WO2020171193A1 - Fluorine rubber coating composition and coated article - Google Patents
Fluorine rubber coating composition and coated article Download PDFInfo
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- WO2020171193A1 WO2020171193A1 PCT/JP2020/006979 JP2020006979W WO2020171193A1 WO 2020171193 A1 WO2020171193 A1 WO 2020171193A1 JP 2020006979 W JP2020006979 W JP 2020006979W WO 2020171193 A1 WO2020171193 A1 WO 2020171193A1
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- coating composition
- fluororubber
- mass
- parts
- amino group
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Classifications
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- 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
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- 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
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- 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
- 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
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- 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
- C09D7/63—Additives non-macromolecular organic
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16J—PISTONS; CYLINDERS; SEALINGS
- F16J15/00—Sealings
- F16J15/02—Sealings between relatively-stationary surfaces
- F16J15/06—Sealings between relatively-stationary surfaces with solid packing compressed between sealing surfaces
- F16J15/10—Sealings between relatively-stationary surfaces with solid packing compressed between sealing surfaces with non-metallic packing
Definitions
- the present disclosure relates to fluororubber coating compositions and coated articles.
- Fluorine rubber is used not only for molded products but also for coating, utilizing its excellent heat resistance, oil resistance, solvent resistance, and chemical resistance.
- the latter includes, for example, woven fabrics, fibers, metals, plastics, It is widely used as an industrial material by coating or impregnating rubber or other various base materials.
- Patent Document 1 describes a coating material containing fluororubber, a polyol-based vulcanizing agent, 15 parts by weight of an amino group-containing metal compound, 100 parts by weight of fluororubber, methyl isobutyl ketone and the like.
- Patent Document 2 describes a coating material containing fluororubber, a polyol-based vulcanizing agent, propylene glycol diacetate (thickener), methyl isobutyl ketone (good solvent), isoparaffin-based solvent (defoaming organic liquid), and the like. There is.
- An object of the present disclosure is to provide a coating composition that gives a coating film that is less likely to drop from a substrate and has a small compression set, and a coated article provided with such a coating film.
- the present disclosure includes a fluororubber, a polyol-based vulcanizing agent, an amino group-containing metal compound and an organic solvent
- the present invention relates to a fluororubber coating composition comprising 100 parts by mass of the fluororubber and 0.1 to 4.99 parts by mass in total of the polyol-based vulcanizing agent and the amino group-containing metal compound.
- the mass ratio of the polyol-based vulcanizing agent to the amino group-containing metal compound is preferably 1.0:0.1 to 1.0:1.2.
- the metal of the amino group-containing metal compound is preferably at least one selected from the group consisting of Si, Al, Ti and Zr.
- the polyol-based vulcanizing agent is 0.1 to 3 parts by mass and the amino group-containing metal compound is 0.1 to 2 parts by mass with respect to 100 parts by mass of the fluororubber.
- the fluororubber coating composition preferably further contains a stabilizer.
- the stabilizer is preferably an orthoester compound.
- the fluororubber coating composition preferably further contains a surface modifier.
- the fluororubber coating composition preferably further contains an antifoaming agent.
- the present disclosure includes a metal plate,
- the present invention also relates to a coated article having a coating film formed from the fluororubber coating composition provided on one side or both sides of the metal plate.
- the coated article is preferably a fluororubber coated gasket material.
- a coating composition that gives a coating film that is less likely to drop from the substrate and has a small compression set, and a coated article provided with such a coating film.
- the present disclosure contains a fluororubber, a polyol-based vulcanizing agent, an amino group-containing metal compound and an organic solvent, and the total amount of the polyol-based vulcanizing agent and the amino group-containing metal compound is 0 with respect to 100 parts by mass of the fluororubber.
- the present invention relates to a fluororubber coating composition containing 1 to 4.99 parts by mass. Since the fluororubber coating composition of the present disclosure contains the above-mentioned components, it is possible to provide a coating film that is unlikely to drop off from the base material (the coating film is unlikely to set) and that has a small compression set. Therefore, when the above coating composition is applied to a sealing material, excellent sealing properties can be obtained.
- 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
- a vulcanizing agent usually used for polyol-vulcanized fluorororubber can be used.
- the polyol-based vulcanizing agent include compounds having at least two hydroxyl groups, particularly phenolic hydroxyl groups, in the molecule and having vulcanization performance, and the compound may be a polymer compound. ..
- polyol-based vulcanizing agent examples include, 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. Compounds represented by the formula: R f 1 (CH 2 OH) 2 (R f 1 represents a perfluoroalkyl polyether group) are preferable.
- any of the commercially available polyol-based vulcanizing agents for fluororubber can be used.
- the above polyol-based vulcanizing agents may be used alone or in combination of two or more.
- the polyol-based vulcanizing agent is preferably used in an amount of 0.1 to 3 parts by mass based on 100 parts by mass of the fluororubber.
- a more preferred lower limit is 0.5 parts by mass and a more preferred upper limit is 2.5 parts by mass.
- a vulcanization aid can 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 amount used is, for example, 0 to 10 parts by mass with respect to 100 parts by mass of the fluororubber.
- the preferred lower limit is 0.1 parts by mass, the more preferred lower limit is 0.3 parts by mass, and the preferred upper limit is 5 parts by mass.
- the amino group-containing metal compound is preferably an amino group-containing metal compound containing at least one metal selected from the group consisting of Si, Al, Ti and Zr.
- Preferred amino group-containing metal compounds include amino group-containing silane coupling agents, amino group-containing aluminum coupling agents, amino group-containing titanium coupling agents, and amino group-containing zirconium coupling agents.
- Preferred amino group-containing silane coupling agents are ⁇ -aminopropyltriethoxysilane, N- ⁇ -aminoethyl- ⁇ -aminopropyltrimethoxysilane, N-(trimethoxysilylpropyl)ethylenediamine and N- ⁇ -aminoethyl.
- Examples include - ⁇ -aminopropylmethyldimethoxysilane, ⁇ -ureidopropyltriethoxysilane, ⁇ -aminoethyl- ⁇ -aminoethyl- ⁇ -aminopropyltrimethoxysilane and the like.
- the amino group-containing metal compound may be used alone or in combination of two or more.
- the amino group-containing metal compound is preferably used in an amount of 0.1 to 2 parts by mass with respect to 100 parts by mass of the fluororubber.
- a more preferred lower limit is 0.5 parts by mass and a more preferred upper limit is 1.5 parts by mass.
- the coating composition of the present disclosure contains 0.1 to 4.99 parts by mass in total of the polyol-based vulcanizing agent and the amino group-containing metal compound with respect to 100 parts by mass of the fluororubber.
- the total amount of the polyol-based vulcanizing agent and the amino group-containing metal compound is preferably 1 part by mass or more, more preferably 2 parts by mass or more, based on 100 parts by mass of the fluororubber. It is more preferably 2 parts by mass or more. Further, it is preferably 4.5 parts by mass or less, and more preferably 4 parts by mass or less.
- the mass ratio between the polyol-based vulcanizing agent and the amino group-containing metal compound is 1.0:0.1 to 1.0:1.2. Is preferred. When the above mass ratio is within the above range, a coating film that is more unlikely to drop from the substrate and has a smaller compression set is obtained.
- the mass ratio is more preferably 1.0:0.2 to 1.0:1.0, further preferably 1.0:0.5 to 1.0:0.9.
- the coating composition of the present disclosure contains an organic solvent.
- the coating composition of the present disclosure may be a solvent-based coating.
- 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 preferably further contains a stabilizer.
- a stabilizer This makes the paint more excellent in stability.
- 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.
- Orthoester compounds such as orthocarbonic acid tetramethyl ester and orthocarbonic acid tetraethyl ester; organic acids such as monocarboxylic acid (formic acid, acetic acid, propionic acid, etc.) and dicarboxylic acid (oxalic acid, malonic acid, succinic acid, etc.)
- organic acids such as monocarboxylic acid (formic acid, acetic acid, propionic acid, etc.) and dicarboxylic acid (oxalic acid, malonic acid, succinic acid, etc.)
- orthoester compounds are preferable, and orthoacetate compounds are more preferable.
- the coating composition of the present disclosure may use only one of the above stabilizers, or may use two or more types of stabilizers.
- the stabilizer is preferably used in an amount of 1 to 8 parts by mass based on 100 parts by mass of the fluororubber. A more preferred lower limit is 2 parts by mass and a more preferred upper limit is 6 parts by mass.
- the coating composition of the present disclosure preferably further contains a surface conditioner.
- the surface modifier include siloxane compounds, acrylic copolymers, methacrylic copolymers and the like. Of these, acrylic copolymers are preferable.
- the surface conditioner is preferably used in an amount of 0.01 to 1 part by mass with respect to 100 parts by mass of the fluororubber.
- a more preferred lower limit is 0.02 part by mass, and a more preferred upper limit is 0.5 part by mass.
- the coating composition of the present disclosure preferably further contains an antifoaming agent.
- an antifoaming agent examples include a silicone defoaming agent and a polymer defoaming agent. Of these, polymer antifoaming agents are preferable.
- the defoaming agent is preferably used in an amount of 0.05 to 4 parts by mass with respect to 100 parts by mass of the fluororubber.
- a more preferred lower limit is 0.1 part by mass
- a more preferred upper limit is 3 parts by mass
- a still more preferred upper limit is 2 parts by mass.
- the coating composition of the present disclosure preferably contains both the above surface modifier and the above defoaming agent. As a result, excellent defoaming properties can be achieved even if the amounts of these components added are small. Further, it is possible to obtain a coating film having excellent interlayer adhesion (particularly, adhesion with the upper layer).
- the mass ratio of the surface conditioner and the defoamer is preferably 1/20 to 1/50, more preferably 1/30 to 1/40.
- various additives such as fillers and colorants 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.
- the colorant include inorganic pigments and complex oxide pigments.
- a coating film can be formed by applying the coating composition of the present disclosure to a substrate and drying.
- the coating composition of the present disclosure may be applied directly to a substrate, or may be applied via another layer such as a primer.
- 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 performed for each layer or may be performed for a plurality of layers collectively. 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 like.
- a substrate to which the coating composition of the present disclosure can be applied a substrate made of metal, concrete, plastic, stone, wood, paper or the like can be used. Of these, a base material made of a metal is preferable.
- the metal examples include iron; stainless steel; aluminum; copper; brass; titanium; galvanized steel plate plated with aluminum and the like. Of these, stainless steel is preferable.
- the present disclosure also relates to a coated article comprising a metal plate and a coating film formed from the above-described fluororubber coating composition of the present disclosure, which is provided on one side or both sides of the metal plate. Since the coated article of the present disclosure has the coating film formed from the coating composition of the present disclosure, the coating film is less likely to drop from the substrate (the coating film is less likely to be set) and the compression set is small. Therefore, when the above-mentioned coated article is applied to a sealing material, excellent sealing properties can be obtained.
- the metal plate it is possible to use a plate made of the metal exemplified as the base material to which the coating composition of the present disclosure can be applied.
- the coating film formed from the coating composition of the present disclosure is provided on one side or both sides of the metal plate.
- the coating film may be directly provided on the metal plate or may be provided via another layer such as a primer layer.
- the coating film preferably has a thickness of 5 to 50 ⁇ m, more preferably 10 to 30 ⁇ m.
- the coated article of the present disclosure can be produced, for example, by applying the coating composition of the present disclosure on the above metal plate and drying. After coating and drying the coating composition, it may be cured if necessary. When other layers are provided, the curing may be performed for each layer or may be performed for a plurality of layers collectively. 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 like.
- the coating composition and the coated article of the present disclosure can be used in a field in which a coating which does not easily fall off from a substrate and has a small compression set is required.
- the coated article of the present disclosure is a fluororubber coated gasket material.
- a compound was prepared by kneading 5 parts by mass with an open roll. This compound was mixed with a mixed solvent composed of 240 parts by mass of diisobutyl ketone and 70 parts by mass of isophorone as an organic solvent to obtain a compound solution.
- a polyol-based vulcanizing agent and 0.5 part by mass of a vulcanization aid are dissolved in 10 parts by mass of ethanol, and 2 parts by mass of an orthoacetic ester compound and 2 parts by mass of an organic acid are used as stabilizers therein.
- This solution was mixed with the previously prepared compound solution with a disper, and further 0.05 part by mass of an acrylic copolymer as a surface conditioner, 1.8 parts by mass of a polymer defoamer as an antifoaming agent, and amino.
- a fluororubber coating composition was obtained by mixing 1.2 parts by mass of the group-containing metal compound.
- Examples 2-6 A fluororubber coating composition was obtained in the same manner as in Example 1 except that the compounding amounts of the surface conditioner and the defoaming agent (or the defoaming organic liquid) were changed as shown in Table 2.
- the defoaming organic liquid an isoparaffin solvent having a surface tension of 0.026 N ⁇ m ⁇ 1 or less was used.
- Example 7 A fluororubber coating composition was obtained in the same manner as in Example 1 except that an orthoacetic acid ester compound was not added as a stabilizer.
- Examples 8 and 9 A fluororubber coating composition was obtained in the same manner as in Example 1 except that the compounding amount of the amino group-containing metal compound was changed as shown in Table 1.
- Comparative Examples 1 and 2 A fluororubber coating composition was obtained in the same manner as in Example 1 except that the compounding amounts of the polyol-based vulcanizing agent and the amino group-containing metal compound were changed as shown in Table 1.
- Example 3 The procedure of Example 1 was repeated except that the amounts of the polyol-based vulcanizing agent and the amino group-containing metal compound were changed as shown in Table 1 and that the orthoacetic acid ester-based compound was not added as a stabilizer. A rubber coating composition was obtained.
- Comparative Example 4 A fluororubber coating composition was obtained in the same manner as in Comparative Example 1 except that an orthoacetic acid ester compound was not added as a stabilizer.
- ⁇ Coating film (missing)> The coated plate was sandwiched in a jig for measuring compression set without using a spacer and held at 200° C. for 5 hours, and then the presence or absence of a missing coating film edge was visually observed and evaluated. The case where the coating film was not squeezed out or completely missing was evaluated as ⁇ , the case where the coating film was not missing but was squeezed out was evaluated as ⁇ , and the coating film which was missing was evaluated as x. The results are shown in Table 1.
- Compression set (rate) 100 ⁇ (t 0 ⁇ t 1 )/(t 0 ⁇ t 2 ).
- t 0 thickness before compression (mm)
- t 1 Thickness after compression (mm)
- t 2 Spacer thickness (mm) Those with a compression set of 50% or less were evaluated as O, 51% to 89% as ⁇ , and 90% or more as X.
- the above-mentioned fluororubber coating composition was sufficiently stirred on a SUS301 plate that had been washed with acetone in advance, and then applied by a screen printing method so that the film thickness of the fired coating film would be 25 ⁇ m.
- the application was performed 5 times, and the stopwatch immediately after the application was completed in each of the 4 times after the second application. After the start, the time required for the bubbles to completely disappear from the coating film was measured, and the average value of four times was taken as the defoaming time.
- the screen printer used for coating is a commercially available manual printing system, and a generally commercially available 70 mesh ring pattern screen was used. The results are shown in Table 2.
Abstract
The present invention provides a coating composition which enables the achievement of a coating film that is not susceptible to falling off from a base material, while having a low compression set. A fluorine rubber coating composition which is characterized by containing a fluorine rubber, a polyol-based vulcanizing agent, an amino group-containing metal compound and an organic solvent, and which is also characterized in that the polyol-based vulcanizing agent and the amino group-containing metal compound are contained in a total amount of 0.1-4.99 parts by mass relative to 100 parts by mass of the fluorine rubber.
Description
本開示は、フッ素ゴム塗料組成物及び塗装物品に関する。
The present disclosure relates to fluororubber coating compositions and coated articles.
フッ素ゴムは、その優れた耐熱性、耐油性、耐溶剤性、耐薬品性を利用して、成形品のほか、コーティングにも用いられ、後者としては、例えば、織物、繊維、金属、プラスチック、ゴム、その他種々の基材に塗装又は含浸して、工業用材料として広く用いられている。
Fluorine rubber is used not only for molded products but also for coating, utilizing its excellent heat resistance, oil resistance, solvent resistance, and chemical resistance. The latter includes, for example, woven fabrics, fibers, metals, plastics, It is widely used as an industrial material by coating or impregnating rubber or other various base materials.
特許文献１には、フッ素ゴム、ポリオール系加硫剤、フッ素ゴム１００重量部に対し１５重量部のアミノ基含有金属化合物、メチルイソブチルケトン等を含む塗料が記載されている。
Patent Document 1 describes a coating material containing fluororubber, a polyol-based vulcanizing agent, 15 parts by weight of an amino group-containing metal compound, 100 parts by weight of fluororubber, methyl isobutyl ketone and the like.
特許文献２には、フッ素ゴム、ポリオール系加硫剤、プロピレングリコールジアセテート（増粘剤）、メチルイソブチルケトン（良溶剤）、イソパラフィン系溶剤（消泡有機液体）等を含む塗料が記載されている。
Patent Document 2 describes a coating material containing fluororubber, a polyol-based vulcanizing agent, propylene glycol diacetate (thickener), methyl isobutyl ketone (good solvent), isoparaffin-based solvent (defoaming organic liquid), and the like. There is.
本開示は、基材から欠落しにくく、圧縮永久歪みが小さい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。
An object of the present disclosure is to provide a coating composition that gives a coating film that is less likely to drop from a substrate and has a small compression set, and a coated article provided with such a coating film.
本開示は、フッ素ゴム、ポリオール系加硫剤、アミノ基含有金属化合物及び有機溶剤を含み、
上記フッ素ゴム１００質量部に対し、上記ポリオール系加硫剤及び上記アミノ基含有金属化合物を合計で０．１～４．９９質量部含むことを特徴とするフッ素ゴム塗料組成物に関する。 The present disclosure includes a fluororubber, a polyol-based vulcanizing agent, an amino group-containing metal compound and an organic solvent,
The present invention relates to a fluororubber coating composition comprising 100 parts by mass of the fluororubber and 0.1 to 4.99 parts by mass in total of the polyol-based vulcanizing agent and the amino group-containing metal compound.
上記フッ素ゴム１００質量部に対し、上記ポリオール系加硫剤及び上記アミノ基含有金属化合物を合計で０．１～４．９９質量部含むことを特徴とするフッ素ゴム塗料組成物に関する。 The present disclosure includes a fluororubber, a polyol-based vulcanizing agent, an amino group-containing metal compound and an organic solvent,
The present invention relates to a fluororubber coating composition comprising 100 parts by mass of the fluororubber and 0.1 to 4.99 parts by mass in total of the polyol-based vulcanizing agent and the amino group-containing metal compound.
上記ポリオール系加硫剤と上記アミノ基含有金属化合物との質量比が１．０：０．１～１．０：１．２であることが好ましい。
The mass ratio of the polyol-based vulcanizing agent to the amino group-containing metal compound is preferably 1.0:0.1 to 1.0:1.2.
上記アミノ基含有金属化合物の金属が、Ｓｉ、Ａｌ、Ｔｉ及びＺｒ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 metal of the amino group-containing metal compound is preferably at least one selected from the group consisting of Si, Al, Ti and Zr.
上記フッ素ゴム１００質量部に対し、上記ポリオール系加硫剤が０．１～３質量部、上記アミノ基含有金属化合物が０．１～２質量部であることが好ましい。
It is preferable that the polyol-based vulcanizing agent is 0.1 to 3 parts by mass and the amino group-containing metal compound is 0.1 to 2 parts by mass with respect to 100 parts by mass of the fluororubber.
上記フッ素ゴム塗料組成物は、更に、安定剤を含むことが好ましい。
The fluororubber coating composition preferably further contains a stabilizer.
上記安定剤は、オルトエステル系化合物であることが好ましい。
The stabilizer is preferably an orthoester compound.
上記フッ素ゴム塗料組成物は、更に、表面調整剤を含むことが好ましい。
The fluororubber coating composition preferably further contains a surface modifier.
上記フッ素ゴム塗料組成物は、更に、消泡剤を含むことが好ましい。
The fluororubber coating composition preferably further contains an antifoaming agent.
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、上記フッ素ゴム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,
The present invention also relates to a coated article having a coating film formed from the fluororubber coating composition provided on one side or both sides of the metal plate.
上記金属板の片面又は両面に設けられた、上記フッ素ゴム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,
The present invention also relates to a coated article having a coating film formed from the fluororubber coating composition provided on one side or both sides of the metal plate.
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、基材から欠落しにくく、圧縮永久歪みが小さい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 that is less likely to drop from the substrate and has a small compression set, 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、ポリオール系加硫剤、アミノ基含有金属化合物及び有機溶剤を含み、上記フッ素ゴム１００質量部に対し、上記ポリオール系加硫剤及び上記アミノ基含有金属化合物を合計で０．１～４．９９質量部含むことを特徴とするフッ素ゴム塗料組成物に関する。
本開示のフッ素ゴム塗料組成物は、上記成分を含むので、基材から欠落しにくく（塗膜がヘタリにくく）、圧縮永久歪みが小さい塗膜を与えることができる。したがって、上記塗料組成物をシール材に適用する場合には、優れたシール性が得られる。
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 contains a fluororubber, a polyol-based vulcanizing agent, an amino group-containing metal compound and an organic solvent, and the total amount of the polyol-based vulcanizing agent and the amino group-containing metal compound is 0 with respect to 100 parts by mass of the fluororubber. The present invention relates to a fluororubber coating composition containing 1 to 4.99 parts by mass.
Since the fluororubber coating composition of the present disclosure contains the above-mentioned components, it is possible to provide a coating film that is unlikely to drop off from the base material (the coating film is unlikely to set) and that has a small compression set. Therefore, when the above coating composition is applied to a sealing material, excellent sealing properties can be obtained.
The coating composition of the present disclosure is also excellent in coating stability.
本開示は、フッ素ゴム、ポリオール系加硫剤、アミノ基含有金属化合物及び有機溶剤を含み、上記フッ素ゴム１００質量部に対し、上記ポリオール系加硫剤及び上記アミノ基含有金属化合物を合計で０．１～４．９９質量部含むことを特徴とするフッ素ゴム塗料組成物に関する。
本開示のフッ素ゴム塗料組成物は、上記成分を含むので、基材から欠落しにくく（塗膜がヘタリにくく）、圧縮永久歪みが小さい塗膜を与えることができる。したがって、上記塗料組成物をシール材に適用する場合には、優れたシール性が得られる。
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 contains a fluororubber, a polyol-based vulcanizing agent, an amino group-containing metal compound and an organic solvent, and the total amount of the polyol-based vulcanizing agent and the amino group-containing metal compound is 0 with respect to 100 parts by mass of the fluororubber. The present invention relates to a fluororubber coating composition containing 1 to 4.99 parts by mass.
Since the fluororubber coating composition of the present disclosure contains the above-mentioned components, it is possible to provide a coating film that is unlikely to drop off from the base material (the coating film is unlikely to set) and that has a small compression set. Therefore, when the above coating composition is applied to a sealing material, excellent sealing properties can be obtained.
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)
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)
上記ポリオール系加硫剤としては、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。上記ポリオール系加硫剤としては、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 above-mentioned polyol-based vulcanizing agent, a vulcanizing agent usually used for polyol-vulcanized fluororubber can be used. Examples of the polyol-based vulcanizing agent include compounds having at least two hydroxyl groups, particularly phenolic hydroxyl groups, in the molecule and having vulcanization performance, and the compound may be a polymer compound. ..
上記ポリオール系加硫剤としては、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。
上記ポリオール系加硫剤としては、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。
上記ポリオール系加硫剤は、１種又は２種以上を用いることができる。 Examples of the polyol-based vulcanizing agent include, 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. Compounds represented by the formula: R f 1 (CH 2 OH) 2 (R f 1 represents a perfluoroalkyl polyether group) are preferable.
As the above-mentioned polyol-based vulcanizing agent, in addition to the above, any of the commercially available polyol-based vulcanizing agents for fluororubber can be used.
The above polyol-based vulcanizing agents may be used alone or in combination of two or more.
上記ポリオール系加硫剤としては、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。
上記ポリオール系加硫剤は、１種又は２種以上を用いることができる。 Examples of the polyol-based vulcanizing agent include, 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. Compounds represented by the formula: R f 1 (CH 2 OH) 2 (R f 1 represents a perfluoroalkyl polyether group) are preferable.
As the above-mentioned polyol-based vulcanizing agent, in addition to the above, any of the commercially available polyol-based vulcanizing agents for fluororubber can be used.
The above polyol-based vulcanizing agents may be used alone or in combination of two or more.
上記ポリオール系加硫剤は、上記フッ素ゴム１００質量部に対して、０．１～３質量部用いることが好ましい。より好ましい下限は０．５質量部であり、より好ましい上限は２．５質量部である。
The polyol-based vulcanizing agent is preferably used in an amount of 0.1 to 3 parts by mass based on 100 parts by mass of the fluororubber. A more preferred lower limit is 0.5 parts by mass and a more preferred upper limit is 2.5 parts by mass.
本開示の塗料組成物においては、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 can 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.
上記加硫助剤を使用する場合の使用量は、例えば、上記フッ素ゴム１００質量部に対して０～１０質量部である。好ましい下限は０．１質量部、より好ましい下限は０．３質量部であり、好ましい上限は５質量部である。
When the vulcanization aid is used, the amount used is, for example, 0 to 10 parts by mass with respect to 100 parts by mass of the fluororubber. The preferred lower limit is 0.1 parts by mass, the more preferred lower limit is 0.3 parts by mass, and the preferred upper limit is 5 parts by mass.
上記アミノ基含有金属化合物としては、Ｓｉ、Ａｌ、Ｔｉ及びＺｒからなる群より選択される少なくとも１種の金属を含むアミノ基含有金属化合物が好ましい。
好ましいアミノ基含有金属化合物としては、アミノ基含有シランカップリング剤、アミノ基含有アルミニウムカップリング剤、アミノ基含有チタンカップリング剤、アミノ基含有ジルコニウムカップリング剤が挙げられる。
好ましいアミノ基含有シランカップリング剤としては、γ－アミノプロピルトリエトキシシラン、Ｎ－β－アミノエチル－γ－アミノプロピルトリメトキシシラン、Ｎ－（トリメトキシシリルプロピル）エチレンジアミン、Ｎ－β－アミノエチル－γ－アミノプロピルメチルジメトキシシラン、γ－ウレイドプロピルトリエトキシシラン、β－アミノエチル－β－アミノエチル－γ－アミノプロピルトリメトキシシラン等が挙げられる。
上記アミノ基含有金属化合物は、１種類を用いてもよいし、２種以上を併用してもよい。 The amino group-containing metal compound is preferably an amino group-containing metal compound containing at least one metal selected from the group consisting of Si, Al, Ti and Zr.
Preferred amino group-containing metal compounds include amino group-containing silane coupling agents, amino group-containing aluminum coupling agents, amino group-containing titanium coupling agents, and amino group-containing zirconium coupling agents.
Preferred amino group-containing silane coupling agents are γ-aminopropyltriethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, N-(trimethoxysilylpropyl)ethylenediamine and N-β-aminoethyl. Examples include -γ-aminopropylmethyldimethoxysilane, γ-ureidopropyltriethoxysilane, β-aminoethyl-β-aminoethyl-γ-aminopropyltrimethoxysilane and the like.
The amino group-containing metal compound may be used alone or in combination of two or more.
好ましいアミノ基含有金属化合物としては、アミノ基含有シランカップリング剤、アミノ基含有アルミニウムカップリング剤、アミノ基含有チタンカップリング剤、アミノ基含有ジルコニウムカップリング剤が挙げられる。
好ましいアミノ基含有シランカップリング剤としては、γ－アミノプロピルトリエトキシシラン、Ｎ－β－アミノエチル－γ－アミノプロピルトリメトキシシラン、Ｎ－（トリメトキシシリルプロピル）エチレンジアミン、Ｎ－β－アミノエチル－γ－アミノプロピルメチルジメトキシシラン、γ－ウレイドプロピルトリエトキシシラン、β－アミノエチル－β－アミノエチル－γ－アミノプロピルトリメトキシシラン等が挙げられる。
上記アミノ基含有金属化合物は、１種類を用いてもよいし、２種以上を併用してもよい。 The amino group-containing metal compound is preferably an amino group-containing metal compound containing at least one metal selected from the group consisting of Si, Al, Ti and Zr.
Preferred amino group-containing metal compounds include amino group-containing silane coupling agents, amino group-containing aluminum coupling agents, amino group-containing titanium coupling agents, and amino group-containing zirconium coupling agents.
Preferred amino group-containing silane coupling agents are γ-aminopropyltriethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, N-(trimethoxysilylpropyl)ethylenediamine and N-β-aminoethyl. Examples include -γ-aminopropylmethyldimethoxysilane, γ-ureidopropyltriethoxysilane, β-aminoethyl-β-aminoethyl-γ-aminopropyltrimethoxysilane and the like.
The amino group-containing metal compound may be used alone or in combination of two or more.
上記アミノ基含有金属化合物は、上記フッ素ゴム１００質量部に対して、０．１～２質量部用いることが好ましい。より好ましい下限は０．５質量部であり、より好ましい上限は１．５質量部である。
The amino group-containing metal compound is preferably used in an amount of 0.1 to 2 parts by mass with respect to 100 parts by mass of the fluororubber. A more preferred lower limit is 0.5 parts by mass and a more preferred upper limit is 1.5 parts by mass.
本開示の塗料組成物は、上記フッ素ゴム１００質量部に対し、上記ポリオール系加硫剤及び上記アミノ基含有金属化合物を合計で０．１～４．９９質量部含む。上記ポリオール系加硫剤及び上記アミノ基含有金属化合物の合計量が上記範囲内にあることにより、基材から欠落しにくく、圧縮永久歪みが小さい塗膜が得られる。また、塗料安定性に優れる。
上記ポリオール系加硫剤及び上記アミノ基含有金属化合物の合計量は、上記フッ素ゴム１００質量部に対し、１質量部以上であることが好ましく、２質量部以上であることがより好ましく、２．２質量部以上であることが更に好ましい。また、４．５質量部以下であることが好ましく、４質量部以下であることがより好ましい。 The coating composition of the present disclosure contains 0.1 to 4.99 parts by mass in total of the polyol-based vulcanizing agent and the amino group-containing metal compound with respect to 100 parts by mass of the fluororubber. When the total amount of the polyol-based vulcanizing agent and the amino group-containing metal compound is within the above range, a coating film that is unlikely to drop from the base material and has a small compression set can be obtained. It also has excellent paint stability.
1. The total amount of the polyol-based vulcanizing agent and the amino group-containing metal compound is preferably 1 part by mass or more, more preferably 2 parts by mass or more, based on 100 parts by mass of the fluororubber. It is more preferably 2 parts by mass or more. Further, it is preferably 4.5 parts by mass or less, and more preferably 4 parts by mass or less.
上記ポリオール系加硫剤及び上記アミノ基含有金属化合物の合計量は、上記フッ素ゴム１００質量部に対し、１質量部以上であることが好ましく、２質量部以上であることがより好ましく、２．２質量部以上であることが更に好ましい。また、４．５質量部以下であることが好ましく、４質量部以下であることがより好ましい。 The coating composition of the present disclosure contains 0.1 to 4.99 parts by mass in total of the polyol-based vulcanizing agent and the amino group-containing metal compound with respect to 100 parts by mass of the fluororubber. When the total amount of the polyol-based vulcanizing agent and the amino group-containing metal compound is within the above range, a coating film that is unlikely to drop from the base material and has a small compression set can be obtained. It also has excellent paint stability.
1. The total amount of the polyol-based vulcanizing agent and the amino group-containing metal compound is preferably 1 part by mass or more, more preferably 2 parts by mass or more, based on 100 parts by mass of the fluororubber. It is more preferably 2 parts by mass or more. Further, it is preferably 4.5 parts by mass or less, and more preferably 4 parts by mass or less.
上記ポリオール系加硫剤と上記アミノ基含有金属化合物との質量比（ポリオール系加硫剤：アミノ基含有金属化合物）は、１．０：０．１～１．０：１．２であることが好ましい。上記質量比が上記範囲内にあると、基材から一層欠落しにくく、圧縮永久歪みが一層小さい塗膜が得られる。
上記質量比は、１．０：０．２～１．０：１．０であることがより好ましく、１．０：０．５～１．０：０．９であることが更に好ましい。 The mass ratio between the polyol-based vulcanizing agent and the amino group-containing metal compound (polyol-based vulcanizing agent: amino group-containing metal compound) is 1.0:0.1 to 1.0:1.2. Is preferred. When the above mass ratio is within the above range, a coating film that is more unlikely to drop from the substrate and has a smaller compression set is obtained.
The mass ratio is more preferably 1.0:0.2 to 1.0:1.0, further preferably 1.0:0.5 to 1.0:0.9.
上記質量比は、１．０：０．２～１．０：１．０であることがより好ましく、１．０：０．５～１．０：０．９であることが更に好ましい。 The mass ratio between the polyol-based vulcanizing agent and the amino group-containing metal compound (polyol-based vulcanizing agent: amino group-containing metal compound) is 1.0:0.1 to 1.0:1.2. Is preferred. When the above mass ratio is within the above range, a coating film that is more unlikely to drop from the substrate and has a smaller compression set is obtained.
The mass ratio is more preferably 1.0:0.2 to 1.0:1.0, further preferably 1.0:0.5 to 1.0:0.9.
本開示の塗料組成物は、有機溶剤を含む。本開示の塗料組成物は、溶剤系塗料であってよい。
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 coating composition of the present disclosure contains an organic solvent. The coating composition of the present disclosure may be a solvent-based coating.
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.
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 coating composition of the present disclosure contains an organic solvent. The coating composition of the present disclosure may be a solvent-based coating.
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、更に、安定剤を含むことが好ましい。これにより、塗料安定性に一層優れたものとなる。
上記安定剤としては、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系化合物；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）等の有機酸が挙げられる。なかでも、オルトエステル系化合物が好ましく、オルト酢酸エステル系化合物がより好ましい。
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 preferably further contains a stabilizer. This makes the paint more excellent in stability.
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. Orthoester compounds such as orthocarbonic acid tetramethyl ester and orthocarbonic acid tetraethyl ester; organic acids such as monocarboxylic acid (formic acid, acetic acid, propionic acid, etc.) and dicarboxylic acid (oxalic acid, malonic acid, succinic acid, etc.) To be Of these, orthoester compounds are preferable, and orthoacetate compounds are more preferable.
The coating composition of the present disclosure may use only one of the above stabilizers, or may use two or more types of stabilizers.
上記安定剤としては、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系化合物；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）等の有機酸が挙げられる。なかでも、オルトエステル系化合物が好ましく、オルト酢酸エステル系化合物がより好ましい。
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 preferably further contains a stabilizer. This makes the paint more excellent in stability.
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. Orthoester compounds such as orthocarbonic acid tetramethyl ester and orthocarbonic acid tetraethyl ester; organic acids such as monocarboxylic acid (formic acid, acetic acid, propionic acid, etc.) and dicarboxylic acid (oxalic acid, malonic acid, succinic acid, etc.) To be Of these, orthoester compounds are preferable, and orthoacetate compounds are more preferable.
The coating composition of the present disclosure may use only one of the above stabilizers, or may use two or more types of stabilizers.
上記安定剤は、上記フッ素ゴム１００質量部に対して、１～８質量部用いることが好ましい。より好ましい下限は２質量部であり、より好ましい上限は６質量部である。
The stabilizer is preferably used in an amount of 1 to 8 parts by mass based on 100 parts by mass of the fluororubber. A more preferred lower limit is 2 parts by mass and a more preferred upper limit is 6 parts by mass.
本開示の塗料組成物は、更に、表面調整剤を含むことが好ましい。
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。なかでも、アクリル系共重合物が好ましい。 The coating composition of the present disclosure preferably further contains a surface conditioner.
Examples of the surface modifier include siloxane compounds, acrylic copolymers, methacrylic copolymers and the like. Of these, acrylic copolymers are preferable.
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。なかでも、アクリル系共重合物が好ましい。 The coating composition of the present disclosure preferably further contains a surface conditioner.
Examples of the surface modifier include siloxane compounds, acrylic copolymers, methacrylic copolymers and the like. Of these, acrylic copolymers are preferable.
上記表面調整剤は、上記フッ素ゴム１００質量部に対して、０．０１～１質量部用いることが好ましい。より好ましい下限は０．０２質量部であり、より好ましい上限は０．５質量部である。
The surface conditioner is preferably used in an amount of 0.01 to 1 part by mass with respect to 100 parts by mass of the fluororubber. A more preferred lower limit is 0.02 part by mass, and a more preferred upper limit is 0.5 part by mass.
本開示の塗料組成物は、更に、消泡剤を含むことが好ましい。
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。なかでも、ポリマー系消泡剤が好ましい。 The coating composition of the present disclosure preferably further contains an antifoaming agent.
Examples of the above defoaming agent include a silicone defoaming agent and a polymer defoaming agent. Of these, polymer antifoaming agents are preferable.
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。なかでも、ポリマー系消泡剤が好ましい。 The coating composition of the present disclosure preferably further contains an antifoaming agent.
Examples of the above defoaming agent include a silicone defoaming agent and a polymer defoaming agent. Of these, polymer antifoaming agents are preferable.
上記消泡剤は、上記フッ素ゴム１００質量部に対して、０．０５～４質量部用いることが好ましい。より好ましい下限は０．１質量部であり、より好ましい上限は３質量部であり、更に好ましい上限は２質量部である。
The defoaming agent is preferably used in an amount of 0.05 to 4 parts by mass with respect to 100 parts by mass of the fluororubber. A more preferred lower limit is 0.1 part by mass, a more preferred upper limit is 3 parts by mass, and a still more preferred upper limit is 2 parts by mass.
本開示の塗料組成物は、上記表面調整剤及び上記消泡剤の両方を含むことが好ましい。これにより、これらの成分の添加量が少なくても、優れた消泡性を実現することができる。更に、層間密着性（特に、上層との密着性）に優れる塗膜を得ることもできる。
上記表面調整剤及び上記消泡剤の質量比（表面調整剤／消泡剤）は、１／２０～１／５０であることが好ましく、１／３０～１／４０であることがより好ましい。 The coating composition of the present disclosure preferably contains both the above surface modifier and the above defoaming agent. As a result, excellent defoaming properties can be achieved even if the amounts of these components added are small. Further, it is possible to obtain a coating film having excellent interlayer adhesion (particularly, adhesion with the upper layer).
The mass ratio of the surface conditioner and the defoamer (surface conditioner/defoamer) is preferably 1/20 to 1/50, more preferably 1/30 to 1/40.
上記表面調整剤及び上記消泡剤の質量比（表面調整剤／消泡剤）は、１／２０～１／５０であることが好ましく、１／３０～１／４０であることがより好ましい。 The coating composition of the present disclosure preferably contains both the above surface modifier and the above defoaming agent. As a result, excellent defoaming properties can be achieved even if the amounts of these components added are small. Further, it is possible to obtain a coating film having excellent interlayer adhesion (particularly, adhesion with the upper layer).
The mass ratio of the surface conditioner and the defoamer (surface conditioner/defoamer) is preferably 1/20 to 1/50, more preferably 1/30 to 1/40.
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。
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。 In addition to the above components, various additives such as fillers and colorants 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.
Examples of the colorant include inorganic pigments and complex oxide pigments.
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。
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。 In addition to the above components, various additives such as fillers and colorants 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.
Examples of the colorant include inorganic pigments and complex oxide pigments.
本開示の塗料組成物を基材に塗布し、乾燥することにより、塗膜を形成することができる。本開示の塗料組成物を基材に直接塗布してもよいし、プライマー等の他の層を介して塗布してもよい。
A coating film can be formed by applying the coating composition of the present disclosure to a substrate and drying. The coating composition of the present disclosure may be applied directly to a substrate, or may be applied via another layer such as a primer.
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。他の層を設ける場合、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. When other layers are provided, the curing may be performed for each layer or may be performed for a plurality of layers collectively. 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 like.
乾燥及び硬化の条件は、本開示の塗料組成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. When other layers are provided, the curing may be performed for each layer or may be performed for a plurality of layers collectively. 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 like.
本開示の塗料組成物を塗布することが可能な基材としては、金属、コンクリート、プラスチック、石材、木材、紙等からなる基材が使用できる。なかでも、金属からなる基材が好ましい。
As a substrate to which the coating composition of the present disclosure can be applied, a substrate made of metal, concrete, plastic, stone, wood, paper or the like can be used. Of these, a base material made of a metal is preferable.
上記金属としては、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が挙げられる。なかでもステンレスが好ましい。
Examples of the metal include iron; stainless steel; aluminum; copper; brass; titanium; galvanized steel plate plated with aluminum and the like. Of these, stainless steel is preferable.
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、上述の本開示のフッ素ゴム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、塗膜が基材から欠落しにくく（塗膜がヘタリにくく）、圧縮永久歪みが小さい。したがって、上記塗装物品をシール材に適用する場合には、優れたシール性が得られる。 The present disclosure also relates to a coated article comprising a metal plate and a coating film formed from the above-described fluororubber coating composition of the present disclosure, which is provided on one side or both sides of the metal plate.
Since the coated article of the present disclosure has the coating film formed from the coating composition of the present disclosure, the coating film is less likely to drop from the substrate (the coating film is less likely to be set) and the compression set is small. Therefore, when the above-mentioned coated article is applied to a sealing material, excellent sealing properties can be obtained.
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、塗膜が基材から欠落しにくく（塗膜がヘタリにくく）、圧縮永久歪みが小さい。したがって、上記塗装物品をシール材に適用する場合には、優れたシール性が得られる。 The present disclosure also relates to a coated article comprising a metal plate and a coating film formed from the above-described fluororubber coating composition of the present disclosure, which is provided on one side or both sides of the metal plate.
Since the coated article of the present disclosure has the coating film formed from the coating composition of the present disclosure, the coating film is less likely to drop from the substrate (the coating film is less likely to be set) and the compression set is small. Therefore, when the above-mentioned coated article is applied to a sealing material, excellent sealing properties can be obtained.
上記金属板としては、本開示の塗料組成物を塗布することが可能な基材として例示した金属からなる板を使用することができる。
As the above-mentioned metal plate, it is possible to use a plate made of the metal exemplified as the base material to which the coating composition of the present disclosure can be applied.
上記本開示の塗料組成物から形成された塗膜は、上記金属板の片面又は両面に設けられる。上記塗膜は、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 coating film formed from the coating composition of the present disclosure is provided on one side or both sides of the metal plate. The coating film may be directly provided on the metal plate or may be provided via another layer such as a primer layer.
上記塗膜は、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 coating film preferably has a thickness of 5 to 50 μm, more preferably 10 to 30 μm.
上記塗膜の上に、他の層を更に設けてもよい。
You may further provide another layer on the said coating film.
本開示の塗装物品は、例えば、上記金属板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。
上記塗料組成物を塗布・乾燥した後、必要に応じて硬化を行ってもよい。他の層を設ける場合、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 can be produced, for example, by applying the coating composition of the present disclosure on the above metal plate and drying.
After coating and drying the coating composition, it may be cured if necessary. When other layers are provided, the curing may be performed for each layer or may be performed for a plurality of layers collectively. 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 like.
上記塗料組成物を塗布・乾燥した後、必要に応じて硬化を行ってもよい。他の層を設ける場合、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 can be produced, for example, by applying the coating composition of the present disclosure on the above metal plate and drying.
After coating and drying the coating composition, it may be cured if necessary. When other layers are provided, the curing may be performed for each layer or may be performed for a plurality of layers collectively. 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 like.
本開示の塗料組成物及び塗装物品は、基材から欠落しにくく、圧縮永久歪みが小さいコーティング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。
INDUSTRIAL APPLICABILITY The coating composition and the coated article of the present disclosure can be used in a field in which a coating which does not easily fall off from a substrate and has a small compression set is required. For example, various seat belts; O-rings, diaphragms, Sealing materials for valve seals, gaskets for chemical plants, engine gaskets, etc.; fluid transport members for chemical liquids such as chemical resistant tubes, fuel hoses, joints; rolls for office automation equipment such as copiers, printers, and facsimiles (eg, fixing rolls). , A pressure-bonding roll), a conveyor belt or the like, and among them, it can be suitably 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.
＜フッ素ゴム塗料組成物の調製＞
実施例１
フッ素ゴムとしてフッ化ビニリデン／ヘキサフルオロプロピレン共重合体（モル比でフッ化ビニリデン：ヘキサフルオロプロピレン＝７８：２２）からなるエラストマーの固形分１００質量部に対し、カーボンブラック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ジイソブチルケトン２４０質量部及びイソホロン７０質量部から構成される混合溶媒と混合し、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質量部をエタノール１０質量部に溶解し、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、更に表面調整剤としてのアクリル系共重合物０．０５質量部、消泡剤としてのポリマー系消泡剤１．８質量部、アミノ基含有金属化合物１．２質量部を混合してフッ素ゴム塗料組成物を得た。 <Preparation of fluororubber coating composition>
Example 1
5 parts by mass of carbon black and an acid acceptor per 100 parts by mass of solid content of an elastomer composed of a vinylidene fluoride/hexafluoropropylene copolymer (vinylidene fluoride:hexafluoropropylene=78:22 in a molar ratio) as a fluororubber. A compound was prepared by kneading 5 parts by mass with an open roll. This compound was mixed with a mixed solvent composed of 240 parts by mass of diisobutyl ketone and 70 parts by mass of isophorone 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 10 parts by mass of ethanol, and 2 parts by mass of an orthoacetic ester compound and 2 parts by mass of an organic acid are used as stabilizers therein. Was added. This solution was mixed with the previously prepared compound solution with a disper, and further 0.05 part by mass of an acrylic copolymer as a surface conditioner, 1.8 parts by mass of a polymer defoamer as an antifoaming agent, and amino. A fluororubber coating composition was obtained by mixing 1.2 parts by mass of the group-containing metal compound.
実施例１
フッ素ゴムとしてフッ化ビニリデン／ヘキサフルオロプロピレン共重合体（モル比でフッ化ビニリデン：ヘキサフルオロプロピレン＝７８：２２）からなるエラストマーの固形分１００質量部に対し、カーボンブラック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ジイソブチルケトン２４０質量部及びイソホロン７０質量部から構成される混合溶媒と混合し、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質量部をエタノール１０質量部に溶解し、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、更に表面調整剤としてのアクリル系共重合物０．０５質量部、消泡剤としてのポリマー系消泡剤１．８質量部、アミノ基含有金属化合物１．２質量部を混合してフッ素ゴム塗料組成物を得た。 <Preparation of fluororubber coating composition>
Example 1
5 parts by mass of carbon black and an acid acceptor per 100 parts by mass of solid content of an elastomer composed of a vinylidene fluoride/hexafluoropropylene copolymer (vinylidene fluoride:hexafluoropropylene=78:22 in a molar ratio) as a fluororubber. A compound was prepared by kneading 5 parts by mass with an open roll. This compound was mixed with a mixed solvent composed of 240 parts by mass of diisobutyl ketone and 70 parts by mass of isophorone 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 10 parts by mass of ethanol, and 2 parts by mass of an orthoacetic ester compound and 2 parts by mass of an organic acid are used as stabilizers therein. Was added. This solution was mixed with the previously prepared compound solution with a disper, and further 0.05 part by mass of an acrylic copolymer as a surface conditioner, 1.8 parts by mass of a polymer defoamer as an antifoaming agent, and amino. A fluororubber coating composition was obtained by mixing 1.2 parts by mass of the group-containing metal compound.
実施例２～６
表面調整剤及び消泡剤（又は消泡有機液体）の配合量を表２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、フッ素ゴム塗料組成物を得た。
なお、上記消泡有機液体としては、表面張力が０．０２６Ｎ・ｍ－１以下のイソパラフィン系溶剤を用いた。 Examples 2-6
A fluororubber coating composition was obtained in the same manner as in Example 1 except that the compounding amounts of the surface conditioner and the defoaming agent (or the defoaming organic liquid) were changed as shown in Table 2.
As the defoaming organic liquid, an isoparaffin solvent having a surface tension of 0.026 N·m −1 or less was used.
表面調整剤及び消泡剤（又は消泡有機液体）の配合量を表２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、フッ素ゴム塗料組成物を得た。
なお、上記消泡有機液体としては、表面張力が０．０２６Ｎ・ｍ－１以下のイソパラフィン系溶剤を用いた。 Examples 2-6
A fluororubber coating composition was obtained in the same manner as in Example 1 except that the compounding amounts of the surface conditioner and the defoaming agent (or the defoaming organic liquid) were changed as shown in Table 2.
As the defoaming organic liquid, an isoparaffin solvent having a surface tension of 0.026 N·m −1 or less was used.
実施例７
安定剤としてオルト酢酸エステル系化合物を配合しなかったこと以外は実施例１と同様にして、フッ素ゴム塗料組成物を得た。 Example 7
A fluororubber coating composition was obtained in the same manner as in Example 1 except that an orthoacetic acid ester compound was not added as a stabilizer.
安定剤としてオルト酢酸エステル系化合物を配合しなかったこと以外は実施例１と同様にして、フッ素ゴム塗料組成物を得た。 Example 7
A fluororubber coating composition was obtained in the same manner as in Example 1 except that an orthoacetic acid ester compound was not added as a stabilizer.
実施例８及び９
アミノ基含有金属化合物の配合量を表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、フッ素ゴム塗料組成物を得た。 Examples 8 and 9
A fluororubber coating composition was obtained in the same manner as in Example 1 except that the compounding amount of the amino group-containing metal compound was changed as shown in Table 1.
アミノ基含有金属化合物の配合量を表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、フッ素ゴム塗料組成物を得た。 Examples 8 and 9
A fluororubber coating composition was obtained in the same manner as in Example 1 except that the compounding amount of the amino group-containing metal compound was changed as shown in Table 1.
比較例１及び２
ポリオール系加硫剤及びアミノ基含有金属化合物の配合量を表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、フッ素ゴム塗料組成物を得た。 Comparative Examples 1 and 2
A fluororubber coating composition was obtained in the same manner as in Example 1 except that the compounding amounts of the polyol-based vulcanizing agent and the amino group-containing metal compound were changed as shown in Table 1.
ポリオール系加硫剤及びアミノ基含有金属化合物の配合量を表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、フッ素ゴム塗料組成物を得た。 Comparative Examples 1 and 2
A fluororubber coating composition was obtained in the same manner as in Example 1 except that the compounding amounts of the polyol-based vulcanizing agent and the amino group-containing metal compound were changed as shown in Table 1.
比較例３
ポリオール系加硫剤及びアミノ基含有金属化合物の配合量を表１に示すように変更し、かつ安定剤としてオルト酢酸エステル系化合物を配合しなかったこと以外は実施例１と同様にして、フッ素ゴム塗料組成物を得た。 Comparative Example 3
The procedure of Example 1 was repeated except that the amounts of the polyol-based vulcanizing agent and the amino group-containing metal compound were changed as shown in Table 1 and that the orthoacetic acid ester-based compound was not added as a stabilizer. A rubber coating composition was obtained.
ポリオール系加硫剤及びアミノ基含有金属化合物の配合量を表１に示すように変更し、かつ安定剤としてオルト酢酸エステル系化合物を配合しなかったこと以外は実施例１と同様にして、フッ素ゴム塗料組成物を得た。 Comparative Example 3
The procedure of Example 1 was repeated except that the amounts of the polyol-based vulcanizing agent and the amino group-containing metal compound were changed as shown in Table 1 and that the orthoacetic acid ester-based compound was not added as a stabilizer. A rubber coating composition was obtained.
比較例４
安定剤としてオルト酢酸エステル系化合物を配合しなかったこと以外は比較例１と同様にして、フッ素ゴム塗料組成物を得た。 Comparative Example 4
A fluororubber coating composition was obtained in the same manner as in Comparative Example 1 except that an orthoacetic acid ester compound was not added as a stabilizer.
安定剤としてオルト酢酸エステル系化合物を配合しなかったこと以外は比較例１と同様にして、フッ素ゴム塗料組成物を得た。 Comparative Example 4
A fluororubber coating composition was obtained in the same manner as in Comparative Example 1 except that an orthoacetic acid ester compound was not added as a stabilizer.
＜塗膜の作製＞
フッ素コートした手札サイズトレーに上記塗料組成物を２５ｇ入れ全面に伸ばした後室温で３日静置した。次に１００℃で２４時間乾燥した後に、２００℃で６０分焼成した。焼成後フィルムを取り出し、膜厚を測定すると約３００μｍであった。 <Preparation of coating film>
25 g of the above coating composition was placed in a fluorine-coated hand-sized tray, spread over the entire surface, and allowed to stand at room temperature for 3 days. Next, after drying at 100° C. for 24 hours, it was baked at 200° C. for 60 minutes. After firing, the film was taken out and the film thickness was measured to be about 300 μm.
フッ素コートした手札サイズトレーに上記塗料組成物を２５ｇ入れ全面に伸ばした後室温で３日静置した。次に１００℃で２４時間乾燥した後に、２００℃で６０分焼成した。焼成後フィルムを取り出し、膜厚を測定すると約３００μｍであった。 <Preparation of coating film>
25 g of the above coating composition was placed in a fluorine-coated hand-sized tray, spread over the entire surface, and allowed to stand at room temperature for 3 days. Next, after drying at 100° C. for 24 hours, it was baked at 200° C. for 60 minutes. After firing, the film was taken out and the film thickness was measured to be about 300 μm.
＜塗装板（塗装物品）の作製＞
予めアセトン洗浄しておいたＳＵＳ３０１板上に、上記塗料組成物を１６ミルのアプリケターで塗装した。予備乾燥後、８０～１００℃で３０分乾燥した後に、２００℃で３０分焼成した。 <Preparation of painted board (painted article)>
The above coating composition was coated on a SUS301 plate that had been washed with acetone in advance with a 16 mil applicator. After preliminary drying, it was dried at 80 to 100° C. for 30 minutes and then baked at 200° C. for 30 minutes.
予めアセトン洗浄しておいたＳＵＳ３０１板上に、上記塗料組成物を１６ミルのアプリケターで塗装した。予備乾燥後、８０～１００℃で３０分乾燥した後に、２００℃で３０分焼成した。 <Preparation of painted board (painted article)>
The above coating composition was coated on a SUS301 plate that had been washed with acetone in advance with a 16 mil applicator. After preliminary drying, it was dried at 80 to 100° C. for 30 minutes and then baked at 200° C. for 30 minutes.
＜塗膜ヘタリ（欠落）＞
上記塗装板を圧縮永久歪み測定用冶具にスペーサーを用いることなく挟み、２００℃で５時間保持した後、塗膜端部の欠落の有無を目視にて観察し、評価した。塗膜のはみだし、欠落の全くないものを○、塗膜の欠落はないが、はみだしのあるものを△、塗膜の欠落のあったものを×とした。結果を表１に示す。 <Coating film (missing)>
The coated plate was sandwiched in a jig for measuring compression set without using a spacer and held at 200° C. for 5 hours, and then the presence or absence of a missing coating film edge was visually observed and evaluated. The case where the coating film was not squeezed out or completely missing was evaluated as ◯, the case where the coating film was not missing but was squeezed out was evaluated as Δ, and the coating film which was missing was evaluated as x. The results are shown in Table 1.
上記塗装板を圧縮永久歪み測定用冶具にスペーサーを用いることなく挟み、２００℃で５時間保持した後、塗膜端部の欠落の有無を目視にて観察し、評価した。塗膜のはみだし、欠落の全くないものを○、塗膜の欠落はないが、はみだしのあるものを△、塗膜の欠落のあったものを×とした。結果を表１に示す。 <Coating film (missing)>
The coated plate was sandwiched in a jig for measuring compression set without using a spacer and held at 200° C. for 5 hours, and then the presence or absence of a missing coating film edge was visually observed and evaluated. The case where the coating film was not squeezed out or completely missing was evaluated as ◯, the case where the coating film was not missing but was squeezed out was evaluated as Δ, and the coating film which was missing was evaluated as x. The results are shown in Table 1.
＜シール性（圧縮永久歪み）：ＪＩＳ Ｋ６２６２－５に準拠＞
上記塗膜を厚みが約１０ｍｍになる様に重ね合わせ、ダイヤルゲージで厚みを測定した。次に試料を２５％圧縮加圧下に温度１７５℃で７２時間炉内に置き、ついでこれを炉から取り出し室温で３０分間放冷後ダイヤルゲージで厚みを測定し、次式に従って計算した。結果を表１に示す。 <Sealability (compression set): In accordance with JIS K6262-5>
The above coating films were stacked so that the thickness was about 10 mm, and the thickness was measured with a dial gauge. Next, the sample was placed in a furnace at a temperature of 175° C. for 72 hours under compression and pressure of 25%, then taken out of the furnace and allowed to cool at room temperature for 30 minutes, and then the thickness was measured with a dial gauge, and calculated according to the following formula. The results are shown in Table 1.
上記塗膜を厚みが約１０ｍｍになる様に重ね合わせ、ダイヤルゲージで厚みを測定した。次に試料を２５％圧縮加圧下に温度１７５℃で７２時間炉内に置き、ついでこれを炉から取り出し室温で３０分間放冷後ダイヤルゲージで厚みを測定し、次式に従って計算した。結果を表１に示す。 <Sealability (compression set): In accordance with JIS K6262-5>
The above coating films were stacked so that the thickness was about 10 mm, and the thickness was measured with a dial gauge. Next, the sample was placed in a furnace at a temperature of 175° C. for 72 hours under compression and pressure of 25%, then taken out of the furnace and allowed to cool at room temperature for 30 minutes, and then the thickness was measured with a dial gauge, and calculated according to the following formula. The results are shown in Table 1.
圧縮永久ひずみ（率）＝１００×（ｔ０－ｔ１）／（ｔ０－ｔ２）
ただし
ｔ０：圧縮前の厚さ（ｍｍ）
ｔ１：圧縮後の厚さ（ｍｍ）
ｔ２：スペーサーの厚さ（ｍｍ）
圧縮永久ひずみが５０％以下のものを○、５１％～８９％のものを△、９０％以上のものを×とした。 Compression set (rate)=100×(t 0 −t 1 )/(t 0 −t 2 ).
However, t 0 : thickness before compression (mm)
t 1 : Thickness after compression (mm)
t 2 : Spacer thickness (mm)
Those with a compression set of 50% or less were evaluated as O, 51% to 89% as Δ, and 90% or more as X.
ただし
ｔ０：圧縮前の厚さ（ｍｍ）
ｔ１：圧縮後の厚さ（ｍｍ）
ｔ２：スペーサーの厚さ（ｍｍ）
圧縮永久ひずみが５０％以下のものを○、５１％～８９％のものを△、９０％以上のものを×とした。 Compression set (rate)=100×(t 0 −t 1 )/(t 0 −t 2 ).
However, t 0 : thickness before compression (mm)
t 1 : Thickness after compression (mm)
t 2 : Spacer thickness (mm)
Those with a compression set of 50% or less were evaluated as O, 51% to 89% as Δ, and 90% or more as X.
＜消泡性（塗装性）＞
予めアセトンで洗浄しておいたＳＵＳ３０１板上に、上記フッ素ゴム塗料組成物を充分に攪拌した後スクリーン印刷方式により焼成後の塗膜の膜厚が２５μｍとなるように塗布した。１回目の塗布はスクリーンの網目中の空気が塗布膜中に移動してなる泡が多く存在するので、塗布を５回実施し、２回目以降の４回それぞれにおいて、塗布終了直後にストップウォッチをスタートし、塗布膜から泡が完全に消失するまでの時間を計測し、４回の平均値を消泡時間とした。塗布に用いたスクリーン印刷機は一般に市販されている手動印刷方式であり、一般に市販されている７０メッシュリング状パターンのスクリーンを使用した。結果を表２に示す。 <Defoaming property (paintability)>
The above-mentioned fluororubber coating composition was sufficiently stirred on a SUS301 plate that had been washed with acetone in advance, and then applied by a screen printing method so that the film thickness of the fired coating film would be 25 μm. In the first application, there are many bubbles formed by the air in the mesh of the screen moving into the application film. Therefore, the application was performed 5 times, and the stopwatch immediately after the application was completed in each of the 4 times after the second application. After the start, the time required for the bubbles to completely disappear from the coating film was measured, and the average value of four times was taken as the defoaming time. The screen printer used for coating is a commercially available manual printing system, and a generally commercially available 70 mesh ring pattern screen was used. The results are shown in Table 2.
予めアセトンで洗浄しておいたＳＵＳ３０１板上に、上記フッ素ゴム塗料組成物を充分に攪拌した後スクリーン印刷方式により焼成後の塗膜の膜厚が２５μｍとなるように塗布した。１回目の塗布はスクリーンの網目中の空気が塗布膜中に移動してなる泡が多く存在するので、塗布を５回実施し、２回目以降の４回それぞれにおいて、塗布終了直後にストップウォッチをスタートし、塗布膜から泡が完全に消失するまでの時間を計測し、４回の平均値を消泡時間とした。塗布に用いたスクリーン印刷機は一般に市販されている手動印刷方式であり、一般に市販されている７０メッシュリング状パターンのスクリーンを使用した。結果を表２に示す。 <Defoaming property (paintability)>
The above-mentioned fluororubber coating composition was sufficiently stirred on a SUS301 plate that had been washed with acetone in advance, and then applied by a screen printing method so that the film thickness of the fired coating film would be 25 μm. In the first application, there are many bubbles formed by the air in the mesh of the screen moving into the application film. Therefore, the application was performed 5 times, and the stopwatch immediately after the application was completed in each of the 4 times after the second application. After the start, the time required for the bubbles to completely disappear from the coating film was measured, and the average value of four times was taken as the defoaming time. The screen printer used for coating is a commercially available manual printing system, and a generally commercially available 70 mesh ring pattern screen was used. The results are shown in Table 2.
＜層間密着性（対上塗り層）＞
上記で得た塗装板の塗膜上に、上塗り層としてフッ素ゴム塗料（ＶｄＦ／ＨＦＰ共重合体のメチルエチルケトン〔ＭＥＫ〕溶液）をディップ塗装して、１００℃で３０分乾燥した後に、２００℃で３０分焼成して試験片を得た。
ＪＩＳ Ｋ５４００に準拠して上記試験片の塗膜面のセロハンテープ剥離を１０回繰り返し、剥離せずに残存した塗膜のマス数（１００マス中）を求めた。
結果を表２に示す。 <Interlayer adhesion (against overcoat layer)>
On the coating film of the coated plate obtained above, a fluororubber paint (methyl ethyl ketone [MEK] solution of VdF/HFP copolymer) was applied as an overcoat layer by dip coating, dried at 100° C. for 30 minutes, and then at 200° C. A test piece was obtained by firing for 30 minutes.
In accordance with JIS K5400, cellophane tape peeling of the coating film surface of the above test piece was repeated 10 times, and the mass number of the coating film remaining without peeling (in 100 masses) was determined.
The results are shown in Table 2.
上記で得た塗装板の塗膜上に、上塗り層としてフッ素ゴム塗料（ＶｄＦ／ＨＦＰ共重合体のメチルエチルケトン〔ＭＥＫ〕溶液）をディップ塗装して、１００℃で３０分乾燥した後に、２００℃で３０分焼成して試験片を得た。
ＪＩＳ Ｋ５４００に準拠して上記試験片の塗膜面のセロハンテープ剥離を１０回繰り返し、剥離せずに残存した塗膜のマス数（１００マス中）を求めた。
結果を表２に示す。 <Interlayer adhesion (against overcoat layer)>
On the coating film of the coated plate obtained above, a fluororubber paint (methyl ethyl ketone [MEK] solution of VdF/HFP copolymer) was applied as an overcoat layer by dip coating, dried at 100° C. for 30 minutes, and then at 200° C. A test piece was obtained by firing for 30 minutes.
In accordance with JIS K5400, cellophane tape peeling of the coating film surface of the above test piece was repeated 10 times, and the mass number of the coating film remaining without peeling (in 100 masses) was determined.
The results are shown in Table 2.
＜塗料安定性（ポットライフ、保管後の塗膜物性）＞
実施例及び比較例で得られたフッ素ゴム塗料組成物を２５℃で表３に示す時間保管した後、Ｂ型粘度計を用いて塗料粘度を測定した。
２５℃で２４時間保管したフッ素ゴム塗料組成物を用いて上記と同様に塗装板を作製し、塗膜物性（塗膜ヘタリ、シール性）を評価した。
結果を表３に示す。 <Paint stability (pot life, coating film properties after storage)>
The fluororubber coating compositions obtained in Examples and Comparative Examples were stored at 25° C. for the time shown in Table 3, and then the coating viscosity was measured using a B-type viscometer.
A coated plate was prepared in the same manner as above using the fluororubber coating composition stored at 25° C. for 24 hours, and the coating film physical properties (coating film settling and sealing properties) were evaluated.
The results are shown in Table 3.
実施例及び比較例で得られたフッ素ゴム塗料組成物を２５℃で表３に示す時間保管した後、Ｂ型粘度計を用いて塗料粘度を測定した。
２５℃で２４時間保管したフッ素ゴム塗料組成物を用いて上記と同様に塗装板を作製し、塗膜物性（塗膜ヘタリ、シール性）を評価した。
結果を表３に示す。 <Paint stability (pot life, coating film properties after storage)>
The fluororubber coating compositions obtained in Examples and Comparative Examples were stored at 25° C. for the time shown in Table 3, and then the coating viscosity was measured using a B-type viscometer.
A coated plate was prepared in the same manner as above using the fluororubber coating composition stored at 25° C. for 24 hours, and the coating film physical properties (coating film settling and sealing properties) were evaluated.
The results are shown in Table 3.
Claims (10)
- フッ素ゴム、ポリオール系加硫剤、アミノ基含有金属化合物及び有機溶剤を含み、
前記フッ素ゴム１００質量部に対し、前記ポリオール系加硫剤及び前記アミノ基含有金属化合物を合計で０．１～４．９９質量部含むことを特徴とするフッ素ゴム塗料組成物。 Includes fluororubber, polyol-based vulcanizing agent, amino group-containing metal compound and organic solvent,
A fluororubber coating composition comprising 100 parts by mass of the fluororubber and 0.1 to 4.99 parts by mass in total of the polyol-based vulcanizing agent and the amino group-containing metal compound. - 前記ポリオール系加硫剤と前記アミノ基含有金属化合物との質量比が１．０：０．１～１．０：１．２である請求項１記載のフッ素ゴム塗料組成物。 The fluororubber coating composition according to claim 1, wherein a mass ratio of the polyol-based vulcanizing agent and the amino group-containing metal compound is 1.0:0.1 to 1.0:1.2.
- 前記アミノ基含有金属化合物の金属が、Ｓｉ、Ａｌ、Ｔｉ及びＺｒ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記載のフッ素ゴム塗料組成物。 The fluororubber coating composition according to claim 1 or 2, wherein the metal of the amino group-containing metal compound is at least one selected from the group consisting of Si, Al, Ti and Zr.
- 前記フッ素ゴム１００質量部に対し、前記ポリオール系加硫剤が０．１～３質量部、前記アミノ基含有金属化合物が０．１～２質量部である請求項１～３のいずれかに記載のフッ素ゴム塗料組成物。 4. The polyol-based vulcanizing agent is 0.1 to 3 parts by mass, and the amino group-containing metal compound is 0.1 to 2 parts by mass, relative to 100 parts by mass of the fluororubber. Fluorine rubber coating composition.
- 更に、安定剤を含む請求項１～４のいずれかに記載のフッ素ゴム塗料組成物。 The fluororubber coating composition according to any one of claims 1 to 4, further comprising a stabilizer.
- 前記安定剤は、オルトエステル系化合物である請求項５記載のフッ素ゴム塗料組成物。 The fluororubber coating composition according to claim 5, wherein the stabilizer is an orthoester compound.
- 更に、表面調整剤を含む請求項１～６のいずれかに記載のフッ素ゴム塗料組成物。 The fluororubber coating composition according to any one of claims 1 to 6, further comprising a surface modifier.
- 更に、消泡剤を含む請求項１～７のいずれかに記載のフッ素ゴム塗料組成物。 The fluororubber coating composition according to any one of claims 1 to 7, further comprising an antifoaming agent.
- 金属板と、
前記金属板の片面又は両面に設けられた、請求項１～８のいずれかに記載のフッ素ゴム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,
A coated article, comprising a coating film formed from the fluororubber coating composition according to any one of claims 1 to 8 provided on one side or both sides of the metal plate. - フッ素ゴムコートガスケット材料である請求項９記載の塗装物品。 The coated article according to claim 9, which is a fluororubber-coated gasket material.
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| Application Number | Priority Date | Filing Date | Title |
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| KR1020217029595A KR20210126711A (en) | 2019-02-21 | 2020-02-21 | Fluoro rubber coating compositions and coating articles |
| CN202080014673.6A CN113490593A (en) | 2019-02-21 | 2020-02-21 | Fluororubber coating composition and coated article |
| JP2021502168A JPWO2020171193A1 (en) | 2019-02-21 | 2020-02-21 | Fluororubber paint composition and painted articles |
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| JP2019-029421 | 2019-02-21 |
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| PCT/JP2020/006979 WO2020171193A1 (en) | 2019-02-21 | 2020-02-21 | Fluorine rubber coating composition and coated article |
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| JP (1) | JPWO2020171193A1 (en) |
| KR (1) | KR20210126711A (en) |
| CN (1) | CN113490593A (en) |
| WO (1) | WO2020171193A1 (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10101985A (en) * | 1996-10-01 | 1998-04-21 | Nof Corp | Coating composition |
| JPH10324840A (en) * | 1997-05-26 | 1998-12-08 | Asahi Glass Co Ltd | Fluororubber coating composition |
| JP2001181551A (en) * | 1999-10-13 | 2001-07-03 | Toagosei Co Ltd | Fluorine coating composition and application method of this composition |
| JP2002012813A (en) * | 2000-06-30 | 2002-01-15 | Asahi Glass Co Ltd | Fluorine rubber coating material composition |
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|---|---|---|---|---|
| JPS5883066A (en) * | 1981-11-12 | 1983-05-18 | Daikin Ind Ltd | Non-tacky, electrically conductive fluororubber paint |
| JP3160395B2 (en) * | 1992-11-27 | 2001-04-25 | ダイネオン リミティド ライアビリティー カンパニー | Fluoro rubber coating composition |
| JPH0734025A (en) * | 1993-07-21 | 1995-02-03 | Asahi Glass Co Ltd | Fluororubber coating composition |
| JP3994493B2 (en) * | 1997-11-14 | 2007-10-17 | Ｂａｓｆコーティングスジャパン株式会社 | Coating composition, coating finishing method, and coated article |
| JP4081929B2 (en) * | 1998-08-04 | 2008-04-30 | Ｊｓｒ株式会社 | Photocurable resin composition and cured film |
| US6416819B1 (en) * | 2000-06-30 | 2002-07-09 | Nex Press Solutions Llc | Method of preparing low-temperature-cure polymer composition |
| JP2002338872A (en) * | 2001-05-11 | 2002-11-27 | Daikin Ind Ltd | Fluororubber coating composition |
| US7037966B2 (en) * | 2004-06-23 | 2006-05-02 | Arkema Inc. | Stain resistant coating |
| JP4759958B2 (en) | 2004-09-01 | 2011-08-31 | ダイキン工業株式会社 | Composition for fluororubber paint |
| US10584220B2 (en) * | 2016-02-26 | 2020-03-10 | Fina Technology, Inc. | Modified polymers and stable emulsions comprising the same |
-
2020
- 2020-02-21 CN CN202080014673.6A patent/CN113490593A/en active Pending
- 2020-02-21 KR KR1020217029595A patent/KR20210126711A/en not_active Application Discontinuation
- 2020-02-21 JP JP2021502168A patent/JPWO2020171193A1/en active Pending
- 2020-02-21 WO PCT/JP2020/006979 patent/WO2020171193A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10101985A (en) * | 1996-10-01 | 1998-04-21 | Nof Corp | Coating composition |
| JPH10324840A (en) * | 1997-05-26 | 1998-12-08 | Asahi Glass Co Ltd | Fluororubber coating composition |
| JP2001181551A (en) * | 1999-10-13 | 2001-07-03 | Toagosei Co Ltd | Fluorine coating composition and application method of this composition |
| JP2002012813A (en) * | 2000-06-30 | 2002-01-15 | Asahi Glass Co Ltd | Fluorine rubber coating material composition |
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| JPWO2020171193A1 (en) | 2021-12-09 |
| CN113490593A (en) | 2021-10-08 |
| KR20210126711A (en) | 2021-10-20 |
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