WO2014050722A1 - コーティング剤組成物 - Google Patents
コーティング剤組成物 Download PDFInfo
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- WO2014050722A1 WO2014050722A1 PCT/JP2013/075431 JP2013075431W WO2014050722A1 WO 2014050722 A1 WO2014050722 A1 WO 2014050722A1 JP 2013075431 W JP2013075431 W JP 2013075431W WO 2014050722 A1 WO2014050722 A1 WO 2014050722A1
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- Prior art keywords
- coating agent
- emulsion
- weight
- component
- resin emulsion
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of 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; Compositions of derivatives of such polymers
- C08L27/02—Compositions of 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/18—Homopolymers or copolymers or tetrafluoroethene
-
- 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
- C09D127/18—Homopolymers or copolymers of tetrafluoroethene
-
- 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
- C09D109/00—Coating compositions based on homopolymers or copolymers of conjugated diene hydrocarbons
- C09D109/02—Copolymers with acrylonitrile
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
- C09D5/022—Emulsions, e.g. oil in water
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers
- Y10T428/31544—Addition polymer is perhalogenated
Definitions
- the present invention relates to a coating agent composition. More specifically, the present invention relates to a coating agent composition that is effectively used as a surface coating agent for vulcanized rubber molded articles.
- Patent Document 1 discloses an electrophotographic apparatus in which an NCO-terminated polyurethane prepolymer obtained from polyolefin polyol, diisocyanate and glycol is chain-extended with water and at the same time a material mainly composed of a urethane resin emulsion obtained by dispersing in water. It has been proposed to be used as a coating agent for members.
- the coating agent comprising this urethane resin emulsion is used as a surface coating agent for general vulcanized rubber molded products, among various measurement items described in Examples below, bleeding evaluation (70 ° C., 30 days), according to a bending test
- bleeding evaluation 70 ° C., 30 days
- the evaluation of the flexibility of the coating agent and the evaluation of the adhesion to the vulcanized rubber by the adhesion test are satisfactory, the evaluation of the adhesion to the rubber by the bloom from the vulcanized rubber by the high-temperature humidification test can provide only an effect that is not satisfied at all. Not.
- Patent Document 2 on an organic resin-based undercoat layer, (a) an organosilane, its hydrolyzate or its condensate, (b) a silyl group-containing vinyl polymer or a silyl group and a UV-safe group-containing vinyl.
- An overcoating coating composition containing a polymer and (c) an organometallic compound that serves as a hydrolysis / condensation catalyst and having a specific (b) component / (a) component weight ratio is described.
- Patent Document 3 includes a combination of an acrylic resin emulsion A and a liquid B containing water-dispersible polyisocyanate as essential components.
- the liquid A contains a hydroxyl group-containing polymerizable monomer and a cycloalkyl group-containing polymerizable monomer.
- Patent Documents 2 to 3 when the coating composition of Patent Documents 2 to 3 is used as a surface coating agent for general vulcanized molded products, it is excellent in terms of evaluation of adhesion to vulcanized rubber by an adhesion test, The results are inferior in any of the other three evaluations: bleeding evaluation, flexibility evaluation of coating agent by bending test, and evaluation of adhesion loss to rubber by bloom from vulcanized rubber by high temperature humidification test. It was confirmed.
- JP 2002-188051 A JP 2003-26997 A Japanese Patent Laid-Open No. 2003-73611 JP-A-2-178305 JP-A-8-100085 Japanese Patent No. 3032210
- the object of the present invention is to use a coating composition as a surface coating agent for general vulcanized rubber molded articles, with little loss of adhesive evaluation with vulcanized rubber by adhesion test, bleeding evaluation, bending test. It is an object of the present invention to provide a coating composition that satisfies both of the evaluation of the flexibility of the coating agent according to the present invention and the evaluation of the decrease in adhesion to rubber due to the bloom from the vulcanized rubber by the high temperature humidification test.
- the object of the present invention is to provide a coating composition comprising (A) a polytetrafluoroethylene resin emulsion, (B) a urethane resin emulsion, and (C) a hydrogenated NBR emulsion, preferably (D) an acrylic resin emulsion. And / or a coating composition comprising an ethylene-vinyl acetate copolymer resin emulsion.
- the coating agent composition according to the present invention When the coating agent composition according to the present invention is used as a surface coating agent for a general vulcanized rubber molded article, the bleeding evaluation without substantially impairing the adhesion evaluation with the vulcanized rubber by the adhesion test, The effect of satisfying both the evaluation of the flexibility of the coating agent by the bending test and the evaluation of the adhesion to rubber by bloom from the vulcanized rubber by the high temperature humidification test is achieved.
- the coating agent composition of the present invention that exhibits such effects is not only a general vulcanized rubber molded product, for example, seal parts such as O-rings, oil seals, gaskets, diaphragms, valves, etc., but also rubber rolls and rubber belts for copying machines, industrial It is applied to rubber parts such as rubber hoses, rubber belts, wipers, weather strips for automobiles, glass runs, etc., and effectively acts to prevent adhesion, reduce friction, and wear.
- seal parts such as O-rings, oil seals, gaskets, diaphragms, valves, etc.
- rubber rolls and rubber belts for copying machines
- rubber parts such as rubber hoses, rubber belts, wipers, weather strips for automobiles, glass runs, etc.
- PTFE polytetrafluoroethylene resin
- component (A) not only a homopolymer of tetrafluoroethylene [TFE], but also a small amount (less than several mol%) of perfluoroalkyl vinyl ether with TFE, hexafluoropropylene, a copolymer of ethylene such as, the number average molecular weight Mn (J. of Applied polymer Science Vol. 17, No. 3253-7, pp, measured by the method described 1973) is preferably 2 ⁇ 10 4 Those of ⁇ 1 ⁇ 10 7 , more preferably 2 ⁇ 10 5 to 8 ⁇ 10 6 are used.
- PTFE having an average particle diameter (measured by a light scattering method) of about 200 to 500 nm, preferably about 200 to 400 nm is used. If the average particle size is less than 200 nm, the particles are likely to aggregate and cause roughness on the coated surface. On the other hand, if the average particle size exceeds 500 nm, the particles are likely to settle and the stability of the aqueous emulsion decreases.
- PTFE is generally obtained by an emulsion polymerization method, and the obtained aqueous dispersion is added with a surfactant necessary for stabilization as necessary, and concentrated and stabilized.
- PTFE is particulate and because of its non-adhesive properties and low friction properties, and because PTFE has a large molecular weight and small particles, it can delay bloom shielding and bloom formation on the vulcanized rubber surface. , PTFE emulsion achieves low friction, reduced adhesion to seal material, and suppression of bloom on the vulcanized rubber surface.
- PTFE is used in a proportion that occupies about 20 to 80% by weight, preferably about 30 to 70% by weight in the total solid content.
- the ratio of the PTFE solid content is lower than this, the coefficient of friction becomes high and it becomes easy to stick, and the bloom from the vulcanized rubber cannot be shielded.
- the PTFE solid content is higher than this, not only the adhesion and flexibility with the rubber will deteriorate, but also PTFE agglomerates will occur on the coated surface, increasing the surface roughness and sealing. In the case of parts, the sealing performance is lowered. In addition, the aggregates fall off and become impurities.
- PTFE emulsion commercially available products such as Daikin product polyflon dispersion D-1 E, Asahi Glass product full-on PTFE AD911E, etc. can be used as they are or appropriately diluted.
- urethane resin emulsion of component (B) a one-component emulsion in which a urethane prepolymer obtained by reaction of a compound having two or more active hydrogen atoms and an organic polyisocyanate is dispersed in water, for example, Patent Document 1 Those described are used.
- the compound having two or more active hydrogen atoms as described above is a polyether, polyester, polyether ester, polythioether, having two or more hydroxyl groups, carboxyl groups, amino groups, mercapto groups, etc.
- a chain extender may be blended with the compound having two or more active hydrogen atoms, if necessary.
- polyester polyol having two or more hydroxyl groups in the molecule include adipic acid, sebacic acid, itaconic acid, maleic anhydride, terephthalic acid, isophthalic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, glutaric acid.
- polyol compounds such as neopentyl glycol, 1,9-nonanediol, 3-methyl-1,5-pentadiol, tripropylene glycol, trimethyl
- organic polyisocyanate conventionally used chain or alicyclic aliphatic or aromatic organic polyisocyanates can be used, for example, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate.
- 2,2,4-trimethylhexamethylene diisocyanate 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, dicyclohexylmethane-4,4'-diisocyanate, methylcyclohexyl-2,4-diisocyanate, methylcyclohexyl-2 , 6-diisocyanate, 1,3-bis (isocyanate) methylcyclohexane, transcyclohexane-1,4-diisocyanate, lysine diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, etc.
- Aliphatic diisocyanates such as alicyclic diisocyanates; tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, 2,4-toluylene diisocyanate, 2,6-toluylene diisocyanate, diphenylmethane-4,4'-diisocyanate ,
- Aromatic diisocyanates such as naphthalene diisocyanate, 1,5'-naphthene diisocyanate, tolidine diisocyanate, tetraalkyldiphenylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, 1,3-phenylene diisocyanate; lysine ester triisocyanate, triphenylmethane Triisocyanate, 1,6,11-undecane triisocyanate, 1,8-isocyanate-4,4-isocyanate methyl
- Each of these monomers is reacted in the presence of a hydrophilic volatile solvent such as acetone or methyl ethyl ketone to synthesize a polyurethane resin, and then the acetone method, prepolymer mixing method, ketimine method, hot melt dispersion method, etc. It can be converted into a urethane resin emulsion by a known method.
- a hydrophilic volatile solvent such as acetone or methyl ethyl ketone
- a reaction control agent such as phosphoric acid or benzoyl chloride, a reaction catalyst such as dibutyltin dilaurate, stannous octoate, triethylamine, or an organic solvent that does not react with isocyanate groups is added during or after the reaction. May be.
- the organic solvent include acetone, methyl ethyl ketone, tetrahydrofuran, dioxane, ethyl acetate, toluene, xylene and the like.
- stabilizers such as an antioxidant and an ultraviolet absorber can be added during the reaction or after the reaction is completed.
- the method of dispersing in water is not particularly limited, and can be performed by a conventionally known method.
- a method of dispersing while adding water to the organic phase while applying mechanical shearing force with a high-speed disperser such as a homomixer or a disper, or a method of adding the organic phase into the aqueous phase may be adopted. It can.
- a mechanical dispersion method dispersion dispersion can be eliminated.
- dispersing in water When dispersing in water, it may be performed in a batch system, or in a continuous system such as a rotor / stator system, a line mill system, a static mixer system, a vibration system, an ultrasonic system, or a high pressure system. Further, in any of the batch type or continuous type dispersion methods, dispersion may be performed by connecting two or more kinds of facilities.
- the dispersion apparatus an apparatus having one dispersion part for dispersing an object to be dispersed in water is used, but an apparatus having two or more dispersion parts may be used.
- the urethane resin used in the form of an emulsion is used in a ratio of about 10 to 50% by weight, preferably about 15 to 40% by weight, based on the total solid content.
- the urethane resin is used in a proportion higher than this, the friction coefficient becomes high and the adhesive becomes easy.
- a urethane resin is used in a proportion smaller than this, the adhesiveness and flexibility with the vulcanized rubber are lowered.
- urethane resin emulsion commercially available products such as Ube Industries UW-1005E, Sanyo Kasei Ucoat UWS-145, etc. can be used as they are or after being appropriately diluted.
- An emulsion obtained by a method of hydrogenating 50 to 99.95% (Patent Documents 4 to 5) or the like is used.
- Hydrogenated NBR emulsion increases the coefficient of friction and increases the adhesion to seal materials, but also improves the water resistance, flexibility, and adhesion to vulcanized rubber of urethane resins.
- hydrogenated NBR used in the form of an emulsion is used in a ratio of about 3 to 50% by weight, preferably about 5 to 40% by weight, based on the total solid content.
- adhesion to the vulcanized rubber molded product, flexibility, water resistance, etc. tend to be deteriorated.
- the coefficient is high and not only is easy to stick, but also sticks when the substrates come into contact with each other during application.
- NBR emulsion that is not hydrogenated When NBR emulsion that is not hydrogenated is used, the water resistance is improved, but the tackiness is higher than when hydrogenated NBR emulsion is used, and the film strength is insufficient. Will occur.
- hydrogenated NBR emulsion As the hydrogenated NBR emulsion, commercially available products such as Nippon Zeon products ZLxB and ZLxA can be used as they are or after being appropriately diluted.
- component PTFE component PTFE emulsion
- component urethane resin emulsion component urethane resin emulsion
- component hydrogenated NBR emulsion acrylic resin emulsion
- EVA ethylene-vinyl acetate copolymer resin
- the acrylic resin that forms the acrylic resin emulsion of component (D) is a homopolymer or copolymer of an alkyl ester of acrylic acid or methacrylic acid, and the homopolymer has a glass transition temperature of -20 ° C or lower. Those having a glass transition temperature of ⁇ 30 ° C. or lower are described in Patent Document 6, for example. The lower the glass transition temperature, the less sticky, the harder and the lower the friction. On the other hand, if a glass transition temperature higher than this is used, there will be adhesion, the strength will decrease, and the friction coefficient will increase.
- a polymer of an alkyl ester of methacrylic acid is used.
- the alkyl group of the (meth) acrylic acid ester include C 2 to C 16 , preferably C 2 to C 12 linear or branched alkyl groups.
- the acrylic resin used in the form of an emulsion is used in a proportion of 0 to 50% by weight, preferably about 5 to 30% by weight, based on the total solid content. Addition of acrylic resin emulsion lowers the coefficient of friction and makes it difficult to stick to the seal partner, but if acrylic resin is used in a proportion higher than this, the adhesiveness and flexibility with vulcanized rubber will decrease. Become.
- acrylic resin emulsion commercially available products such as Nippon Carbide products Nicazole FX-329 and RX-66E can be used as they are or after being appropriately diluted.
- EVA used in the form of an emulsion is used in a proportion of 0 to 50% by weight, preferably about 5 to 40% by weight, based on the total solid content. Addition of EVA emulsion improves adhesion with vulcanized rubber and improves flexibility. However, if EVA is used at a rate higher than this, the coefficient of friction is increased, the adhesion to the seal partner material is increased, and adhesion becomes easier when the substrates come into contact with each other during application.
- EVA emulsion commercially available products such as Nippon Carbide product Nicazole ME-702XT, Denka EVA product 80 Denka EVA tex 80, etc. can be used as they are or after being appropriately diluted.
- the coating agent composition is prepared by mixing each of the above emulsions. Preferably, the respective components are charged into the container in the following order, and the solid content concentration is about 5 to 50% by weight, preferably about Prepared as 10-40 wt% coating agent.
- Ethylene-vinyl acetate copolymer resin [EVA] emulsion ii) Water (iii) Hydrogenated NBR emulsion, acrylic resin emulsion (iv) Urethane resin emulsion (v) PTFE emulsion
- Coating of the vulcanized rubber molded product with the coating agent composition is performed by a commonly used coating method such as a spray method or a dipping method.
- the type of rubber of the vulcanized rubber molded article to be coated is not particularly limited, and can be applied to vulcanized molded articles such as NBR, hydrogenated NBR, acrylic rubber, and fluororubber.
- Examples 1-5, Comparative Examples 1-5 (1) In a container equipped with a stirring device such as a rotor or propeller, (i) Ethylene-vinyl acetate copolymer resin [EVA] emulsion (ii) Water (iii) Hydrogenated NBR emulsion, Acrylic resin emulsion (iv) Urethane resin emulsion (v) Add each component in the order of PTFE emulsion The mixture was stirred until it became homogeneous to prepare a coating agent having a solid content of 30% by weight.
- EVA Ethylene-vinyl acetate copolymer resin
- PTFE emulsion Daikin polyflon dispersion D-1 E Solid content 61% by weight, Mn6,000,000, average particle size 220 nm
- Urethane resin emulsion Ube Industries UW-1005E Solid content concentration 27.4% by weight
- Hydrogenated NBR emulsion Nippon Zeon product ZLxB Solid concentration 40.5% by weight
- Acrylic resin emulsion Nippon Carbide product Nicazole FX-329 Solid concentration 45% by weight
- NBR Emulsion Nippon Zeon product Nipol 1562 Solid content 41% by weight
- NBR JSR product JSR N220S
- Carbon black Shin Nikka Carbon product HTC # S ⁇ S
- Zinc Hana No.3 Zinc Hana No.3 (Shodo Chemical Industry Product) 5 ⁇ Stearic acid (Miyoshi oil and fat products) 2 ⁇ Anti-aging agent (Seiko Chemical Product Santite R) 3 ⁇ Anti-aging agent (Ouchi Shinsei Chemical 6C) 2 ⁇ Plasticizer (ADEKA product RS-107) 15 ⁇ Sulfur (Hosoi Chemical products) 1.2 ⁇ Vulcanization accelerator (Ouchi Emerging Chemical Industry Noxeller TT) 2) Vulcanization accelerator (Ouchi Emerging Chemical Industry Noxeller CZ) 2.5 ⁇
- Each of the above components was kneaded using a roll, and then press vulcanized at 180 ° C. for 6 minutes to vulcanize and mold a 2 mm thick sheet and an O-ring.
- Haydon Tribogear used Coefficient of friction of coated rubber sheet surface measured under the following test conditions
- Partner SUS304 steel ball with a diameter of 10 mm Movement speed: 50mm / min Load: 0.49N Amplitude: 50mm Bending test: JIS K5600-5-1 (1999), ISO 1519 (1973) compliant
- the coated rubber sheet is bent into a 6 mm diameter mandrel, and in the bent state, the tape is peeled in the same way as the Gobang eye test. According to the following evaluation criteria, whether or not the coating agent was peeled was evaluated, in other words, the flexibility of the coating agent was evaluated.
- the presence or absence of transfer of the coating agent to the metal was evaluated as a metal adhesion test according to the following evaluation criteria: ⁇ : No transfer of coating agent to SUS430 ⁇ : Partial transfer of coating agent to SUS430 ⁇ : After release, the entire compression surface is transferred to SUS430. Note) When the adhesion between the vulcanized rubber and the coating agent is weak, when the adhesiveness decreases due to bloom from the vulcanized rubber, or when the coating agent sticks. The coating material is transferred to the metal side of the mating material.
- High-temperature humidification test Compatible with ASTM D395 Adhesion test and water resistance test with vulcanized rubber compliant with JIS K6262 (2006) Vulcanized O-ring (inner diameter 34.7 mm, thickness 3.5 mm) was coated in the same manner as above, and 2 O-rings Compressed under the conditions of compression rate 20%, temperature 60 ° C, humidity 90% RH, time 70 hours, and evaluated the peeling condition of the coating agent between the O-rings according to the following criteria after the compression test ⁇ : There is no peeling of the coating agent. ⁇ : Some peeling occurs on the coating agent on the O-ring compression surface. ⁇ : Peeling occurs on almost the entire surface of the coating agent on the O-ring compression surface.
- ⁇ Transport is faster than when the silicone oil is applied without coating. Although the speed is high, there is an O-ring that is being transported in a state where two or more O-rings overlap each other. Note) If silicone oil is applied to vulcanized rubber that is not coated, the transfer will be slow due to the stickiness of silicone oil, and the blocked O-ring will remain on the parts feeder. The lower the dynamic friction coefficient, the higher the transport speed.
- O-ring leak test V-shaped O-ring (inner diameter 119.6 mm, thickness 7 mm) ; No. P120) was coated in the same manner as above, the O-ring was compressed 5%, and the leak amount after 3 minutes of He gas injection was measured using a helium leak detector, and evaluated according to the following criteria: : Less leak ⁇ : More leak
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Abstract
Description
(i) エチレン-酢酸ビニル共重合体樹脂〔EVA〕エマルジョン
(ii) 水
(iii) 水素化NBRエマルジョン、アクリル樹脂エマルジョン
(iv) ウレタン樹脂エマルジョン
(v) PTFEエマルジョン
(1) ロータやプロペラ等の攪拌装置を備えた容器中に、
(i) エチレン-酢酸ビニル共重合体樹脂〔EVA〕エマルジョン
(ii) 水
(iii) 水素化NBRエマルジョン、アクリル樹脂エマルジョン
(iv) ウレタン樹脂エマルジョン
(v) PTFEエマルジョン
の順番で各配合成分を投入し、均一になる迄攪拌し、固形分濃度30重量%のコーティング剤を調製した。
ここでは、次のよう市販品が各配合成分として用いられた。
PTFEエマルジョン:ダイキン製品ポリフロンディスパージョンD-1 E
固形分濃度61重量%、Mn6,000,000、平均粒子径220
nm
ウレタン樹脂エマルジョン:宇部興産製品 UW-1005E
固形分濃度27.4重量%
水素化NBRエマルジョン:日本ゼオン製品ZLxB
固形分濃度40.5重量%
アクリル樹脂エマルジョン:日本カーバイド製品ニカゾールFX-329
固形分濃度45重量%
エチレン-酢酸ビニル共重合体樹脂エマルジョン
〔EVAエマルジョン〕:日本カーバイド製品ニカゾールME-702XT
固形分濃度56重量%
NBRエマルジョン:日本ゼオン製品Nipol 1562
固形分濃度41重量%
カーボンブラック(新日化カーボン製品HTC#S・S) 40 〃
亜鉛華3号(正同化学工業製品) 5 〃
ステアリン酸(ミヨシ油脂製品) 2 〃
老化防止剤(精工化学製品サンタイトR) 3 〃
老化防止剤(大内新興化学工業製品6C) 2 〃
可塑剤(ADEKA製品RS-107) 15 〃
硫黄(細井化学製品) 1.2 〃
加硫促進剤(大内新興化学工業製品ノクセラーTT) 2 〃
加硫促進剤(大内新興化学工業製品ノクセラーCZ) 2.5 〃
以上の各成分をロールを用いて混練した後、180℃、6分間のプレス加硫を行い、厚さ2mmのシートおよびOリングを加硫成形した。
動摩擦係数:ASTM D-1894(-11el)、JIS K7125(1999年)、JIS P8147
(2010年)、ISO 8295(1995年)準拠
新東化学製表面性試験機ヘイドン・トライボギア使用
コーティングしたゴムシート表面の動摩擦係数を次の試
験条件下で測定
相手材:直径10mmのSUS304鋼球
移動速度:50mm/分
荷重:0.49N
振幅:50mm
屈曲試験:JIS K5600-5-1(1999年)、ISO 1519(1973年)準拠
コーティング処理したゴムシートを直径6mmのマンドレル
に屈曲させ、屈曲した状態でゴバン目試験と同様のテープ
剥離を行い、次の評価基準に従って、コーティング剤が剥
離したか否か、換言すればコーティング剤の柔軟性を評価
した
○:屈曲部の剥がれやテープへの転写なし
×:屈曲部の剥がれやテープへの転写あり
粘着試験:コーティング処理したゴムシートを直径13mmの円板状に打
ち抜き、室温条件下に1週間放置した後、相手材SUS430、
圧縮率33.3%でコーティング層同士が対向するように挟み
込み、100℃で60分間加熱した後室温条件下に1時間放置し
てから、圧縮型から解放し、コーティング剤がSUS430に粘
着することによるコーティング剤の金属への転写の有無を
次の評価基準に従い、金属との粘着試験として評価した
○:SUS430に対してコーティング剤の転写がない
△:SUS430に対してコーティング剤が一部転写
×:離型後コーティング剤がSUS430に圧縮面全面が
転写
注)加硫ゴムとコーティング剤との接着が弱い場合、加
硫ゴムからのブルームにより接着性が低下した場合
、コーティング剤が粘着する場合などには、相手材
金属側にコーティング剤が転写する
高温加湿試験:ASTM D395に対応するJIS K6262(2006年)準拠した加硫
ゴムとの粘着試験および耐水試験
加硫成形したOリング(内径34.7mm、太さ3.5mm)に、上
記と同様にしてコーティングを施し、Oリング2個を重
ねて、圧縮率20%、温度60℃、湿度90%RH、時間70時
間の条件下で圧縮し、圧縮試験後にOリング間のコー
ティング剤の剥がれ状態を、次の基準によって評価し
た
○:コーティング剤の剥がれがない
△:Oリング圧縮面のコーティング剤に一部の剥
がれが発生
×:Oリング圧縮面のコーティング剤のほぼ全面
に剥がれが発生
注)Oリング同士の圧縮面端部に水が存在したり、Oリン
グ同士の粘着、ウレタン樹脂の加水分解、ウレタン
樹脂と加硫ゴムとの接着性の低下などにより剥がれ
が発生する
ブリーディング評価:シートについて70℃、30日間の加熱試験を行い
、コーティング表面に加硫ゴムからのブルーム
成分が析出しているかどうかを目視によって観
察し、次の基準によって評価した
○:表面への固形物の析出が判断できない
×:表面への固形物の析出が判断できる
Oリングの搬送特性評価:加硫成形したOリング(内径7.8mm、太さ1.9
mm;呼び番号ASTM D2240およびD1414に対応
するJIS B2401-4種D P8)に上記と同様にし
てコーティングを施し、パーツフィーダに
よるOリングの搬送特性を、次の基準によっ
て評価した
○:Oリング同士が重なった状態での搬
送は起こらず、コーティング処理を
せずにシリコーンオイルを塗布した
ものよりも搬送速度が速い
△:コーティング処理をせずにシリコー
ンオイルを塗布したものよりも搬送
速度は速いが、Oリング同士が2個以
上重なった状態で搬送しているOリ
ングが存在する
×:コーティング処理をせずにシリコー
ンオイルを塗布したものと同等また
はそれよりも遅い
注)コーティングしない加硫ゴムにシリ
コーンオイルを塗布して搬送すると
、シリコーンオイルのベトツキで搬
送が遅くなり、またブロッキングし
たOリングはパーツフィーダ上に残
る
粘着せず、動摩擦係数が低い程、搬
送速度は速くなる
Oリングのリーク試験:加硫成形したOリング(内径119.6mm、太さ7mm
;呼び番号P120)に、上記と同様にコーティン
グを施し、Oリングを5%圧縮し、ヘリウムリ
ークディテクタを用いて、Heガス投入3分後の
漏れ量を測定し、次の基準によって評価した
○:漏れが少ない
×:漏れが多い
表1(実施例)
1 2 3 4 5
〔コーティング剤成分〕
PTFEエマルジョン 98.3 108.2 108.2 98.4 65.6
(60%) (66%) (66%) (60%) (40%)
ウレタン樹脂エマルジョン 87.6 73.0 73.0 69.3 109.5
(24%) (20%) (20%) (19%) (30%)
水素化NBRエマルジョン 39.5 17.3 17.1 17.3 29.6
(16%) ( 7%) ( 7%) ( 7%) (12%)
アクリル樹脂エマルジョン - 15.6 - 15.5 40.0
( 7%) ( 7%) (18%)
EVAエマルジョン - - 12.5 12.5 -
( 7%) ( 7%)
蒸留水 101.1 119.3 119.6 117.5 88.6
〔測定・評価結果〕
動摩擦係数 0.5 0.3 0.3 0.3 0.5
屈曲試験 ○ ○ ○ ○ ○
粘着試験 △ ○ △ ○ △
高温加湿試験 △ △ ○ ○ ○
ブリーディング評価 ○ ○ ○ ○ ○
Oリング搬送特性評価 △ ○ ○ ○ ○
Oリングリーク試験 ○ ○ ○ ○ ○
表2(比較例)
1 2 3 4 5
〔コーティング剤成分〕
PTFEエマルジョン 108.2 108.2 - - 98.3
(60%) (66%) (60%)
ウレタン樹脂エマルジョン - 146.0 273.7 182.5 87.6
(40%) (75%) (50%) (24%)
水素化NBRエマルジョン - - 61.7 - 39.5
(25%) (16%)
NBRエマルジョン - - - - 39.5
(16%)
アクリル樹脂エマルジョン 37.8 - - 111.1 -
(17%) (50%)
EVAエマルジョン 30.3 - - - -
(17%)
蒸留水 150.4 99.1 - 39.7 101.1
〔測定・評価結果〕
動摩擦係数 0.5 0.4 1.0 0.5 0.7
屈曲試験 ○ ○ ○ × ○
粘着試験 × △ × △ ×
高温加湿試験 × × × × ×
ブリーディング評価 ○ ○ × × ○
Oリング搬送特性評価 ○ ○ × ○ ○
Oリングリーク試験 ○ ○ ○ ○ ○
Claims (8)
- (A)ポリテトラフルオロエチレン樹脂エマルジョン、(B)ウレタン樹脂エマルジョンおよび(C)水素化NBRエマルジョンを含有してなるコーティング剤組成物。
- さらに、(D)アクリル樹脂エマルジョンおよび/またはエチレン-酢酸ビニル共重合体樹脂エマルジョンを含有せしめた請求項1記載のコーティング剤組成物。
- 樹脂固形分として、(A)成分20~80重量%、(B)成分10~50重量%、(C)成分3~50重量%および(D)成分0~50重量%の割合で含有してなる請求項1または2記載のコーティング剤組成物。
- 樹脂固形分として、(A)成分30~70重量%、(B)成分15~40重量%、(C)成分5~40重量%および(D)成分5~30重量%の割合で含有してなる請求項1または2記載のコーティング剤組成物。
- 数平均分子量Mnが2×104~1×107で、平均粒子径が200~500nmのポリテトラフルオロエチレン樹脂粒子が(A)成分エマルジョン形成に用いられた請求項1または2記載のコーティング剤組成物。
- 加硫ゴム成形品の表面コーティング剤として用いられる請求項1または2記載のコーティング剤組成物。
- NBR、水素化NBR、アクリルゴムまたはフッ素ゴムの加硫ゴム成形品の表面コーティング剤として用いられる請求項6記載のコーティング剤組成物。
- 請求項6記載のコーティング剤組成物で表面をコーティングした加硫ゴム成形品。
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JP2014538454A JP5979236B2 (ja) | 2012-09-25 | 2013-09-20 | コーティング剤組成物 |
EP13841826.4A EP2902457B1 (en) | 2012-09-25 | 2013-09-20 | Coating agent composition |
CN201380049941.8A CN104640945B (zh) | 2012-09-25 | 2013-09-20 | 涂布剂组合物 |
US14/430,527 US9828497B2 (en) | 2012-09-25 | 2013-09-20 | Coating agent composition |
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EP (1) | EP2902457B1 (ja) |
JP (1) | JP5979236B2 (ja) |
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WO (1) | WO2014050722A1 (ja) |
Cited By (3)
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WO2016052702A1 (ja) * | 2014-10-01 | 2016-04-07 | Nok株式会社 | コーティング剤水性分散液 |
EP3199583A4 (en) * | 2014-09-22 | 2018-05-09 | NOK Corporation | Surface treatment agent for vulcanized rubber |
WO2018105531A1 (ja) * | 2016-12-06 | 2018-06-14 | ニチアス株式会社 | ゴム被覆シリンダヘッドガスケット用コーティング剤及びシリンダヘッドガスケット |
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CN112592649A (zh) * | 2020-12-02 | 2021-04-02 | 安徽凯瑞捷成新材料科技有限公司 | 一种汽车橡胶密封件耐溶剂 |
CN112608666A (zh) * | 2020-12-02 | 2021-04-06 | 安徽凯瑞捷成新材料科技有限公司 | 一种油田用耐油、耐磨、耐腐蚀密封圈涂层的生产工艺 |
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Also Published As
Publication number | Publication date |
---|---|
JPWO2014050722A1 (ja) | 2016-08-22 |
EP2902457B1 (en) | 2018-11-14 |
US20150252181A1 (en) | 2015-09-10 |
JP5979236B2 (ja) | 2016-08-24 |
CN104640945A (zh) | 2015-05-20 |
EP2902457A4 (en) | 2016-08-31 |
EP2902457A1 (en) | 2015-08-05 |
US9828497B2 (en) | 2017-11-28 |
CN104640945B (zh) | 2018-12-04 |
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