred.
  • the colorant include inorganic pigments and complex oxide pigments.
  • the above defoaming agent include a silicone defoaming agent and a polymer defoaming agent.
  • the surface modifier include siloxane compounds, acrylic copolymers, methacrylic copolymers and the like.
  • a coating film can be formed by applying the coating composition of the present disclosure to an object to be coated and drying.
  • the coating composition can be applied by known coating methods such as brush coating, spray coating, dip coating, flow coating, dispenser coating, and screen coating.
  • curing may be performed if necessary.
  • the curing may be carried out layer by layer or collectively for a plurality of layers. Further, the curing may be performed simultaneously with the drying.
  • the drying and curing conditions can be appropriately set according to the type of the coating composition of the present disclosure and the object to be coated.
  • the coating composition of the present disclosure provides a coating film excellent in non-adhesiveness and scratch resistance, and thus can be suitably used as a non-adhesive treatment coating composition.
  • the object to be treated is an elastomer layer, non-adhesiveness and scratch resistance are more remarkably exhibited, and therefore, it can be particularly suitably used as a coating composition for non-adhesive treatment of an elastomer layer.
  • the elastomer layer is preferably a coating film of a coating composition containing an elastomer.
  • IR ethylene- ⁇ -olefin rubber, ethylene- ⁇ -olefin-non-conjugated diene rubber, chlorinated polyolefin rubber, chlorosulfonated polyolefin rubber, acrylic rubber, ethylene-based acrylic rubber, epichlorohydrin rubber, silicone rubber, butyl rubber (IIR) , Ethylene-vinyl ester rubber, ethylene-methacrylate rubber and the like. Of these, fluororubber is preferable.
  • fluororubber examples include vinylidene fluoride [VdF] fluorororubber, tetrafluoroethylene [TFE]/propylene [Pr] fluorororubber, TFE/Pr/VdF fluororubber, ethylene [Et]/hexafluoropropylene [HFP]. ] Fluorine rubber, Et/HFP/VdF type fluorinated rubber, Et/HFP/TFE type fluorinated rubber, fluorosilicone type fluorinated rubber, fluorophosphazene type fluorinated rubber and the like. Of these, VdF fluororubber is preferable.
  • the fluororubber may be used alone or in combination of two or more.
  • VdF fluororubber examples include VdF/HFP copolymer, VdF/TFE/HFP copolymer, VdF/chlorotrifluoroethylene [CTFE] copolymer, VdF/CTFE/TFE copolymer, VdF/perfluoro.
  • CTFE chlorotrifluoroethylene
  • the present disclosure has a metal plate, an elastomer layer provided on one side or both sides of the metal plate, and a coating film formed from the above-described coating composition of the present disclosure provided on the elastomer layer. It also relates to a coated article characterized by the above. Since the coated article of the present disclosure has a coating film formed from the coating composition of the present disclosure, it is excellent in non-tackiness and scratch resistance.
  • the metal plate examples include a plate made of iron; stainless steel; aluminum; copper; brass; titanium; galvanized, aluminum-plated steel plate, or the like. Of these, a stainless plate and an aluminum plate are preferable.
  • the elastomers exemplified for the elastomer layer that can be treated with the coating composition of the present disclosure described above can be used, and among them, fluororubber is preferable.
  • the elastomer layer is preferably a coating film of a coating composition containing the elastomer.
  • the elastomer layer preferably has a thickness of 5 to 50 ⁇ m, more preferably 10 to 30 ⁇ m.
  • the elastomer layer is provided on one side or both sides of the metal plate.
  • the elastomer layer may be provided directly on the metal plate, or may be provided via another layer such as a primer layer.
  • the coating film formed from the coating composition of the present disclosure is provided on the elastomer layer.
  • the coating film may be provided directly on the elastomer layer or may be provided via another layer, but the non-adhesiveness and the scratch resistance are more remarkably exhibited. It is preferably provided directly on the elastomer layer.
  • the coating film preferably has a thickness of 0.5 ⁇ m or more and less than 10 ⁇ m, more preferably 1 to 5 ⁇ m.
  • the coating film On the coating film, further other layers may be provided, but in the point that non-adhesiveness and scratch resistance are more significantly exhibited, no other layer is provided on the coating film. That is, it is preferable that the coating film is the outermost surface of the coated article.
  • the coated article of the present disclosure includes, for example, applying the coating composition containing the elastomer on the metal plate, and drying the coating composition obtained by applying the coating composition of the present disclosure on a coating film obtained by drying. Can be manufactured. After coating and drying the coating composition forming each layer, curing may be carried out if necessary. The curing may be carried out layer by layer or collectively for a plurality of layers. Further, the curing may be performed simultaneously with the drying. Drying and curing conditions can be appropriately set according to the type of the coating composition and the elastomer layer of the present disclosure.
  • the coating composition and coated article of the present disclosure can be used in fields requiring non-adhesiveness, scratch resistance and the like.
  • Sealing materials for plant gaskets, engine gaskets, etc. chemical-resistant tubes, fuel hoses, fluid transport members for chemicals such as joints; rolls for office automation equipment such as copiers, printers, facsimiles (eg, fixing rolls, pressure rolls)
  • it can be used for a conveyor belt and the like, and above all, it can be preferably used for a gasket.
  • the coated article of the present disclosure is a fluororubber coated gasket material.
  • Example 1 As a fluororubber, vinylidene fluoride/tetrafluoroethylene/hexafluoropropylene copolymer (fluorine concentration: 68% by mass) is used for 100 parts by mass of solid content of an elastomer, and 37.5 parts by mass of graphite and fluororesin (polytetrafluoro). 112.5 parts by mass of ethylene [PTFE] and 5 parts by mass of the acid acceptor were kneaded with an open roll to prepare a compound. This compound was mixed with 700 parts by mass of methyl ethyl ketone as an organic solvent to obtain a compound solution.
  • PTFE ethylene
  • a polyol-based vulcanizing agent and 0.5 part by mass of a vulcanization aid are dissolved in a mixed solvent composed of 200 parts by mass of methyl ethyl ketone as an organic solvent and 5 parts by mass of ethanol, and a stabilizer is added therein.
  • a mixed solvent composed of 200 parts by mass of methyl ethyl ketone as an organic solvent and 5 parts by mass of ethanol, and a stabilizer is added therein.
  • 2 parts by mass of the orthoacetic acid ester compound and 2 parts by mass of the organic acid were added.
  • This solution was mixed with the previously prepared compound solution with a disper to obtain a non-adhesive treatment coating composition.
  • Examples 2 and 6 A coating composition for non-adhesive treatment was obtained in the same manner as in Example 1 except that the compounding amounts of fluororubber, fluororesin and graphite were changed as shown in Table 1 and that carbon black was compounded.
  • Examples 3-5 A non-adhesive treatment coating composition was obtained in the same manner as in Example 1 except that the compounding amounts of fluororubber, fluororesin and graphite were changed as shown in Table 1.
  • Examples 7-10 A non-stick treatment coating composition was obtained in the same manner as in Example 1 except that graphite was changed as shown in Table 1.
  • Comparative Example 1 A coating composition for non-adhesive treatment was obtained in the same manner as in Example 1 except that the compounding amounts of fluororubber, fluororesin and graphite were changed as shown in Table 1.
  • Comparative example 2 100 parts by mass of an aqueous dispersion of fluororubber (vinylidene fluoride/tetrafluoroethylene/hexafluoropropylene copolymer) (60% by mass of fluororubber content), an aqueous dispersion of a fluororesin (polytetrafluoroethylene [PTFE]) (Fluorine resin content 60% by mass) 100 parts by mass, 6 parts by mass of amino group-containing silane coupling agent, and 3800 parts by mass of water were mixed to obtain a non-adhesive treatment coating composition.
  • fluororubber vinylene fluoride/tetrafluoroethylene/hexafluoropropylene copolymer
  • PTFE polytetrafluoroethylene
  • ⁇ Preparation of test piece (painted article)> A fluororubber coating (diisobutyl ketone solution of VdF/HFP copolymer) was applied to an aluminum plate that had been washed with acetone in advance with a flow coater, dried at 100°C for 30 minutes, and then baked at 200°C for 30 minutes. Thus, a coated plate having a rubber layer thickness of 25 ⁇ m was obtained.
  • the coated plate obtained above is dip coated at room temperature with the coating composition for non-adhesive treatment obtained in Examples and Comparative Examples, followed by drying at 80 to 100° C. for 5 minutes, and then at 200° C. for 5 minutes. After baking for 1 minute, a test piece (painted article) having a non-adhesive treated layer having a thickness of 1 ⁇ m was obtained.
  • ⁇ Scratch resistance> The HEIDON tester was used to measure the scratch generation load of the coating film of the test piece, and the load was evaluated according to the following criteria. ⁇ : 80g or more ⁇ : 60 to 70g X: 40 to 50 g
  • ⁇ Paint stability> The coating compositions for non-adhesive treatment obtained in Examples and Comparative Examples were redispersed after being stored at 25° C. for 24 hours, filtered with a 100 mesh wire mesh, the concentration of the filtration residue was measured, and evaluated according to the following criteria. ⁇ : Less than 1% by mass ⁇ : 2 to 4% by mass X: 5 mass% or more

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
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Abstract

Provided is a coating composition from which a coating film having excellent non-adhesiveness and scratch resistance is formed. The coating composition is characterized by containing a fluororubber, a vulcanizing agent, a solid lubricant, and an organic solvent, wherein the solid lubricant includes: a solid lubricant (A); and a solid lubricant (B) different from the solid lubricant (A).

Description

塗料組成物及び塗装物品Paint composition and coated article
本開示は、塗料組成物及び塗装物品に関する。 The present disclosure relates to coating compositions and coated articles.
ゴムコートの塗装物品は、表面がゴム層によって覆われているので、その製造又は保管工程においてゴム層同士が固着しやすい問題がある。そこでゴム層の固着を防止する目的で、非粘着層をゴム層上に設けた材料が提案されている。 Since the surface of a rubber-coated article is covered with a rubber layer, there is a problem in that the rubber layers tend to adhere to each other in the manufacturing or storage process. Therefore, in order to prevent the rubber layer from sticking, a material in which a non-adhesive layer is provided on the rubber layer has been proposed.
特許文献１には、フッ素ゴム層の上に、フッ素樹脂（固体潤滑剤）、フッ素ゴム、アミノ基含有シランカップリング剤及び水を含む非粘着処理用塗料組成物から形成される非粘着処理層を設けることが記載されている。 Patent Document 1 discloses a non-adhesive treatment layer formed from a non-adhesive treatment coating composition containing a fluororesin (solid lubricant), fluororubber, an amino group-containing silane coupling agent and water on a fluororubber layer. Is provided.
国際公開第２００７／１３５９５６号International Publication No. 2007/1359596
本開示は、非粘着性及び耐引掻き傷性に優れる塗膜を与える塗料組成物、並びに、そのような塗膜を備える塗装物品を提供することを目的とする。 It is an object of the present disclosure to provide a coating composition which gives a coating film excellent in non-stickiness and scratch resistance, and a coated article provided with such a coating film.
本開示は、フッ素ゴム、加硫剤、固体潤滑剤及び有機溶剤を含み、
上記固体潤滑剤は、固体潤滑剤（Ａ）と、上記固体潤滑剤（Ａ）とは異なる固体潤滑剤（Ｂ）とを含むことを特徴とする塗料組成物に関する。 The present disclosure includes a fluororubber, a vulcanizing agent, a solid lubricant and an organic solvent,
The solid lubricant includes a solid lubricant (A) and a solid lubricant (B) different from the solid lubricant (A), and relates to a coating composition.
上記固体潤滑剤（Ａ）はフッ素樹脂であることが好ましい。 The solid lubricant (A) is preferably a fluororesin.
上記固体潤滑剤（Ｂ）はグラファイト、二硫化モリブデン、二硫化タングステン、フッ化黒鉛及び窒化ホウ素からなる群より選択される少なくとも１種であることが好ましい。 The solid lubricant (B) is preferably at least one selected from the group consisting of graphite, molybdenum disulfide, tungsten disulfide, graphite fluoride and boron nitride.
上記フッ素ゴムと上記固体潤滑剤との質量比（フッ素ゴム／固体潤滑剤）が２０／８０～８０／２０であることが好ましい。 The mass ratio of the fluororubber to the solid lubricant (fluororubber/solid lubricant) is preferably 20/80 to 80/20.
上記固体潤滑剤（Ａ）と上記固体潤滑剤（Ｂ）との質量比（固体潤滑剤（Ａ）／固体潤滑剤（Ｂ））が５０／５０～９０／１０であることが好ましい。 The mass ratio of the solid lubricant (A) and the solid lubricant (B) (solid lubricant (A)/solid lubricant (B)) is preferably 50/50 to 90/10.
上記塗料組成物は、非粘着処理用塗料組成物であることが好ましい。 The coating composition is preferably a non-adhesive treatment coating composition.
上記塗料組成物は、エラストマー層の非粘着処理用塗料組成物であることが好ましい。 The coating composition is preferably a coating composition for non-stick treatment of an elastomer layer.
本開示は、金属板と、
上記金属板の片面又は両面に設けられたエラストマー層と、
上記エラストマー層の上に設けられた、本開示の塗料組成物から形成された塗膜と
を有することを特徴とする塗装物品にも関する。 The present disclosure includes a metal plate,
An elastomer layer provided on one side or both sides of the metal plate,
It also relates to a coated article having a coating film formed from the coating composition of the present disclosure, which is provided on the elastomer layer.
上記エラストマー層は、フッ素ゴム層であることが好ましい。 The elastomer layer is preferably a fluororubber layer.
上記塗装物品は、フッ素ゴムコートガスケット材料であることが好ましい。 The coated article is preferably a fluororubber coated gasket material.
本開示によれば、非粘着性及び耐引掻き傷性に優れる塗膜を与える塗料組成物、並びに、そのような塗膜を備える塗装物品を提供することができる。 According to the present disclosure, it is possible to provide a coating composition that gives a coating film excellent in non-adhesiveness and scratch resistance, and a coated article provided with such a coating film.
以下、本開示を具体的に説明する。
本開示は、フッ素ゴム、加硫剤、固体潤滑剤及び有機溶剤を含み、上記固体潤滑剤は、固体潤滑剤（Ａ）と、上記固体潤滑剤（Ａ）とは異なる固体潤滑剤（Ｂ）とを含むことを特徴とする塗料組成物に関する。
本開示の塗料組成物は、上記成分を含むので、非粘着性及び耐引掻き傷性に優れる塗膜を与えることができる。
上記非粘着性としては、例えば、本開示の塗料組成物から形成される塗膜の製造又は保管時における、当該塗膜同士の非粘着性や、本開示の塗料組成物から形成される塗膜の製造又は使用時における、当該塗膜の表面と接触する他の材料（プレス金型等）に対する非粘着性が挙げられる。
本開示の塗料組成物は、また、塗料安定性にも優れる。 The present disclosure will be specifically described below.
The present disclosure includes a fluororubber, a vulcanizing agent, a solid lubricant and an organic solvent, and the solid lubricant is a solid lubricant (A) and a solid lubricant (B) different from the solid lubricant (A). And a coating composition comprising:
Since the coating composition of the present disclosure contains the above-mentioned components, it can provide a coating film having excellent non-adhesiveness and scratch resistance.
Examples of the non-adhesiveness include, for example, non-adhesiveness between the coating films during production or storage of the coating film formed from the coating composition of the present disclosure, and a coating film formed from the coating composition of the present disclosure. The non-adhesiveness to other materials (press dies etc.) that come into contact with the surface of the coating film at the time of production or use of.
The coating composition of the present disclosure is also excellent in coating stability.
上記フッ素ゴムとしては、ビニリデンフルオライド［ＶｄＦ］系フッ素ゴム、テトラフルオロエチレン［ＴＦＥ］／プロピレン［Ｐｒ］系フッ素ゴム、ＴＦＥ／Ｐｒ／ＶｄＦ系フッ素ゴム、エチレン［Ｅｔ］／ヘキサフルオロプロピレン［ＨＦＰ］系フッ素ゴム、Ｅｔ／ＨＦＰ／ＶｄＦ系フッ素ゴム、Ｅｔ／ＨＦＰ／ＴＦＥ系フッ素ゴム、フルオロシリコーン系フッ素ゴム、フルオロホスファゼン系フッ素ゴム等が挙げられる。なかでもＶｄＦ系フッ素ゴムが好ましい。
上記フッ素ゴムは、１種又は２種以上を用いることができる。 Examples of the fluororubber include vinylidene fluoride [VdF] fluororubber, tetrafluoroethylene [TFE]/propylene [Pr] fluororubber, TFE/Pr/VdF fluororubber, ethylene [Et]/hexafluoropropylene [HFP]. ] Fluorine rubber, Et/HFP/VdF type fluorinated rubber, Et/HFP/TFE type fluorinated rubber, fluorosilicone type fluorinated rubber, fluorophosphazene type fluorinated rubber and the like. Of these, VdF fluororubber is preferable.
The fluororubber may be used alone or in combination of two or more.
上記ＶｄＦ系フッ素ゴムとしては、ＶｄＦ／ＨＦＰ共重合体、ＶｄＦ／ＴＦＥ／ＨＦＰ共重合体、ＶｄＦ／クロロトリフルオロエチレン［ＣＴＦＥ］共重合体、ＶｄＦ／ＣＴＦＥ／ＴＦＥ共重合体、ＶｄＦ／パーフルオロ（アルキルビニルエーテル）［ＰＡＶＥ］共重合体、ＶｄＦ／ＴＦＥ／ＰＡＶＥ共重合体、ＶｄＦ／ＨＦＰ／ＰＡＶＥ共重合体、ＶｄＦ／ＨＦＰ／ＴＦＥ／ＰＡＶＥ共重合体、ＶｄＦ／ＴＦＥ／Ｐｒ共重合体、ＶｄＦ／Ｅｔ／ＨＦＰ共重合体、ＶｄＦ／式（１）で表される含フッ素単量体の共重合体等が挙げられる。
式（１）：
ＣＨ２＝ＣＦＲｆ　　　　　　（１）
（式中、Ｒｆは炭素数１～１２の直鎖状又は分岐状のフルオロアルキル基） Examples of the VdF fluororubber include VdF/HFP copolymer, VdF/TFE/HFP copolymer, VdF/chlorotrifluoroethylene [CTFE] copolymer, VdF/CTFE/TFE copolymer, VdF/perfluoro. (Alkyl vinyl ether) [PAVE] copolymer, VdF/TFE/PAVE copolymer, VdF/HFP/PAVE copolymer, VdF/HFP/TFE/PAVE copolymer, VdF/TFE/Pr copolymer, VdF /Et/HFP copolymer, VdF/fluorine-containing monomer copolymer represented by the formula (1), and the like.
Formula (1):
CH 2 =CFRf (1)
(In the formula, Rf is a linear or branched fluoroalkyl group having 1 to 12 carbon atoms)
上記加硫剤としては、例えば、アミン加硫剤、ポリオール加硫剤（ポリヒドロキシ芳香族化合物、パーオキサイド加硫剤等が挙げられるが、なかでもポリオール加硫剤が好ましい。 Examples of the vulcanizing agent include amine vulcanizing agents, polyol vulcanizing agents (polyhydroxy aromatic compounds, peroxide vulcanizing agents, etc., among which polyol vulcanizing agents are preferable.
上記ポリオール加硫剤としては、ポリオール加硫系フッ素ゴムに通常使用される加硫剤を用いることができる。上記ポリオール加硫剤としては、水酸基、特にフェノール性水酸基を分子内に少なくとも２個有する化合物であって、加硫性能を有するものが挙げられ、この化合物は、高分子化合物であってもよい。 As the polyol vulcanizing agent, a vulcanizing agent usually used for polyol vulcanizing fluororubber can be used. Examples of the above-mentioned polyol vulcanizing agent include compounds having at least two hydroxyl groups, particularly phenolic hydroxyl groups, in the molecule and having vulcanization performance, and this compound may be a polymer compound.
上記ポリオール加硫剤としては、なかでも、ビスフェノールＡ、ビスフェノールＡＦ、ヒドロキノン等のフェノール誘導体及びそれらの塩；フェノール樹脂等のエノール型水酸基を分子内に２個以上有するポリヒドロキシ化合物及びそれらの塩；式：Ｒｆ １（ＣＨ２ＯＨ）２（Ｒｆ １はパーフルオロアルキルポリエーテル基を示す。）で表される化合物等が好ましい。
上記ポリオール加硫剤としては、上記以外にも、フッ素ゴム用ポリオール系加硫剤として市販されているものはいずれも使用することができる。
上記ポリオール加硫剤は、１種又は２種以上を用いることができる。 As the above-mentioned polyol vulcanizing agent, among others, phenol derivatives such as bisphenol A, bisphenol AF, hydroquinone and salts thereof; polyhydroxy compounds having two or more enol type hydroxyl groups in the molecule such as phenol resin and salts thereof; A compound represented by the formula: R f 1 (CH 2 OH) 2 (R f 1 represents a perfluoroalkyl polyether group) and the like are preferable.
As the above-mentioned polyol vulcanizing agent, in addition to the above, any commercially available polyol-based vulcanizing agent for fluororubber can be used.
The polyol vulcanizing agent may be used alone or in combination of two or more.
本開示の塗料用組成物においては、加硫を促進させるために、加硫助剤を用いることもできる。上記加硫助剤としては、アルキル及びアラルキル第４級アンモニウム塩；第４級１，８－ジアザ－ビシクロ［５．４．０］－７－ウンデセニウム塩等の第４級アンモニウム塩；３級アミン；４級ホスホニウム塩等が挙げられる。 In the coating composition of the present disclosure, a vulcanization aid may be used to accelerate vulcanization. Examples of the vulcanization aid include alkyl and aralkyl quaternary ammonium salts; quaternary ammonium salts such as quaternary 1,8-diaza-bicyclo[5.4.0]-7-undecenium salt; tertiary amines. A quaternary phosphonium salt and the like can be mentioned.
上記加硫剤及び上記加硫助剤の添加量は、使用するフッ素ゴムの種類や量に応じて適宜選択することができ、特に限定されない。また、上述したもののうち２種類以上を併用してもよい。 The addition amounts of the vulcanizing agent and the vulcanization aid can be appropriately selected according to the type and amount of the fluororubber used, and are not particularly limited. Also, two or more of the above may be used in combination.
本開示の塗料組成物は、上記固体潤滑剤として、固体潤滑剤（Ａ）と、上記固体潤滑剤（Ａ）とは異なる固体潤滑剤（Ｂ）とを含む。このように異なる固体潤滑剤を併用することにより、非粘着性だけでなく、耐引掻き傷性にも優れる塗膜が得られる。 The coating composition of the present disclosure includes, as the solid lubricant, a solid lubricant (A) and a solid lubricant (B) different from the solid lubricant (A). By using different solid lubricants together in this way, it is possible to obtain a coating film which is not only non-tacky but also excellent in scratch resistance.
上記固体潤滑剤（固体潤滑剤（Ａ）及び（Ｂ））としては、フッ素樹脂、グラファイト、二硫化モリブデン、二硫化タングステン、フッ化黒鉛、窒化ホウ素等を挙げることができ、これらの２種以上を組み合わせて使用することができる。 Examples of the solid lubricants (solid lubricants (A) and (B)) include fluororesin, graphite, molybdenum disulfide, tungsten disulfide, graphite fluoride, and boron nitride. Can be used in combination.
上記固体潤滑剤（Ａ）は、フッ素樹脂であることが好ましい。 The solid lubricant (A) is preferably a fluororesin.
上記フッ素樹脂としては、例えば、ポリテトラフルオロエチレン〔ＰＴＦＥ〕、テトラフルオロエチレン〔ＴＦＥ〕／ヘキサフルオロプロピレン〔ＨＦＰ〕共重合体〔ＦＥＰ〕、ＴＦＥ／パーフルオロ（アルキルビニルエーテル）〔ＰＡＶＥ〕共重合体〔ＰＦＡ〕、ＴＦＥ／ＨＦＰ／ＰＡＶＥ共重合体〔ＥＰＡ〕、ポリクロロトリフルオロエチレン〔ＰＣＴＦＥ〕、ＴＦＥ／クロロトリフルオロエチレン〔ＣＴＦＥ〕共重合体、ＴＦＥ／エチレン〔Ｅｔ〕共重合体〔ＥＴＦＥ〕、ポリビニリデンフルオライド〔ＰＶＤＦ〕等が挙げられ、なかでも耐熱性、耐磨耗性等の点で、ＰＴＦＥが好ましい。 Examples of the fluororesin include polytetrafluoroethylene [PTFE], tetrafluoroethylene [TFE]/hexafluoropropylene [HFP] copolymer [FEP], TFE/perfluoro(alkyl vinyl ether) [PAVE] copolymer. [PFA], TFE/HFP/PAVE copolymer [EPA], polychlorotrifluoroethylene [PCTFE], TFE/chlorotrifluoroethylene [CTFE] copolymer, TFE/ethylene [Et] copolymer [ETFE] Polyvinylidene fluoride [PVDF] and the like are mentioned, and among them, PTFE is preferable in terms of heat resistance, abrasion resistance and the like.
上記固体潤滑剤（Ｂ）は、グラファイト、二硫化モリブデン、二硫化タングステン、フッ化黒鉛及び窒化ホウ素からなる群より選択される少なくとも１種であることが好ましく、グラファイト及び二硫化モリブデンからなる群より選択される少なくとも１種であることがより好ましく、グラファイトであることが更に好ましい。 The solid lubricant (B) is preferably at least one selected from the group consisting of graphite, molybdenum disulfide, tungsten disulfide, graphite fluoride and boron nitride, and from the group consisting of graphite and molybdenum disulfide. More preferably, it is at least one selected, and it is even more preferably graphite.
上記固体潤滑剤（Ａ）と上記固体潤滑剤（Ｂ）との質量比（Ａ／Ｂ）は、５０／５０～９０／１０であることが好ましく、５５／４５～８５／１５であることがより好ましく、６０／４０～８０／２０であることが更に好ましく、６５／４５～８０／２０であることが特に好ましい。 The mass ratio (A/B) of the solid lubricant (A) to the solid lubricant (B) is preferably 50/50 to 90/10, and 55/45 to 85/15. It is more preferably 60/40 to 80/20, still more preferably 65/45 to 80/20.
上記固体潤滑剤は、塗膜中に安定に保持させる点で、平均粒径が０．１～１０μｍであることが好ましく、より好ましい下限が０．１５μｍであり、より好ましい上限が５μｍである。
本明細書において、平均粒径は、堀場製作所製ＣＡＰＡ７００（遠心沈降式粒度分布測定装置）にて測定した値である。 The solid lubricant preferably has an average particle diameter of 0.1 to 10 μm, more preferably has a lower limit of 0.15 μm, and more preferably has an upper limit of 5 μm in order to stably retain the solid lubricant in the coating film.
In the present specification, the average particle size is a value measured by CAPA700 (centrifugal sedimentation type particle size distribution measuring device) manufactured by Horiba Ltd.
上記フッ素ゴムと上記固体潤滑剤との質量比（フッ素ゴム／固体潤滑剤）は、２０／８０～８０／２０であることが好ましく、２５／７５～７５／２５であることがより好ましく、３０／７０～７０／３０であることが更に好ましい。 The mass ratio of the fluororubber to the solid lubricant (fluororubber/solid lubricant) is preferably 20/80 to 80/20, more preferably 25/75 to 75/25, and 30 It is more preferably /70 to 70/30.
上記有機溶剤は、特に限定されず、例えば、メチルエチルケトン〔ＭＥＫ〕、メチルイソブチルケトン〔ＭＩＢＫ〕、ジイソブチルケトン〔ＤＩＢＫ〕、ジアセトンアルコール、シクロヘキサノン、イソホロン等のケトン類、酢酸ブチル、酢酸イソペンチル等のエステル類、ジエチレングリコールジメチルエーテル等のエーテル類、トルエン、キシレン等の炭化水素類、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチル－２－ピロリドン等のアミド類を用いることができる。本開示の塗料組成物は、上記有機溶剤を１種のみ用いるものであってもよいし、２種以上の有機溶剤を用いるものであってもよい。上記有機溶剤の配合量は、上記塗料組成物に配合するフッ素ゴムの種類に応じて適宜調整することができる。 The organic solvent is not particularly limited, and examples thereof include ketones such as methyl ethyl ketone [MEK], methyl isobutyl ketone [MIBK], diisobutyl ketone [DIBK], diacetone alcohol, cyclohexanone, and isophorone, and esters such as butyl acetate and isopentyl acetate. It is possible to use ethers such as diethylene glycol dimethyl ether, hydrocarbons such as toluene and xylene, and amides such as N,N-dimethylacetamide and N-methyl-2-pyrrolidone. The coating composition of the present disclosure may use only one type of the above organic solvent, or may use two or more types of organic solvents. The blending amount of the organic solvent can be appropriately adjusted according to the type of fluororubber blended in the coating composition.
本開示の塗料組成物は、上記有機溶剤を含むことから、溶剤系塗料とすることができる。このため、水を溶媒とする水系塗料のように、分散剤として界面活性剤を使用する必要がなく、当該界面活性剤が塗膜に残存することによる塗膜物性の低下を防止することができる。また、水系塗料と比較して、塗料安定性にも優れる。 Since the coating composition of the present disclosure contains the above organic solvent, it can be a solvent-based coating composition. Therefore, unlike a water-based paint using water as a solvent, it is not necessary to use a surfactant as a dispersant, and it is possible to prevent deterioration of coating film physical properties due to the surfactant remaining in the coating film. .. Further, it is superior in paint stability as compared with water-based paint.
本開示の塗料組成物は、上述のフッ素ゴム、加硫剤、固体潤滑剤及び有機溶剤に加え、安定剤を含むものであってもよい。安定剤としては例えば、オルトギ酸エステル、オルト炭酸エステル、環状オルトエステル、ラクトンアセタール、オルトギ酸トリメチルエステル、オルトギ酸トリエチルエステル、オルト酢酸トリメチルエステル、オルト酢酸トリエチルエステル、オルト炭酸トリメチルエステル、オルト炭酸トリエチルエステル、オルト炭酸テトラメチルエステル、オルト炭酸テトラエチルエステル等のオルトエステル類；モノカルボン酸（蟻酸、酢酸、プロピオン酸等）、ジカルボン酸（シュウ酸、マロン酸、コハク酸等）等の有機酸等を用いることができる。本開示の塗料組成物は、上記安定剤を１種のみ用いるものであってもよいし、２種以上の安定剤を用いるものであってもよい。 The coating composition of the present disclosure may include a stabilizer in addition to the above-mentioned fluororubber, vulcanizing agent, solid lubricant and organic solvent. Examples of the stabilizer include orthoformate ester, orthocarbonate ester, cyclic orthoester, lactone acetal, trimethyl orthoformate ester, triethyl orthoformate ester, trimethyl orthoacetate ester, triethyl orthoacetate ester, trimethyl orthocarbonate ester, and triethyl orthocarbonate ester. , Orthoesters such as tetramethyl orthocarbonate, tetraethyl orthocarbonate; organic acids such as monocarboxylic acids (formic acid, acetic acid, propionic acid, etc.) and dicarboxylic acids (oxalic acid, malonic acid, succinic acid, etc.), etc. be able to. The coating composition of the present disclosure may use only one of the above stabilizers, or may use two or more types of stabilizers.
本開示の塗料組成物には、上記成分に加え各種添加剤、例えば充填材、着色剤、消泡剤、表面調整剤等を配合することができる。
上記充填材としては、カーボンブラック、ホワイトカーボン、炭酸カルシウム、硫酸バリウム、タルク、珪酸カルシウム等が例示できる。なかでもカーボンブラックが好ましい。
上記着色剤としては、無機顔料、複合酸化物顔料等が例示できる。
上記消泡剤としてはシリコン系消泡剤、ポリマー系消泡剤等が例示できる。
上記表面調整剤としてはシロキサン化合物、アクリル系共重合物、メタクリル系共重合物等が例示できる。 In addition to the above components, various additives such as a filler, a colorant, a defoaming agent, and a surface conditioner can be added to the coating composition of the present disclosure.
Examples of the filler include carbon black, white carbon, calcium carbonate, barium sulfate, talc, calcium silicate and the like. Of these, carbon black is preferred.
Examples of the colorant include inorganic pigments and complex oxide pigments.
Examples of the above defoaming agent include a silicone defoaming agent and a polymer defoaming agent.
Examples of the surface modifier include siloxane compounds, acrylic copolymers, methacrylic copolymers and the like.
本開示の塗料組成物を塗布対象物に塗布し、乾燥することにより、塗膜を形成することができる。 A coating film can be formed by applying the coating composition of the present disclosure to an object to be coated and drying.
上記塗料組成物の塗布は、ハケ塗り、スプレーコーティング、浸漬塗布、フローコーティング、ディスペンサーコーティング、スクリーンコーティング等、公知の塗布方法により行うことができる。 The coating composition can be applied by known coating methods such as brush coating, spray coating, dip coating, flow coating, dispenser coating, and screen coating.
上記塗布・乾燥の後、必要に応じて硬化を行ってもよい。上記硬化は、一層ごとに行ってもよく、複数の層についてまとめて行ってもよい。また、上記硬化を、上記乾燥と同時に行ってもよい。
乾燥及び硬化の条件は、本開示の塗料組成物及び塗布対象物の種類等に応じて適宜設定することができる。 After the application and drying, curing may be performed if necessary. The curing may be carried out layer by layer or collectively for a plurality of layers. Further, the curing may be performed simultaneously with the drying.
The drying and curing conditions can be appropriately set according to the type of the coating composition of the present disclosure and the object to be coated.
本開示の塗料組成物は、非粘着性及び耐引掻き傷性に優れる塗膜を与えることから、非粘着処理用塗料組成物として好適に使用することができる。処理対象がエラストマー層である場合に、非粘着性及び耐引掻き傷性が一層顕著に発揮されることから、エラストマー層の非粘着処理用塗料組成物として特に好適に使用することができる。上記エラストマー層は、エラストマーを含む塗料組成物の塗膜であることが好ましい。 The coating composition of the present disclosure provides a coating film excellent in non-adhesiveness and scratch resistance, and thus can be suitably used as a non-adhesive treatment coating composition. When the object to be treated is an elastomer layer, non-adhesiveness and scratch resistance are more remarkably exhibited, and therefore, it can be particularly suitably used as a coating composition for non-adhesive treatment of an elastomer layer. The elastomer layer is preferably a coating film of a coating composition containing an elastomer.
上記エラストマー層に使用し得るエラストマーとしては、フッ素ゴム、ニトリルゴム、水素化ニトリルゴム、スチレン－ブタジエンゴム（ＳＢＲ）、クロロプレンゴム（ＣＲ）、ブタジエンゴム（ＢＲ）、天然ゴム（ＮＲ）、イソプレンゴム（ＩＲ）、エチレン－α－オレフィンゴム、エチレン－α－オレフィン－非共役ジエンゴム、塩素化ポリオレフィンゴム、クロロスルホン化ポリオレフィンゴム、アクリルゴム、エチレン系アクリルゴム、エピクロルヒドリンゴム、シリコーンゴム、ブチルゴム（ＩＩＲ）、エチレン－ビニルエステルゴム及びエチレン－メタクリレートゴム等が挙げられる。なかでも、フッ素ゴムが好ましい。 Elastomers that can be used in the elastomer layer include fluororubber, nitrile rubber, hydrogenated nitrile rubber, styrene-butadiene rubber (SBR), chloroprene rubber (CR), butadiene rubber (BR), natural rubber (NR), isoprene rubber. (IR), ethylene-α-olefin rubber, ethylene-α-olefin-non-conjugated diene rubber, chlorinated polyolefin rubber, chlorosulfonated polyolefin rubber, acrylic rubber, ethylene-based acrylic rubber, epichlorohydrin rubber, silicone rubber, butyl rubber (IIR) , Ethylene-vinyl ester rubber, ethylene-methacrylate rubber and the like. Of these, fluororubber is preferable.
上記フッ素ゴムとしては、ビニリデンフルオライド［ＶｄＦ］系フッ素ゴム、テトラフルオロエチレン［ＴＦＥ］／プロピレン［Ｐｒ］系フッ素ゴム、ＴＦＥ／Ｐｒ／ＶｄＦ系フッ素ゴム、エチレン［Ｅｔ］／ヘキサフルオロプロピレン［ＨＦＰ］系フッ素ゴム、Ｅｔ／ＨＦＰ／ＶｄＦ系フッ素ゴム、Ｅｔ／ＨＦＰ／ＴＦＥ系フッ素ゴム、フルオロシリコーン系フッ素ゴム、フルオロホスファゼン系フッ素ゴム等が挙げられる。なかでもＶｄＦ系フッ素ゴムが好ましい。
上記フッ素ゴムは、１種又は２種以上を用いることができる。 Examples of the fluororubber include vinylidene fluoride [VdF] fluororubber, tetrafluoroethylene [TFE]/propylene [Pr] fluororubber, TFE/Pr/VdF fluororubber, ethylene [Et]/hexafluoropropylene [HFP]. ] Fluorine rubber, Et/HFP/VdF type fluorinated rubber, Et/HFP/TFE type fluorinated rubber, fluorosilicone type fluorinated rubber, fluorophosphazene type fluorinated rubber and the like. Of these, VdF fluororubber is preferable.
The fluororubber may be used alone or in combination of two or more.
上記ＶｄＦ系フッ素ゴムとしては、ＶｄＦ／ＨＦＰ共重合体、ＶｄＦ／ＴＦＥ／ＨＦＰ共重合体、ＶｄＦ／クロロトリフルオロエチレン［ＣＴＦＥ］共重合体、ＶｄＦ／ＣＴＦＥ／ＴＦＥ共重合体、ＶｄＦ／パーフルオロ（アルキルビニルエーテル）［ＰＡＶＥ］共重合体、ＶｄＦ／ＴＦＥ／ＰＡＶＥ共重合体、ＶｄＦ／ＨＦＰ／ＰＡＶＥ共重合体、ＶｄＦ／ＨＦＰ／ＴＦＥ／ＰＡＶＥ共重合体、ＶｄＦ／ＴＦＥ／Ｐｒ共重合体、ＶｄＦ／Ｅｔ／ＨＦＰ共重合体、ＶｄＦ／式（１）で表される含フッ素単量体の共重合体等が挙げられる。
式（１）：
ＣＨ２＝ＣＦＲｆ　　　　　　（１）
（式中、Ｒｆは炭素数１～１２の直鎖状又は分岐状のフルオロアルキル基） Examples of the VdF fluororubber include VdF/HFP copolymer, VdF/TFE/HFP copolymer, VdF/chlorotrifluoroethylene [CTFE] copolymer, VdF/CTFE/TFE copolymer, VdF/perfluoro. (Alkyl vinyl ether) [PAVE] copolymer, VdF/TFE/PAVE copolymer, VdF/HFP/PAVE copolymer, VdF/HFP/TFE/PAVE copolymer, VdF/TFE/Pr copolymer, VdF /Et/HFP copolymer, VdF/fluorine-containing monomer copolymer represented by the formula (1), and the like.
Formula (1):
CH 2 =CFRf (1)
(In the formula, Rf is a linear or branched fluoroalkyl group having 1 to 12 carbon atoms)
本開示は、金属板と、上記金属板の片面又は両面に設けられたエラストマー層と、上記エラストマー層の上に設けられた、上述の本開示の塗料組成物から形成された塗膜とを有することを特徴とする塗装物品にも関する。
本開示の塗装物品は、本開示の塗料組成物から形成された塗膜を有するので、非粘着性及び耐引掻き傷性に優れる。 The present disclosure has a metal plate, an elastomer layer provided on one side or both sides of the metal plate, and a coating film formed from the above-described coating composition of the present disclosure provided on the elastomer layer. It also relates to a coated article characterized by the above.
Since the coated article of the present disclosure has a coating film formed from the coating composition of the present disclosure, it is excellent in non-tackiness and scratch resistance.
上記金属板としては、鉄；ステンレス；アルミニウム；銅；真鍮；チタン；亜鉛メッキ、アルミニウムメッキ等を施したメッキ鋼鈑等からなる板が挙げられる。なかでもステンレス板、アルミニウム板が好ましい。 Examples of the metal plate include a plate made of iron; stainless steel; aluminum; copper; brass; titanium; galvanized, aluminum-plated steel plate, or the like. Of these, a stainless plate and an aluminum plate are preferable.
上記エラストマー層を構成するエラストマーとしては、上述の本開示の塗料組成物により処理することが可能なエラストマー層について例示したエラストマーを使用することができ、なかでもフッ素ゴムが好ましい。 As the elastomer forming the elastomer layer, the elastomers exemplified for the elastomer layer that can be treated with the coating composition of the present disclosure described above can be used, and among them, fluororubber is preferable.
上記エラストマー層は、上記エラストマーを含む塗料組成物の塗膜であることが好ましい。 The elastomer layer is preferably a coating film of a coating composition containing the elastomer.
上記エラストマー層は、厚みが５～５０μｍであることが好ましく、１０～３０μｍであることがより好ましい。 The elastomer layer preferably has a thickness of 5 to 50 μm, more preferably 10 to 30 μm.
上記エラストマー層は、上記金属板の片面又は両面に設けられる。上記エラストマー層は、上記金属板の上に直接設けられてもよく、プライマー層等の他の層を介して設けられてもよい。 The elastomer layer is provided on one side or both sides of the metal plate. The elastomer layer may be provided directly on the metal plate, or may be provided via another layer such as a primer layer.
上記本開示の塗料組成物から形成された塗膜は、上記エラストマー層の上に設けられる。上記塗膜は、上記エラストマー層の上に直接設けられてもよく、他の層を介して設けられてもよいが、非粘着性及び耐引掻き傷性が一層顕著に発揮される点で、上記エラストマー層の上に直接設けられることが好ましい。 The coating film formed from the coating composition of the present disclosure is provided on the elastomer layer. The coating film may be provided directly on the elastomer layer or may be provided via another layer, but the non-adhesiveness and the scratch resistance are more remarkably exhibited. It is preferably provided directly on the elastomer layer.
上記塗膜は、厚みが０．５μｍ以上１０μｍ未満であることが好ましく、１～５μｍであることがより好ましい。 The coating film preferably has a thickness of 0.5 μm or more and less than 10 μm, more preferably 1 to 5 μm.
上記塗膜の上に、更に他の層を設けてもよいが、非粘着性及び耐引掻き傷性が一層顕著に発揮される点で、上記塗膜の上に他の層を設けないこと、すなわち上記塗膜が上記塗装物品の最表面であることが好ましい。 On the coating film, further other layers may be provided, but in the point that non-adhesiveness and scratch resistance are more significantly exhibited, no other layer is provided on the coating film. That is, it is preferable that the coating film is the outermost surface of the coated article.
本開示の塗装物品は、例えば、上記金属板上に上記エラストマーを含む塗料組成物を塗布し、乾燥して得られた塗膜の上に、本開示の塗料組成物を塗布し、乾燥することにより、製造することができる。
各層を形成する塗料組成物を塗布・乾燥した後、必要に応じて硬化を行ってもよい。上記硬化は、一層ごとに行ってもよく、複数の層についてまとめて行ってもよい。また、上記硬化を、上記乾燥と同時に行ってもよい。
乾燥及び硬化の条件は、本開示の塗料組成物及びエラストマー層の種類等に応じて適宜設定することができる。 The coated article of the present disclosure includes, for example, applying the coating composition containing the elastomer on the metal plate, and drying the coating composition obtained by applying the coating composition of the present disclosure on a coating film obtained by drying. Can be manufactured.
After coating and drying the coating composition forming each layer, curing may be carried out if necessary. The curing may be carried out layer by layer or collectively for a plurality of layers. Further, the curing may be performed simultaneously with the drying.
Drying and curing conditions can be appropriately set according to the type of the coating composition and the elastomer layer of the present disclosure.
本開示の塗料組成物及び塗装物品は、非粘着性、耐引掻き傷性等が要求される分野において使用することができ、例えば、各種シート・ベルト類；Ｏ－リング、ダイヤフラム、バルブシール、化学プラント用ガスケット、エンジンガスケット等のシーリング材；耐薬品性チューブ、燃料ホース、継手等の薬液等流体輸送部材；複写機、プリンター、ファクシミリ等のＯＡ機器用のロール（例えば、定着ロール、圧着ロール）又は搬送ベルト等に使用することができ、中でも、ガスケットに好適に使用することができる。本開示の塗装物品がフッ素ゴムコートガスケット材料であることは、好適な態様の１つである。 The coating composition and coated article of the present disclosure can be used in fields requiring non-adhesiveness, scratch resistance and the like. For example, various seats and belts; O-rings, diaphragms, valve seals, chemicals. Sealing materials for plant gaskets, engine gaskets, etc.; chemical-resistant tubes, fuel hoses, fluid transport members for chemicals such as joints; rolls for office automation equipment such as copiers, printers, facsimiles (eg, fixing rolls, pressure rolls) Alternatively, it can be used for a conveyor belt and the like, and above all, it can be preferably used for a gasket. It is one of the preferred embodiments that the coated article of the present disclosure is a fluororubber coated gasket material.
次に実施例を挙げて本開示を更に詳しく説明するが、本開示はこれらの実施例のみに限定されるものではない。 Next, the present disclosure will be described in more detail with reference to examples, but the present disclosure is not limited to these examples.
＜非粘着処理用塗料組成物の調製＞
実施例１
フッ素ゴムとしてビニリデンフルオライド／テトラフルオロエチレン／ヘキサフルオロプロピレン共重合体（フッ素濃度：６８質量％）からなるエラストマーの固形分１００質量部に対し、グラファイト３７．５質量部、フッ素樹脂（ポリテトラフルオロエチレン〔ＰＴＦＥ〕）１１２．５質量部及び受酸剤５質量部をオープンロールにて混練しコンパウンドとした。このコンパウンドを有機溶剤としてのメチルエチルケトン７００質量部と混合し、コンパウンド溶液を得た。
一方、ポリオール系加硫剤２質量部と加硫助剤０．５質量部を、有機溶剤としてのメチルエチルケトン２００質量部及びエタノール５質量部から構成される混合溶媒に溶解し、その中に安定剤として、オルト酢酸エステル系化合物２質量部及び有機酸２質量部を加えた。この溶液を、先に調製したコンパウンド溶液とディスパーで混合して非粘着処理用塗料組成物を得た。 <Preparation of non-stick treatment coating composition>
Example 1
As a fluororubber, vinylidene fluoride/tetrafluoroethylene/hexafluoropropylene copolymer (fluorine concentration: 68% by mass) is used for 100 parts by mass of solid content of an elastomer, and 37.5 parts by mass of graphite and fluororesin (polytetrafluoro). 112.5 parts by mass of ethylene [PTFE] and 5 parts by mass of the acid acceptor were kneaded with an open roll to prepare a compound. This compound was mixed with 700 parts by mass of methyl ethyl ketone as an organic solvent to obtain a compound solution.
On the other hand, 2 parts by mass of a polyol-based vulcanizing agent and 0.5 part by mass of a vulcanization aid are dissolved in a mixed solvent composed of 200 parts by mass of methyl ethyl ketone as an organic solvent and 5 parts by mass of ethanol, and a stabilizer is added therein. As the above, 2 parts by mass of the orthoacetic acid ester compound and 2 parts by mass of the organic acid were added. This solution was mixed with the previously prepared compound solution with a disper to obtain a non-adhesive treatment coating composition.
実施例２及び６
フッ素ゴム、フッ素樹脂及びグラファイトの配合量を表１に示すように変更し、かつカーボンブラックを配合したこと以外は実施例１と同様にして、非粘着処理用塗料組成物を得た。 Examples 2 and 6
A coating composition for non-adhesive treatment was obtained in the same manner as in Example 1 except that the compounding amounts of fluororubber, fluororesin and graphite were changed as shown in Table 1 and that carbon black was compounded.
実施例３～５
フッ素ゴム、フッ素樹脂及びグラファイトの配合量を表１に示すように変更したこと以外は実施例１と同様にして、非粘着処理用塗料組成物を得た。 Examples 3-5
A non-adhesive treatment coating composition was obtained in the same manner as in Example 1 except that the compounding amounts of fluororubber, fluororesin and graphite were changed as shown in Table 1.
実施例７～１０
グラファイトを表１に示すように変更したこと以外は実施例１と同様にして、非粘着処理用塗料組成物を得た。 Examples 7-10
A non-stick treatment coating composition was obtained in the same manner as in Example 1 except that graphite was changed as shown in Table 1.
比較例１
フッ素ゴム、フッ素樹脂及びグラファイトの配合量を表１に示すように変更したこと以外は実施例１と同様にして、非粘着処理用塗料組成物を得た。 Comparative Example 1
A coating composition for non-adhesive treatment was obtained in the same manner as in Example 1 except that the compounding amounts of fluororubber, fluororesin and graphite were changed as shown in Table 1.
比較例２
フッ素ゴム（ビニリデンフルオライド／テトラフルオロエチレン／ヘキサフルオロプロピレン共重合体）の水性ディスパージョン（フッ素ゴム含有量６０質量％）１００質量部、フッ素樹脂（ポリテトラフルオロエチレン〔ＰＴＦＥ〕）の水性ディスパージョン（フッ素樹脂含有量６０質量％）１００質量部、アミノ基含有シランカップリング剤６質量部、水３８００質量部を混合し非粘着処理用塗料組成物を得た。 Comparative example 2
100 parts by mass of an aqueous dispersion of fluororubber (vinylidene fluoride/tetrafluoroethylene/hexafluoropropylene copolymer) (60% by mass of fluororubber content), an aqueous dispersion of a fluororesin (polytetrafluoroethylene [PTFE]) (Fluorine resin content 60% by mass) 100 parts by mass, 6 parts by mass of amino group-containing silane coupling agent, and 3800 parts by mass of water were mixed to obtain a non-adhesive treatment coating composition.
＜試験片（塗装物品）の作製＞
予めアセトン洗浄しておいたアルミ板に、フッ素ゴム塗料（ＶｄＦ／ＨＦＰ共重合体のジイソブチルケトン溶液）をフローコーターにて塗装し、１００℃で３０分乾燥した後に、２００℃で３０分焼成して、ゴム層厚み２５μｍの塗装板を得た。
上記で得られた塗装板を実施例及び比較例で得られた非粘着処理用塗料組成物に、常温で浸漬塗装し、次いで８０～１００℃で５分間乾燥を行った後、２００℃で５分間焼成し、厚み１μｍの非粘着処理層をもつ試験片（塗装物品）を得た。 <Preparation of test piece (painted article)>
A fluororubber coating (diisobutyl ketone solution of VdF/HFP copolymer) was applied to an aluminum plate that had been washed with acetone in advance with a flow coater, dried at 100°C for 30 minutes, and then baked at 200°C for 30 minutes. Thus, a coated plate having a rubber layer thickness of 25 μm was obtained.
The coated plate obtained above is dip coated at room temperature with the coating composition for non-adhesive treatment obtained in Examples and Comparative Examples, followed by drying at 80 to 100° C. for 5 minutes, and then at 200° C. for 5 minutes. After baking for 1 minute, a test piece (painted article) having a non-adhesive treated layer having a thickness of 1 μm was obtained.
以下の方法により各物性を評価した。結果を表１に示す。
＜非粘着性試験（塗膜同士の非粘着性）＞
上記試験片を２ｃｍ幅で切り出して２ｃｍ×３ｃｍの塗膜面同士を重ね、荷重１ｋｇ、２００℃の条件下で１時間保持した。上記条件で重ね合わせた状態の試験片について、室温下でＪＩＳ　Ｋ６８５０の引張せん断接着強さ試験法に従い、万能試験機（島津製作所社製）を用いて引張強さを測定し、下記の基準で表面の粘着力を評価した。
○：引張強さ０ＭＰａ
△：引張強さ１．０×１０－２ＭＰａ未満
×：引張強さ１．０×１０－２ＭＰａ以上 Each physical property was evaluated by the following methods. The results are shown in Table 1.
<Non-adhesion test (non-adhesion between coating films)>
The above-mentioned test piece was cut out in a width of 2 cm, the coated surfaces of 2 cm×3 cm were overlapped with each other, and held under a load of 1 kg and 200° C. for 1 hour. The tensile strength of the test piece in the state of being piled up under the above conditions was measured at room temperature using a universal testing machine (manufactured by Shimadzu Corporation) in accordance with the tensile shear adhesive strength test method of JIS K6850, and the following criteria were used. The adhesive strength of the surface was evaluated.
○: Tensile strength 0 MPa
Δ: Tensile strength less than 1.0×10 −2 MPa ×: Tensile strength 1.0×10 −2 MPa or more
＜型汚染性（塗膜とアルミ板との非粘着性）＞
上記試験片を２ｃｍ幅で切り出し、別途用意したアルミ板（２ｃｍ幅）を２ｃｍ×３ｃｍの塗膜面に重ね、荷重１ｋｇ、２００℃の条件下で、１時間保持した。重ね合わせた試験片を剥がした後のアルミ板の汚染度を以下の基準で目視評価した。
○：汚染無し
△：わずかに汚染
×：全面に汚染 <Type contamination (non-adhesiveness between coating film and aluminum plate)>
The above test piece was cut out in a width of 2 cm, a separately prepared aluminum plate (2 cm width) was laid on a coating surface of 2 cm×3 cm, and held for 1 hour under a load of 1 kg and 200° C. The degree of contamination of the aluminum plate after peeling off the overlapped test pieces was visually evaluated according to the following criteria.
○: No pollution △: Slightly polluted ×: Contamination on the entire surface
＜耐引掻き傷性＞
ＨＥＩＤＯＮ試験機を用いて、上記試験片の塗膜の傷発生荷重を測定し、以下の基準で評価した。
○：８０ｇ以上
△：６０～７０ｇ
×：４０～５０ｇ <Scratch resistance>
The HEIDON tester was used to measure the scratch generation load of the coating film of the test piece, and the load was evaluated according to the following criteria.
○: 80g or more △: 60 to 70g
X: 40 to 50 g
＜塗料安定性＞
実施例及び比較例で得られた非粘着処理用塗料組成物を２５℃で２４時間保管後に再分散し、１００メッシュ金網でろ過し、ろ過残渣の濃度を測定し、以下の基準で評価した。
○：１質量％未満
△：２～４質量％
×：５質量％以上 <Paint stability>
The coating compositions for non-adhesive treatment obtained in Examples and Comparative Examples were redispersed after being stored at 25° C. for 24 hours, filtered with a 100 mesh wire mesh, the concentration of the filtration residue was measured, and evaluated according to the following criteria.
○: Less than 1% by mass △: 2 to 4% by mass
X: 5 mass% or more
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001

Claims (10)

  1. フッ素ゴム、加硫剤、固体潤滑剤及び有機溶剤を含み、
    前記固体潤滑剤は、固体潤滑剤（Ａ）と、前記固体潤滑剤（Ａ）とは異なる固体潤滑剤（Ｂ）とを含むことを特徴とする塗料組成物。     Contains fluororubber, vulcanizing agent, solid lubricant and organic solvent,
    The coating composition comprising the solid lubricant (A) and a solid lubricant (B) different from the solid lubricant (A).
  2. 前記固体潤滑剤（Ａ）はフッ素樹脂である請求項１記載の塗料組成物。 The coating composition according to claim 1, wherein the solid lubricant (A) is a fluororesin.
  3. 前記固体潤滑剤（Ｂ）はグラファイト、二硫化モリブデン、二硫化タングステン、フッ化黒鉛及び窒化ホウ素からなる群より選択される少なくとも１種である請求項１又は２記載の塗料組成物。 The coating composition according to claim 1 or 2, wherein the solid lubricant (B) is at least one selected from the group consisting of graphite, molybdenum disulfide, tungsten disulfide, graphite fluoride and boron nitride.
  4. 前記フッ素ゴムと前記固体潤滑剤との質量比（フッ素ゴム／固体潤滑剤）が２０／８０～８０／２０である請求項１～３のいずれかに記載の塗料組成物。 The coating composition according to any one of claims 1 to 3, wherein a mass ratio of the fluororubber and the solid lubricant (fluororubber/solid lubricant) is 20/80 to 80/20.
  5. 前記固体潤滑剤（Ａ）と前記固体潤滑剤（Ｂ）との質量比（固体潤滑剤（Ａ）／固体潤滑剤（Ｂ））が５０／５０～９０／１０である請求項１～４のいずれかに記載の塗料組成物。 5. The mass ratio (solid lubricant (A)/solid lubricant (B)) of the solid lubricant (A) and the solid lubricant (B) is 50/50 to 90/10. The coating composition according to any one of the above.
  6. 非粘着処理用塗料組成物である請求項１～５のいずれかに記載の塗料組成物。 The coating composition according to any one of claims 1 to 5, which is a non-adhesive treatment coating composition.
  7. エラストマー層の非粘着処理用塗料組成物である請求項１～６のいずれかに記載の塗料組成物。 The coating composition according to any one of claims 1 to 6, which is a coating composition for non-adhesive treatment of an elastomer layer.
  8. 金属板と、
    前記金属板の片面又は両面に設けられたエラストマー層と、
    前記エラストマー層の上に設けられた、請求項１～７のいずれかに記載の塗料組成物から形成された塗膜と
    を有することを特徴とする塗装物品。     A metal plate,
    An elastomer layer provided on one side or both sides of the metal plate,
    A coated article formed on the elastomer layer, the coating film being formed from the coating composition according to any one of claims 1 to 7.
  9. 前記エラストマー層は、フッ素ゴム層である請求項８記載の塗装物品。 The coated article according to claim 8, wherein the elastomer layer is a fluororubber layer.
  10. フッ素ゴムコートガスケット材料である請求項８又は９記載の塗装物品。 The coated article according to claim 8 or 9, which is a fluororubber-coated gasket material.
PCT/JP2020/006986 2019-02-21 2020-02-21 Coating composition and coated article WO2020171196A1 (en)

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JP2005344052A (en) * 2004-06-04 2005-12-15 Daikin Ind Ltd Solvent type coating composition
JP2007146096A (en) * 2005-10-31 2007-06-14 Toyoda Gosei Co Ltd Sealing member for fuel system and fluororubber coating composition therefor
WO2007135956A1 (en) * 2006-05-18 2007-11-29 Daikin Industries, Ltd. Multilayer body whose surface is treated to be nonadhesive and use thereof

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