WO2019208665A1 - Feuille à surface modifiée, élément à surface modifiée, article revêtu, article imprimé, corps assemblé et procédé de fabrication d'élément à surface modifiée - Google Patents

Feuille à surface modifiée, élément à surface modifiée, article revêtu, article imprimé, corps assemblé et procédé de fabrication d'élément à surface modifiée Download PDF

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Publication number
WO2019208665A1
WO2019208665A1 PCT/JP2019/017524 JP2019017524W WO2019208665A1 WO 2019208665 A1 WO2019208665 A1 WO 2019208665A1 JP 2019017524 W JP2019017524 W JP 2019017524W WO 2019208665 A1 WO2019208665 A1 WO 2019208665A1
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Prior art keywords
thermosetting resin
modified
resin
component
layer
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PCT/JP2019/017524
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English (en)
Japanese (ja)
Inventor
陽介 巻幡
明日香 遠藤
絵里子 中尾
岡田　研一
郁佳 川竹
直幸 西山
佳世 下川
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日東電工株式会社
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Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to US17/050,569 priority Critical patent/US20210238454A1/en
Priority to KR1020207030705A priority patent/KR20210005869A/ko
Priority to CN201980028024.9A priority patent/CN112004668A/zh
Priority to EP19793788.1A priority patent/EP3785899A4/fr
Priority claimed from JP2019082960A external-priority patent/JP2019194015A/ja
Publication of WO2019208665A1 publication Critical patent/WO2019208665A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/052—Forming heat-sealable coatings
    • 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
    • B32B25/20—Layered products comprising a layer of natural or synthetic rubber comprising silicone rubber
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers

Definitions

  • the present invention relates to a surface modified sheet, a surface modified member, a coated product, a printed material, a joined body, and a method for producing the surface modified member.
  • thermosetting resins that are lightweight and have excellent impact resistance have been used for members such as railway vehicles, aircraft, ships, automobiles, and other transportation equipment, electronic equipment, and housing equipment.
  • the adherend is joined.
  • thermosetting resin In order to firmly bond the adherend to the thermosetting resin, the surface of the thermosetting resin is applied with a primer layer, pre-heating treatment, corona discharge treatment, electron irradiation treatment, ultraviolet irradiation treatment, flame plasma treatment, Pretreatment such as atmospheric pressure plasma treatment or low pressure plasma treatment is performed.
  • silicone-based adhesives and pressure-sensitive adhesive tapes are used for bonding an adherend to a nonpolar thermosetting elastomer such as silicone rubber.
  • a nonpolar thermosetting elastomer such as silicone rubber.
  • the adhesive strength is insufficient for bonding with a silicone-based pressure-sensitive adhesive. Therefore, silane coupling agents and condensates thereof, reaction products thereof, and organic titanium compounds such as alkoxy titanium and titanate coupling agents are known as primer compositions used for silicone rubber.
  • Patent Document 1 describes an adhesive silicone composition containing an organosilicon compound having a specific structure and an organotitanium compound, which is used for adhesion of materials other than silicone rubber and silicone rubber.
  • Patent Document 2 is mainly composed of a saturated hydrocarbon polymer having a reactive silicon group and excellent adhesion on a base material surface such as glass or metal and a joint surface with a pre-sealing sealant such as silicone rubber.
  • the primer composition applied to the sealing material and the adhesion method are described.
  • Patent Document 3 describes a primer composition containing an organic titanium compound and a solvent, which is used for adhesion between silicone rubber and various adherends.
  • thermosetting resin in order to perform pretreatment before bonding the adherend to the surface of the thermosetting resin, or before coating or printing, a step of removing the release agent used at the time of molding is required. In addition, pretreatment and the like are also required before forming the primer layer. Further, it is difficult to bond a low polarity resin and a polar resin, or a thermosetting resin and a thermoplastic resin even when a primer layer is used. In addition, since the coated surface and the printed surface need to be uniformly formed on the surface of the thermosetting resin, it is required that the primer layer be uniformly formed on the surface of the thermosetting resin. .
  • the present invention is excellent in adhesive force, can form a surface modified layer (primer layer) without unevenness, and the surface modified layer and the thermosetting resin are formed during the formation of the surface modified member.
  • An object of the present invention is to provide a surface-modified sheet that can be integrally formed with the sheet.
  • Another object of the present invention is to provide a surface modified member, a coated product, a printed product, a bonded body, and a method for producing the surface modified member using the surface modified sheet.
  • the present inventor has intensively studied to solve the above problems.
  • the surface-modified layer is formed into a sheet shape and contains a component that reacts with the thermosetting resin, so that sufficient adhesion can be obtained when joining the low-polarity resin and the polar resin or between the thermosetting resin and the thermoplastic resin. It has been demonstrated that the surface modified layer can be formed uniformly in any location, and the present invention has been completed.
  • One aspect of the present invention relates to a surface modified sheet comprising a release sheet and a surface modified layer, wherein the surface modified layer contains a component that reacts with a thermosetting resin.
  • the surface-modified sheet includes a component that reacts with the thermosetting resin, a polymer component including a curing agent, a group having a reactive unsaturated bond, or a reactive unsaturated component. It may contain at least one of a mixture of a polymer component not containing a group having a bond and a peroxide.
  • the thermosetting resin in the surface modified sheet, may be a thermosetting elastomer.
  • the thermosetting resin in the surface modified sheet, may be a non-diene rubber that does not contain a double bond.
  • the thermosetting resin in the surface modified sheet, may be a silicone resin or a silicone rubber.
  • One aspect of the present invention is a surface modification member in which a surface modification layer is laminated on the surface of a thermosetting resin, and the surface modification layer contains a component that reacts with the thermosetting resin, It is a surface modification member in which the thermosetting resin and the surface modification layer are bonded by a chemical reaction.
  • the surface modifying member is a polymer component in which the component that reacts with the thermosetting resin includes a curing agent, a reactive group having an unsaturated bond, or a reactive unsaturated bond. It may contain at least one of a mixture of a polymer component not containing a group having a hydrogen peroxide and a peroxide.
  • the thermosetting resin in the surface modifying member, may be a thermosetting elastomer.
  • the surface-modifying member may be a non-diene rubber in which the thermosetting resin does not contain a double bond.
  • the thermosetting resin may be a silicone resin or a silicone rubber.
  • One aspect of the present invention is a coated article having a coating film on at least a part of the surface of the surface modifying member on the surface modifying layer side.
  • One embodiment of the present invention is a printed matter obtained by printing on at least a part of the surface of the surface modifying member on the surface modifying layer side.
  • One embodiment of the present invention is a joined body in which an article is joined to at least a part of the surface of the surface modifying member on the surface modifying layer side using an adhesive.
  • One aspect of the present invention is a method for producing a surface modified member molded using the surface modified sheet and the thermosetting resin, wherein the thermosetting is performed during the molding step of the surface modified member. It is a manufacturing method of the surface modification member which provides the surface modification layer in at least a part of the surface of resin.
  • the thermosetting resin in the method for producing a surface modifying member, is an uncured thermosetting resin,
  • the component that reacts with the thermosetting resin is a mixture of a polymer component and a peroxide that does not include a reactive unsaturated group, or a polymer component that includes a reactive unsaturated bond group. It is preferable to include.
  • the thermosetting resin in the method for producing the surface modifying member, is a cured thermosetting resin
  • the component that reacts with the thermosetting resin includes a mixture of a polymer component and a peroxide that do not include a reactive unsaturated group, or a group that includes a curing agent and a reactive unsaturated bond. It preferably contains a polymer component.
  • the thermosetting resin in the method for producing the surface modifying member, may be a thermosetting elastomer.
  • the thermosetting resin in the method for producing the surface modifying member, may be a non-diene rubber that does not contain a double bond.
  • the thermosetting resin in the method for producing the surface modifying member, may be a silicone resin or a silicone rubber.
  • the surface-modified sheet according to one embodiment of the present invention is excellent in adhesive strength with a thermosetting resin and can form a surface-modified layer without unevenness. Further, it is possible to provide a surface modified sheet that can be integrally formed with the surface modified layer and the thermosetting resin when the surface modified member is formed.
  • thermosetting resin means at least part of all the surfaces of the thermosetting resin.
  • thermosetting resin is plate-shaped, sheet-shaped, or film-shaped, it means a part of at least one surface, the whole of at least one surface, or the like.
  • a surface modified sheet according to an embodiment of the present invention includes a release sheet and a surface modified layer, and the surface modified layer contains a component that reacts with a thermosetting resin.
  • the surface-modified sheet in the embodiment of the present invention can be formed into a laminated body or integrally formed by being loaded instead of being coated on the surface of a member or the like because the surface-modified layer is in a sheet form. Therefore, it is possible to prevent the occurrence of unevenness due to the occurrence of repelling or the like and to form the surface modified layer with a uniform thickness on the surface of the member or the like. Further, when the surface modification layer is applied to a part of the surface of the member, it is possible to suppress the yield from being lowered due to protrusion or the like.
  • the surface modification layer in the embodiment of the present invention contains a component that reacts with the thermosetting resin.
  • the surface modified layer contains a component that reacts with the thermosetting resin, when used for a member containing the thermosetting resin, a chemical bond is generated by a chemical reaction, and a mixed layer is easily formed. Thereby, it can be set as the surface modification layer excellent in adhesive force.
  • thermosetting resin is not particularly limited as long as it is a resin that cures when heated.
  • a thermosetting elastomer a phenol resin, an amino resin, an unsaturated polyester resin, an epoxy resin, and a polyurethane resin.
  • examples thereof include resins, silicone resins, thermosetting polyimide resins, and the like.
  • the thermosetting resin may be a thermosetting elastomer.
  • a thermosetting elastomer refers to a resin that is elastically deformed after heat curing.
  • the thermosetting elastomer may be cured or uncured, and examples thereof include a diene rubber containing a double bond or a non-diene rubber containing no double bond.
  • the thermosetting elastomer is preferably one that is crosslinked by heating, and typical crosslinking methods of the thermosetting elastomer include sulfur crosslinking, peroxide crosslinking, and resin crosslinking.
  • the thermosetting resin may be a diene rubber containing a double bond.
  • the component that reacts with the thermosetting resin contained in the surface modification layer is diene rubber and sulfur crosslinking, peroxide crosslinking, or resin crosslinking. It is preferable that the component to be included is included, and it is more preferable that a curing agent is included.
  • diene rubber containing a double bond examples include natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene-butadiene rubber (SBR), chloroprene rubber (CR), nitrile rubber, norbornene rubber. (NOR), acrylonitrile butadiene rubber (NBR) and the like.
  • NR natural rubber
  • IR isoprene rubber
  • BR butadiene rubber
  • SBR styrene-butadiene rubber
  • CR chloroprene rubber
  • NOR acrylonitrile butadiene rubber
  • NBR acrylonitrile butadiene rubber
  • the thermosetting resin may be a non-diene rubber that does not contain a double bond.
  • the component that reacts with the thermosetting resin contained in the surface modification layer contains a group that undergoes peroxide crosslinking with the non-diene rubber.
  • a mixture of a polymer component not containing a reactive unsaturated group and a peroxide is more preferable.
  • peroxide crosslinking radicals are generated by thermal decomposition of the peroxide, and the generated peroxide radicals draw hydrogen from the carbon-carbon bonds contained in the non-diene rubber, and the polymer contained in the surface modification layer Reacts with double bond sites in the ingredients.
  • the polymer component contained in the surface modification layer is a polymer component that does not contain a double bond
  • hydrogen is also extracted from the non-diene rubber and the polymer component by the peroxide, and thus reacts even between saturated bonds.
  • the component that reacts with the thermosetting resin contained in the surface-modified layer does not contain a peroxide-crosslinking group with the non-diene rubber, silanol condensation is also possible by adding a catalyst.
  • Non-diene rubbers that do not contain double bonds include nitrile rubber, ethylene / propylene rubber (EPM), ethylene / propylene / diene rubber (EPDM), butyl rubber (IIR), acrylic rubber (ACM), urethane rubber, and chlorinated polyethylene. , Polysulfide rubber, fluorine rubber (FKM), silicone rubber, chlorosulfonated polyethylene, epichlorohydrin rubber (CO / ECO), and the like.
  • the non-diene rubber not containing a double bond is preferably a silicone rubber.
  • the thermosetting resin is preferably a silicone resin or silicone rubber.
  • the reaction between the component that reacts with the thermosetting resin and the silicone rubber is peroxide cross-linking, and the radicals generated by removing hydrogen from the silicone rubber and the thermosetting resin The double bond site of the reacting component reacts. Even if the surface modification layer does not contain a double bond site, the radical generated by extracting hydrogen from the carbon-carbon bond site of the surface modification layer and the radical generated in the silicone rubber react with each other. To do.
  • any appropriate silicone resin can be adopted as long as the effects of the present invention are not impaired. Only one type of silicone resin may be used, or two or more types may be used.
  • a silicone resin may be a silicone resin that is liquid at room temperature, or may be a silicone resin that is solid at room temperature. Further, as such a silicone resin, a condensation type silicone resin or an addition type silicone resin may be used, and an addition type silicone resin is preferable.
  • a one-component silicone resin for example, a one-component room temperature curable (RTV) resin
  • RTV room temperature curable
  • It may be a resin (for example, a two-component room temperature curable (RTV) resin).
  • the component that reacts with the thermosetting resin is not particularly limited as long as it is a component that causes a chemical reaction with the thermosetting resin or a component that generates a bond such as a chemical bond, and any component can be used. Examples thereof include a curing agent, a polymer component containing a group having a reactive unsaturated bond, a mixture of a polymer component not containing a reactive unsaturated group and a peroxide, and a halogenated compound. , A curing agent, a polymer component containing a group having a reactive unsaturated bond, or a mixture of a polymer component not containing a reactive unsaturated group and a peroxide. More preferred.
  • thermosetting resin in the surface modification layer when the surface modification sheet is used for, for example, a surface modification member by containing a component that reacts with the thermosetting resin in the surface modification layer.
  • a mixed layer in which the thermosetting resin and the thermosetting resin are mixed is likely to cause a chemical reaction or a chemical bond.
  • the mixed layer is formed by providing a surface modification layer on at least a part of the surface of the thermosetting resin and performing heat welding, so that the interface between the surface modification layer and the thermosetting resin is fused and mixed. It is a layer of the welding mixing part obtained by. Further, by containing a curing agent, chemical reaction and chemical bond are more likely to occur.
  • the component that reacts with the thermosetting resin is a mixture of a polymer component not containing a reactive unsaturated group and a peroxide, and a curing agent.
  • a polymer component including a group having a reactive unsaturated bond more preferably including a polymer component including a group having a reactive unsaturated bond, and a curing agent and a reactive component.
  • a polymer component including a group having a saturated bond is further preferable to include a polymer component including a group having a saturated bond.
  • thermosetting resin When an uncured thermosetting resin is heat-cured, a polymer component containing a group having an unsaturated bond having reactivity between the thermosetting resin and the surface modified layer, or a group having a reactive unsaturated bond This is because a chemical reaction or chemical bond is likely to occur due to mixing with a polymer component that does not contain.
  • the component that reacts with the thermosetting resin is a mixture of a polymer component and a peroxide that does not include a reactive group having an unsaturated bond
  • the component that reacts with the thermosetting resin is a mixture of a polymer component and a peroxide that does not include a reactive group having an unsaturated bond
  • it is preferable to include a polymer component including a curing agent and a group having a reactive unsaturated bond it is more preferable to include a polymer component including a curing agent and a group having a reactive unsaturated bond.
  • the surface modification layer contains a curing agent and a polymer component containing a group having a reactive unsaturated bond, thereby causing a chemical reaction or chemical bonding with the cured thermosetting resin.
  • the component that reacts with the thermosetting resin is a polymer component containing a group having a reactive unsaturated bond
  • the polymer component containing a group having a reactive unsaturated bond acts as a binder. It becomes easy to form a surface-modified sheet.
  • the unsaturated bond having reactivity include an ethylenic double bond and a non-aromatic double bond, and an ethylenic double bond is preferable.
  • the polymer component containing a group having an ethylenic double bond is not particularly limited as long as it reacts with a thermosetting resin, and is preferably a polymer component having an ethylenic double bond in the side chain. This is because the adhesive force is improved by a chemical reaction between the thermosetting resin and the double bond site of the polymer component containing a group having an ethylenic double bond.
  • the polymer component containing a group having a reactive unsaturated bond is preferably a polymer component containing a group having an ethylenic double bond, and is selected from, for example, an isobutylene polymer, a butadiene polymer, an isoprene polymer, and the like. It is preferable that any one of the copolymers containing at least 1 type is included, and it is more preferable that either the isobutylene type polymer or the butadiene type polymer and the copolymer containing at least 1 type selected from these are included.
  • radicals are generated by hydrogen abstraction from the methyl group of the thermosetting elastomer, and the double bond site in the butadiene-based polymer is react.
  • the isobutylene polymer may be a homopolymer of isobutylene (homoisobutylene) or a copolymer having isobutylene as a main monomer.
  • the copolymer includes, for example, a copolymer of isobutylene and normal butylene, a copolymer of isobutylene and isoprene (regular butyl rubber, chlorinated butyl rubber, brominated butyl rubber, partially crosslinked butyl rubber, etc.), vulcanized products and modified products thereof. (For example, those modified with a functional group such as a hydroxyl group, a carboxyl group, an amino group, and an epoxy group).
  • the butadiene-based polymer may be a butadiene homopolymer or a copolymer containing butadiene as a main monomer.
  • the copolymer include a copolymer of butadiene and styrene, a copolymer of butadiene and acrylonitrile, and the like.
  • the isoprene-based polymer may be a homopolymer of isoprene or a copolymer having isoprene as a main monomer.
  • examples of the copolymer include a copolymer of isoprene and isobutylene.
  • copolymer examples include a styrene-based AB type diblock copolymer (diblock copolymer) such as styrene / butadiene copolymer (SB) and styrene / isoprene copolymer (SI); styrene / butadiene. ⁇ Styrene copolymer (SBS), styrene-based ABA block copolymer (triblock copolymer) such as styrene / isoprene / styrene copolymer (SIS); styrene / butadiene / styrene / butadiene copolymer (SBSB) ), Styrene-based ABAB type block copolymer (tetrablock copolymer) such as styrene / isoprene / styrene / isoprene copolymer
  • the component that reacts with the thermosetting resin is a mixture of a polymer component that does not contain a reactive unsaturated bond group and a peroxide, it has an unsaturated bond that is reactive with the peroxide. Since hydrogen is also drawn from a polymer component not containing a group, when the thermosetting resin is silicone rubber, the silicone rubber reacts with a polymer component not containing a group having a reactive unsaturated bond.
  • Examples of the peroxide include organic peroxides.
  • An organic peroxide is a compound having an oxygen-oxygen (—O—O—) bond in the molecule, and this oxygen-oxygen (—O—O—) bond is relatively easily cleaved by heat. Produces radicals rich in nature.
  • Specific examples of organic peroxides include hydroperoxides, dialkyl peroxides, peroxyesters, diacyl peroxides, peroxydicarbonates, peroxymonocarbonates, peroxyketals, alkylperoxyesters, and ketone peroxides. Can be mentioned.
  • the polymer component not containing a reactive unsaturated bond group is at least one selected from, for example, a styrene polymer, a polyurethane polymer, a polyester polymer, a polyamide polymer, and a (meth) acrylic polymer. It is preferable.
  • styrene polymers examples include styrene AB type diblock copolymers (diblock copolymers) such as styrene / butylene copolymers; styrene ABA type block copolymers such as styrene / butylene / styrene copolymers ( Triblock copolymer); styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (SEPS), and the like.
  • styrene polymers include styrene AB type diblock copolymers (diblock copolymers) such as styrene / butylene copolymers; styrene ABA type block copolymers such as styrene / butylene / styrene copolymers ( Triblock copo
  • polyurethane-based polymers examples include those based on polyester or polyether and isocyanate.
  • polyester polymer examples include saturated polyester (for example, polyethylene terephthalate, polybutylene terephthalate, etc.), modified polyolefin (for example, acid-modified polyolefin such as acrylic acid-modified polyethylene and acrylic acid-modified polypropylene; epoxy-modified polyolefin, etc.) or rubber.
  • a polymer for example, a thermoplastic elastomer such as ethylene-propylene rubber, polyester elastomer, ethylene-acrylic rubber
  • those based on polyethylene naphthalate examples include saturated polyester (for example, polyethylene terephthalate, polybutylene terephthalate, etc.), modified polyolefin (for example, acid-modified polyolefin such as acrylic acid-modified polyethylene and acrylic acid-modified polypropylene; epoxy-modified polyolefin, etc.) or rubber.
  • Blends with a polymer for example, a thermoplastic elastomer such as ethylene-propylene
  • polyamide polymers include those based on amino acids, lactams or diamines and dicarboxylic acids. Examples include nylon 6 and nylon 66.
  • the main component is (meth) acrylic acid alkyl ester such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, isononyl acrylate, etc., and if necessary, acrylonitrile, Polymers of monomers made by adding modifying monomers such as vinyl acetate, styrene, methyl methacrylate, acrylic acid, maleic anhydride, vinyl pyrrolidone, glycidyl methacrylate, dimethylaminoethyl methacrylate, hydroxyethyl acrylate, and acrylamide Is the main agent.
  • acrylic acid alkyl ester such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, isononyl acrylate, etc., and if necessary, acrylonitrile
  • the main agent is a component that occupies the largest mass ratio among the contained components.
  • the curing agent may be one that reacts with the thermosetting resin, or one that promotes the reaction with the polymer component containing a group having an unsaturated bond that is reactive with the thermosetting resin, although there is no restriction
  • a silane curing agent or an organic titanium curing agent is more preferable, and an organic titanium curing agent is more preferable.
  • Two or more curing agents may be used in combination, and it is preferable to use a silane curing agent and an organic titanium curing agent in combination.
  • Examples of the silane curing agent include silicone alkoxy oligomers and alkoxysilanes.
  • Examples of the organic titanium curing agent include tetrabutyl titanate, tetraethyl titanate, tetraisopropyl titanate, and tetraphenyl titanate.
  • Examples of the amine-based curing agent include “Epomin” (registered trademark) series (manufactured by Nippon Shokubai Co., Ltd.) and the like as polyethyleneimine as a tertiary amine compound.
  • Examples of the imidazole-based curing agent include “Curazole” series (imidazole-based epoxy resin curing agent, Shikoku Kasei Kogyo Co., Ltd.).
  • Examples of the acid anhydride curing agent include methyltetrahydrophthalic anhydride and (methyl) hexahydrophthalic anhydride.
  • curing agent should just become said range.
  • the surface modification layer may contain a halogenated compound as a component that reacts with the thermosetting resin.
  • a halogenated compound include chlorinated compounds, which are preferably chlorinated polymers, and more preferably chlorinated polypropylene.
  • a surface modified layer containing a chlorine-based compound for a member containing a thermosetting resin when using a surface modified layer containing a chlorine-based compound for a member containing a thermosetting resin, a surface modifying composition described later may be applied to a member containing a thermosetting resin, The surface modified layer formed into a sheet may be thermally transferred to a member containing a thermosetting resin or the like, and is preferably thermally transferred.
  • the thermosetting resin is a diene rubber containing a double bond
  • the surface modification layer can be formed using a surface modification composition described later.
  • a surface modification composition the solution which melt
  • the main component is a polymer component containing a group having a reactive unsaturated bond or a polymer component not containing a reactive unsaturated bond, and optionally contains a curing agent or a peroxide.
  • the mixture may be soaked in a solution by a conventional method and heated to obtain a polymer solution, which may be prepared by adding a crosslinking agent or the like as necessary.
  • the surface modification layer may further contain any appropriate additive as required.
  • the additive include an initiator, a crosslinking agent, a tackifier, a plasticizer, a pigment, a dye, a filler, an anti-aging agent, a conductive material, an antistatic agent, an ultraviolet absorber, a light stabilizer, and a release modifier. , Softeners, surfactants, flame retardants, antioxidants and the like.
  • the thickness of the surface modification layer is preferably 0.001 ⁇ m or more, more preferably 0.01 ⁇ m or more, and further preferably 0.05 ⁇ m or more from the viewpoint of adhesive strength. Further, from the viewpoint of adhesive strength, it is preferably 100 ⁇ m or less, more preferably 30 ⁇ m or less, and further preferably 10 ⁇ m or less.
  • release sheet Although it does not specifically limit as a release sheet, It is preferable that heat resistance is 100 degreeC or more, and it is preferable that the tensile elasticity modulus in 100 degreeC is 1 GPa or less. Further, it is preferably a non-silicon-based resin sheet, for example, a fluororesin sheet film (manufactured by Nitto Denko, Nitoflon), a polyester resin sheet, a polymethylpentene resin sheet (manufactured by Mitsui Chemicals, Inc., Opyran (registered trademark)), Examples thereof include a polystyrene resin sheet (manufactured by Kurabo Industries, Eudis (registered trademark)).
  • the thickness of the release sheet is preferably 1 ⁇ m to 1000 ⁇ m, more preferably 10 ⁇ m to 500 ⁇ m, still more preferably 10 ⁇ m to 300 ⁇ m, and particularly preferably 5 ⁇ m to 200 ⁇ m from the viewpoint of shape followability.
  • the surface-modified sheet can be produced by any appropriate method. For example, a method of drying the release sheet as necessary after dipping the release sheet into a solution (surface modification composition) containing the material of the surface modification layer and a solvent, and the surface modification composition on the surface of the release sheet A method of drying as needed after brush coating, a method of drying the surface modifying composition on the surface of the release sheet with various coaters after drying, a surface modifying composition on the surface of the release sheet The method of drying as needed after the spray application of a thing is mentioned.
  • dissolved the material which comprises a surface modification layer in the solvent is mentioned.
  • the solvent include alcohols such as methanol, ethanol and isopropyl alcohol; ketones such as methyl ethyl ketone; esters; aliphatic, alicyclic, and aromatic hydrocarbons; halogenated hydrocarbons; amides such as dimethylformamide; And sulfoxides such as dimethyl sulfoxide; ethers such as dimethyl ether and tetrahydrofuran;
  • One type of solvent may be sufficient and 2 or more types may be sufficient as it.
  • the solid content concentration in the surface modifying composition can be appropriately set according to the purpose.
  • the mass ratio is preferably 0.01% by mass to 80% by mass, more preferably 0.05% by mass to 60% by mass, and further preferably 0.1% by mass. % To 50% by mass.
  • a pH adjuster For the surface modification composition, a pH adjuster, a crosslinking agent, a viscosity adjuster (thickener, etc.), a leveling agent, a release adjuster, a plasticizer, a softener, a filler, a colorant (pigment) as necessary. , Dyes, etc.), surfactants, antistatic agents, preservatives, anti-aging agents, ultraviolet absorbers, antioxidants, light stabilizers and the like.
  • a laminate according to an embodiment of the present invention is a laminate in which a surface modification layer is laminated on the surface of a thermosetting resin, and the thermosetting resin is interposed between the thermosetting resin and the surface modification layer. It is preferable to provide a mixed layer in which the resin and the surface modified layer are mixed.
  • the laminate may further have a layer containing another resin component, and the other resin component may be a thermoplastic resin or a thermosetting resin.
  • a surface modification member according to an embodiment of the present invention is a surface modification member in which a surface modification layer is laminated on a surface of a thermosetting resin, and the surface modification layer reacts with the thermosetting resin.
  • the thermosetting resin and the surface modification layer are combined by a chemical reaction.
  • the surface modifying member preferably includes a mixed layer in which the thermosetting resin and the surface modified layer are mixed between the thermosetting resin and the surface modified layer. It is preferable that the surface modified layer is bonded to the surface modified layer by a chemical reaction.
  • thermosetting resin As the thermosetting resin, the thermosetting elastomer, and the surface modification layer, the above description can be used as it is.
  • the mixed layer is a layer in which the thermosetting resin and the surface modification layer are mixed, and the surface modification is performed by providing a surface modification layer on at least a part of the surface of the thermosetting resin and performing heat welding.
  • the interface between the layer and the thermosetting resin is melt-contacted and welded and mixed, whereby the layer of the welded mixed portion obtained.
  • the thickness of the mixed layer can be appropriately determined according to the heat welding conditions and the type of the thermosetting resin or the surface modification layer.
  • the thickness of the mixed layer is preferably 1.5 nm or more, more preferably 2.0 nm or more.
  • the thickness of the thermosetting resin is, for example, 0.001 mm to 100 mm.
  • the thickness of the surface modified layer is not particularly limited, is preferably 0.001 ⁇ m to 100 ⁇ m, more preferably 0.01 ⁇ m to 10 ⁇ m, and still more preferably.
  • the thickness is 0.05 to 5 ⁇ m, particularly preferably 0.1 to 3 ⁇ m.
  • the surface modifying member according to the embodiment of the present invention is preferably obtained by the method for producing a surface modifying member of the present invention.
  • the coated object according to the embodiment of the present invention is provided with a coating film on at least a part of the surface of the surface modifying member on the surface modifying layer side. Since the surface modification layer is formed using the surface modification sheet formed in a sheet shape, it is possible to prevent the occurrence of unevenness due to repellency or the like that has occurred on the surface of the member in the application. Moreover, since the surface modification layer is in the form of a sheet, it can be formed on the surface of the member with a uniform thickness.
  • the coating film is not particularly limited, and examples thereof include various coating films such as polyester / melamine system, alkyd / melamine system, acrylic / melamine system, acrylic / urethane system, acrylic / polyacid curing agent system, and plating treatment. .
  • coating method of the coating film and general methods such as brush coating, roller coating, spray coating, and various coater coating can be used, and the coating amount is not particularly limited.
  • the time, temperature, etc. which heat a coating film can be suitably determined with the coating material to be used, the application quantity, etc.
  • the printed matter according to the embodiment of the present invention is obtained by printing on at least a part of the surface of the surface modifying member on the surface modifying layer side. Since the surface modification layer is formed using a sheet-like surface modification sheet, it can be uniformly formed on the surface of the non-printing medium. In addition, since the surface modification layer can be formed evenly in a three-dimensional shape, a printed matter with a uniform film thickness can be obtained. Examples of printing include inkjet printing.
  • the joined body according to the embodiment of the present invention is obtained by joining an article to at least a part of the surface of the surface modified member on the surface modified layer side using an adhesive.
  • articles that can be joined include electronic parts, automobile exterior parts (particularly, flexible rubber hollow members such as weather strips), body protection parts, and decorative parts.
  • the adhesive is not particularly limited, and for example, rubber adhesive, urethane adhesive (acrylic urethane adhesive), acrylic adhesive, silicone adhesive, polyester adhesive, polyamide adhesive, epoxy Known adhesives such as adhesives based on vinyl, vinyl alkyl ether, and fluorine can be used. Among these, rubber adhesives and urethane (acrylic urethane) adhesives are particularly preferable.
  • the said adhesive agent may be individual, and 2 or more types of combinations may be sufficient as it.
  • a method for producing a surface modified member according to an embodiment of the present invention is a method for producing a surface modified member formed by using a surface modified sheet and a thermosetting resin, and the step of molding the surface modified member
  • a surface modification layer is provided on at least a part of the surface of the thermosetting resin.
  • the component that reacts with the thermosetting resin is a mixture of a polymer component and a peroxide that does not include a group having a reactive unsaturated bond, Or it is preferable that the polymer component containing the group which has an unsaturated bond which has reactivity is included.
  • the polymer component not containing a reactive unsaturated bond group is at least one selected from a styrene polymer, a polyurethane polymer, a polyester polymer, a polyamide polymer, and a (meth) acrylic polymer, It is preferable that the polymer component containing a group having a reactive unsaturated bond includes any of an isobutylene polymer, a butadiene polymer, an isoprene polymer, and a copolymer containing at least one selected from these.
  • the component that reacts with the thermosetting resin is a mixture of a polymer component and a peroxide that do not contain a reactive group having an unsaturated bond, or It is preferable to include a polymer component including a curing agent and a group having a reactive unsaturated bond.
  • the polymer component not containing a group having an ethylenic double bond is at least one selected from a styrene polymer, a polyurethane polymer, a polyester polymer, a polyamide polymer, and a (meth) acrylic polymer, and is reactive.
  • the polymer component containing a group having an unsaturated bond having any of the following includes any of an isobutylene polymer, a butadiene polymer, an isoprene polymer, and a copolymer containing at least one selected from these, and the curing agent is a silane It is preferably at least one selected from a system curing agent, an organic titanium curing agent, an amine curing agent, an imidazole curing agent, and an acid anhydride curing agent.
  • thermosetting resin a thermosetting elastomer, a surface modification layer, a curing agent, a polymer component containing a group having a reactive unsaturated bond, or a polymer component not containing a reactive unsaturated group;
  • a thermosetting resin a thermosetting elastomer, a surface modification layer, a curing agent, a polymer component containing a group having a reactive unsaturated bond, or a polymer component not containing a reactive unsaturated group
  • the above description can be used as it is.
  • the surface modified layer is provided on at least a part of the surface of the thermosetting resin during the molding process of the surface modified member.
  • a molding method a known method such as press molding, injection molding, blow molding or the like can be appropriately used.
  • a hot press apparatus, an injection molding apparatus, or a double belt press molding apparatus can be used. Examples of the heating method include oven heating, infrared heating, and high-frequency heating.
  • the thermosetting resin is filled in the mold and integrally formed by injection molding, so that the surface modified sheet is formed during the molding process.
  • the surface modification layer can be provided on at least a part of the surface of the thermosetting resin. Moreover, it mounts
  • the heating temperature at the time of molding varies depending on the type of thermosetting resin and the type of resin used for the surface modified sheet, it can be appropriately selected, but is preferably 400 ° C. or lower.
  • the pressure at the time of molding is not particularly limited, and is preferably determined appropriately in consideration of the shape and physical properties of the surface modifying member, and is preferably 0 to 10 MPa.
  • the release sheet is peeled off, so that the surface-modified layer is transferred to the surface of the thermosetting resin, and the surface is modified.
  • a surface-modified member can be obtained.
  • the release sheet may be peeled off before the forming step, or may be peeled off at any point in the forming step or after the forming step. In this way, it is possible to easily obtain a surface-modified member having good adhesion between the surface-modified layer and the thermosetting resin and having a uniform surface-modified layer thickness.
  • the surface modification layer 10 is provided on the surface of the resin 100, and a surface modification member is obtained.
  • the resin 100 here is a thermosetting resin.
  • the surface modification layer 10 is laminated on the surface of the resin 100, but preferably the resin (thermosetting resin) and the resin are between the resin 100 and the surface modification layer 10.
  • a mixed layer (not shown) mixed with the surface modification layer is provided.
  • the surface modified sheet which is a laminate of the release sheet and the surface modified layer is a surface modified sheet 200 which is a laminate of the release sheet 20 and the surface modified layer 10 as shown in FIG.
  • the surface modified layer side of the surface modified sheet which is a laminate of the release sheet and the surface modified layer is made of the resin (thermosetting resin).
  • the form to be placed on at least a part of the surface is such that the surface-modified sheet 200 is arranged such that the surface-modified layer 10 side of the surface-modified sheet 200 is the surface side of the resin 100.
  • the modified sheet 200 is placed on the surface of the resin 100.
  • the coating film 30 is provided on the surface of the surface modification member having the surface modification layer 10 provided on the surface of the resin 100 in FIG.
  • the coated object 300 provided is shown.
  • the surface modifying member according to the embodiment of the present invention has at least a part of the surface of the thermosetting resin modified by the surface modifying layer, the surface modifying member has excellent adhesive strength with other resin components, and is a thermoplastic resin. Also exhibits excellent adhesion.
  • coatings, printing, and bonding of articles before preheating treatment, corona discharge treatment, electron irradiation treatment, ultraviolet irradiation treatment, flame plasma treatment, atmospheric pressure plasma treatment or low pressure plasma treatment, etc. Although a treatment may be performed, a coated material, a printed material, and a bonded body having sufficient adhesive strength can be obtained without performing a pretreatment.
  • Example 1 A surface modification composition (20% by mass toluene solution) containing the following surface modification layer component was applied to a release sheet (No. 900UL, 50 ⁇ m, manufactured by Nitto Denko Corporation) and dried (120 ° C. ⁇ 3 min), A surface modified sheet having a surface modified layer having a thickness of 1 ⁇ m was prepared. The surface-modified sheet thus prepared is placed on a curable silicone rubber (product number: K-125, manufactured by Togawa Rubber Co., Ltd.) so that the surface-modified layer side is on the inside, and is subjected to thermal transfer by press molding (165 ° C. ⁇ 7 min) A modified member was produced.
  • a curable silicone rubber product number: K-125, manufactured by Togawa Rubber Co., Ltd.
  • the silicone rubber and the surface modification layer are cross-linked by the peroxide contained in the curable silicone rubber by heat treatment during press molding. Thereafter, the release sheet of the produced surface-modifying member was peeled off, and 80 mm ⁇ 20 mm VR5300 (manufactured by Nitto Denko Corporation, SIS adhesive tape (containing SIS block polymer)) was attached to prepare a joined body.
  • Example 2 to 7 A surface modified sheet was produced in the same manner as in Example 1 except that the composition of the surface modified layer was changed as shown in Table 1.
  • a surface-modified member and a joined body were produced in the same manner as in Example 1 using the produced surface-modified sheet. The evaluation results of the manufactured joined body are shown in Table 1.
  • a surface modification composition (20% by mass toluene solution) containing the following surface modification layer component was applied to a release sheet (No. 900UL, 50 ⁇ m, manufactured by Nitto Denko Corporation) and dried (120 ° C. ⁇ 3 min), A surface modified sheet having a surface modified layer having a thickness of 1 ⁇ m was prepared.
  • the surface-modified sheet thus prepared is placed on a curable silicone rubber (product number: K-125, manufactured by Togawa Rubber Co., Ltd.) so that the surface-modified layer side is on the inside, and is subjected to thermal transfer (165 ° C. ⁇ 7 min) by press molding.
  • a modified member was produced.
  • the release sheet of the produced surface-modifying member was peeled off, and 80 mm ⁇ 20 mm VR5300 (manufactured by Nitto Denko Corporation, SIS adhesive tape (containing SIS block polymer)) was attached to prepare a joined body.
  • a curable silicone rubber (product number: K-125, manufactured by Togawa Rubber Co., Ltd.) was subjected to no. 5303W (silicone-based adhesive tape, manufactured by Nitto Denko Corporation) was applied to prepare a joined body.
  • Table 1 shows the evaluation results of the joined bodies produced in Examples 1 to 7, Comparative Examples 1 to 3, and Reference Example.
  • the surface modified sheets according to Examples 1 to 6 containing a polymer component and a curing agent have excellent adhesion to SIS-based adhesive tapes regardless of whether they are applied to curable silicone rubber or uncured silicone rubber. Expressed power. The adhesive strength was inferior to that of the reference example in which the silicone adhesive tape was bonded.
  • the surface-modified sheets according to Examples 3 to 5 have better adhesive force than the surface-modified sheet according to Example 6, and more excellent adhesive force is achieved by using a titanium-based curing agent and a silicone curing agent in combination. Was shown to do.
  • the surface-modified sheet according to Example 7 containing no curing agent exhibited excellent adhesion when applied to uncured silicone rubber.
  • the surface modified sheet according to Comparative Example 2 had a low adhesive force, and was comparable to Comparative Examples 1 and 3 in which no surface modified sheet was used.
  • Example 8 The surface modification composition shown in Table 2 was applied to a release sheet (No. 900UL, 50 ⁇ m, manufactured by Nitto Denko Corporation) and dried (120 ° C. ⁇ 3 min) to provide a surface modification layer having a 5 ⁇ m thick surface modification layer A quality sheet was prepared.
  • the prepared surface modified sheet is placed on butadiene rubber (manufactured by Standard Test Piece Co., Ltd.) so that the surface modified layer side is on the inside, and is subjected to thermal transfer (160 ° C. ⁇ 5 min, pressure 2 MPa) by press molding.
  • A) was prepared. Thereafter, a polyurethane (PU) adhesive was applied and dried (60 ° C.
  • PU polyurethane
  • Example 9 A surface modified member and a joined body were prepared in the same manner as in Example 8 except that the composition of the surface modified layer, the thermosetting resin, and the adhesive were changed as shown in Table 2.
  • thermosetting resin body provided with an adhesive layer. Then, the adhesive surfaces of the thermosetting resin bodies provided with two adhesive layers were pasted together, and heated and stored (40 ° C. ⁇ 24 hr) under a load of about 20 kg / m 2 to prepare a joined body. .
  • Table 2 shows the evaluation results of the joined bodies produced in Examples 8 to 13 and Comparative Examples 4 to 6.
  • P740NT No Tape Industrial Co., Ltd., chloroprene rubber adhesive
  • UH2170 manufactured by Toa Gosei, hydroxyl-containing acrylic polymer
  • RC-1028K manufactured by Road Japan Inc., chlorinated polypropylene
  • UCECOAT7850 manufactured by Daicel Ornex Co., Ltd.
  • thermosetting resin BR: Butadiene rubber (manufactured by Standard Test Piece Co., Ltd.)
  • IIR Butyl rubber (manufactured by Akitsu Industry Co., Ltd.)
  • SIR with respect to a mixture of silicone rubber (uncured silicone rubber KE9490-U (manufactured by Shin-Etsu Chemical Co., Ltd.)) and C-8 (manufactured by Shin-Etsu Chemical Co., Ltd.) (composition: KE9490-U (100 parts by mass)) Silicone rubber compounded with C-8 (2 parts by mass) (adhesive)
  • Polyurethane rubber (PU) adhesive 5 parts by mass of solid content of curing agent UFE (manufactured by Notape Industry Co., Ltd., isocyanate compound) with respect to 100 parts by mass of solid content of AS-560 (manufactured by Notape Industry Co., Ltd., polyurethane resin) Part addition and stirring were performed to obtain an adhesive.
  • Chloroprene rubber (CR) adhesive 3 parts by mass of a curing agent UFE (manufactured by Notape Industry Co., Ltd., isocyanate compound) is added to 100 parts by mass of solids of 9000NT (Notape Industries Co., Ltd., chloroprene rubber). The mixture was stirred to obtain an adhesive.
  • Adhesive tape VR5300: Nitto Denko Corporation, SIS adhesive tape H7008: Nitto Denko Corporation, acrylic foam adhesive tape

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne : une feuille à surface modifiée comportant une feuille de libération et une couche à surface modifiée, la couche à surface modifiée contenant un composant qui réagit avec une résine thermodurcissable ; Un élément à surface modifiée, un article revêtu, un article imprimé, et un corps de jonction dans lesquels la feuille modifiée en surface est utilisée ; et un procédé de fabrication de l'élément à surface modifiée.
PCT/JP2019/017524 2018-04-26 2019-04-24 Feuille à surface modifiée, élément à surface modifiée, article revêtu, article imprimé, corps assemblé et procédé de fabrication d'élément à surface modifiée WO2019208665A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US17/050,569 US20210238454A1 (en) 2018-04-26 2019-04-24 Surface-modifying sheet, surface-modified member, coated article, printed article, joined body, and method for producing surface-modified member
KR1020207030705A KR20210005869A (ko) 2018-04-26 2019-04-24 표면 개질 시트, 표면 개질 부재, 도장물, 인쇄물, 접합체, 및 표면 개질 부재의 제조 방법
CN201980028024.9A CN112004668A (zh) 2018-04-26 2019-04-24 表面改性片材、表面改性构件、涂装物、印刷物、接合体及表面改性构件的制造方法
EP19793788.1A EP3785899A4 (fr) 2018-04-26 2019-04-24 Feuille à surface modifiée, élément à surface modifiée, article revêtu, article imprimé, corps assemblé et procédé de fabrication d'élément à surface modifiée

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JP2018085670 2018-04-26
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JP2019082960A JP2019194015A (ja) 2018-04-26 2019-04-24 表面改質シート、表面改質部材、塗装物、印刷物、接合体、及び表面改質部材の製造方法

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US11345136B2 (en) * 2019-08-23 2022-05-31 Honda Motor Co., Ltd. Resin molded article and manufacturing method therefor
WO2022181423A1 (fr) * 2021-02-26 2022-09-01 日東電工株式会社 Élément à surface modifiée, objet revêtu, procédé de production d'un élément à surface modifiée et procédé de production d'un objet revêtu

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JPS612107B2 (fr) 1980-01-21 1986-01-22 Toray Silicone Co
JPS6021220A (ja) * 1983-07-18 1985-02-02 Toshiba Chem Corp 化学メツキ用積層板の製造方法
JPH04506485A (ja) * 1989-05-08 1992-11-12 エイティー　ディー　コーポレーション 感圧接着剤積層体
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Publication number Priority date Publication date Assignee Title
US11345136B2 (en) * 2019-08-23 2022-05-31 Honda Motor Co., Ltd. Resin molded article and manufacturing method therefor
WO2022181423A1 (fr) * 2021-02-26 2022-09-01 日東電工株式会社 Élément à surface modifiée, objet revêtu, procédé de production d'un élément à surface modifiée et procédé de production d'un objet revêtu

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