WO2019208665A1 - Surface-modified sheet, surface-modified member, coated article, printed article, joined body, and method for manufacturing surface-modified member - Google Patents

Surface-modified sheet, surface-modified member, coated article, printed article, joined body, and method for manufacturing surface-modified member 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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French (fr)
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 CN201980028024.9A priority Critical patent/CN112004668A/en
Priority to EP19793788.1A priority patent/EP3785899A4/en
Priority to US17/050,569 priority patent/US20210238454A1/en
Priority to KR1020207030705A priority patent/KR20210005869A/en
Priority claimed from JP2019082960A external-priority patent/JP2019194015A/en
Publication of WO2019208665A1 publication Critical patent/WO2019208665A1/en

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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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  • Organic Chemistry (AREA)
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Abstract

The present invention pertains to: a surface-modified sheet provided with a release sheet and a surface-modified layer, the surface-modified layer containing a component that reacts with a thermosetting resin; a surface-modified member, a coated article, a printed article, and a joining body in which the surface-modified sheet is used; and a method for manufacturing the surface-modified member.

Description

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Surface-modified sheet, surface-modified member, painted product, printed material, joined body, and method for producing surface-modified member
　本発明は、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に関する。 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.
　近年、鉄道車両、航空機、船舶、自動車等の輸送機器、電子機器、住宅設備等の部材には、軽量かつ対衝撃性に優れた熱硬化性樹脂が用いられ、その表面には種々の材質の被着体が接合されている。 In recent years, 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.
　熱硬化性樹脂に被着体を強固に接合させるため、熱硬化性樹脂の表面にはプライマー層の塗布や、予め加熱する処理、コロナ放電処理、電子照射処理、紫外線照射処理、フレームプラズマ処理、大気圧プラズマ処理または低圧プラズマ処理等の前処理が施されている。 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.
　また、シリコーンゴムのような非極性な熱硬化性エラストマーに被着体を接合させるにはシリコーン系の接着剤や粘着テープが使用されている。しかし、シリコーン系粘着剤で接合するには接着力が不十分である。
　そのため、シリコーンゴムに用いるプライマー組成物として、シランカップリング剤やその縮合物、またそれらの反応生成物、およびアルコキシチタンやチタネート系カップリング剤などの有機チタン化合物などが知られている。 In addition, silicone-based adhesives and pressure-sensitive adhesive tapes are used for bonding an adherend to a nonpolar thermosetting elastomer such as silicone rubber. However, 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.
　例えば、特許文献１には、シリコーンゴムとシリコーンゴム以外の材料の接着に用いる、特定構造を有する有機けい素化合物及び有機チタン化合物を含有する接着用シリコーン組成物が記載されている。
　特許文献２にはガラスや金属などの基材面や、シリコーンゴム等の先打ちシーリング材との打継ぎ面での接着性に優れ、反応性ケイ素基を有する飽和炭化水素系重合体を主成分とするシーリング材に適用されるプライマー組成物および接着方法が記載されている。
　特許文献３には、シリコーンゴムと各種の被着体との接着に用いる、有機チタン化合物及び溶媒を含むプライマー組成物が記載されている。 For example, 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.
日本国特公昭６１－２１０７号公報Japanese Patent Publication No. 61-2107 日本国特開平１１－２０９７０２号公報Japanese Patent Laid-Open No. 11-209702 日本国特開２０１７－０６９２９０号公報Japanese Unexamined Patent Publication No. 2017-069290
　しかしながら、熱硬化性樹脂の表面に被着体を接合させる前や、塗装、印刷を施す前に前処理を施すには、成形の際に用いる離型剤を除去する工程が必要となる。また、プライマー層形成の前にも前処理等が必要である。さらに、低極性樹脂と極性樹脂や、熱硬化性樹脂と熱可塑性樹脂はプライマー層を用いても接着が困難であった。
　また、塗装面や印刷面は塗膜や印刷が熱硬化性樹脂の表面にむら無く形成されることが必要であるため、プライマー層も熱硬化性樹脂の表面にむら無く形成することが求められる。
　しかしながら、特許文献１～３に記載のプライマー組成物は、プライマー層を塗布により形成しているため、プライマー層のハジキ発生等により熱硬化性樹脂の表面にプライマー層をむら無く形成することが困難である。また、熱硬化性樹脂の表面の一部にプライマー層を施す際には、はみだし等により歩留りが低下するという課題がある。
　また、低極性の熱硬化性樹脂に対し有機系ポリマーを主剤とするプライマー層は相溶性が悪く、接着力が充分でないという問題もある。 However, 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. .
However, since the primer compositions described in Patent Documents 1 to 3 are formed by coating the primer layer, it is difficult to form the primer layer uniformly on the surface of the thermosetting resin due to the occurrence of repellency of the primer layer. It is. Moreover, when applying a primer layer to a part of surface of a thermosetting resin, there exists a subject that a yield falls by protrusion etc.
Moreover, the primer layer which has an organic polymer as a main ingredient with respect to a low-polarity thermosetting resin has bad compatibility, and there also exists a problem that adhesive force is not enough.
　以上のような問題を鑑みて、本発明は、接着力に優れ、むら無く表面改質層（プライマー層）を形成でき、表面改質部材の形成の際に表面改質層と熱硬化性樹脂との一体成形が可能な表面改質シートを提供することを目的とする。また、この表面改質シートを用いた、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を提供することを目的とする。 In view of the above problems, 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.
　本発明者は前記課題を解決するために鋭意検討を行った。その結果、表面改質層をシート状にし、熱硬化性樹脂と反応する成分を含有させることにより、低極性樹脂と極性樹脂や、熱硬化性樹脂と熱可塑性樹脂の接合に際し十分な接着力を発揮し、任意の箇所にむら無く表面改質層を形成し得ることを見出し、本発明を完成するに至った。 The present inventor has intensively studied to solve the above problems. As a result, 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.
　本発明の一態様は、離型シートと表面改質層とを備え、前記表面改質層は、熱硬化性樹脂と反応する成分を含有する表面改質シートに関する。 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.
　本発明の一態様において、前記表面改質シートは、前記熱硬化性樹脂と反応する成分が、硬化剤、反応性を有する不飽和結合を有する基を含むポリマー成分、または反応性を有する不飽和結合を有する基を含まないポリマー成分と過酸化物との混合物の少なくともいずれかを含んでいてもよい。 In one aspect of the present invention, 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.
　本発明の一態様において、前記表面改質シートは、前記熱硬化性樹脂が、熱硬化性エラストマーであってもよい。 In one aspect of the present invention, in the surface modified sheet, the thermosetting resin may be a thermosetting elastomer.
　本発明の一態様において、前記表面改質シートは、前記熱硬化性樹脂が、二重結合を含まない非ジエン系ゴムであってもよい。 In one aspect of the present invention, in the surface modified sheet, the thermosetting resin may be a non-diene rubber that does not contain a double bond.
　本発明の一態様において、前記表面改質シートは、前記熱硬化性樹脂が、シリコーン系樹脂またはシリコーンゴムであってもよい。 In one aspect of the present invention, in the surface modified sheet, the thermosetting resin may be a silicone resin or a silicone rubber.
　本発明の一態様は、熱硬化性樹脂の表面に表面改質層が積層された表面改質部材であって、前記表面改質層は、前記熱硬化性樹脂と反応する成分を含有し、前記熱硬化性樹脂と、前記表面改質層とが化学反応により結合した表面改質部材である。 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.
　本発明の一態様において、表面改質部材は、前記熱硬化性樹脂と反応する成分が、硬化剤、反応性を有する不飽和結合を有する基を含むポリマー成分、または反応性を有する不飽和結合を有する基を含まないポリマー成分と過酸化物との混合物の少なくともいずれかを含んでいてもよい。 In one embodiment of the present invention, 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.
　本発明の一態様において、表面改質部材は、前記熱硬化性樹脂が、熱硬化性エラストマーであってもよい。 In one aspect of the present invention, in the surface modifying member, the thermosetting resin may be a thermosetting elastomer.
　本発明の一態様において、表面改質部材は、前記熱硬化性樹脂が、二重結合を含まない非ジエン系ゴムであってもよい。 In one aspect of the present invention, the surface-modifying member may be a non-diene rubber in which the thermosetting resin does not contain a double bond.
　本発明の一態様において、前記表面改質部材は、前記熱硬化性樹脂が、シリコーン系樹脂またはシリコーンゴムであってもよい。 In one aspect of the present invention, in the surface modifying member, the thermosetting resin may be a silicone resin or a silicone rubber.
　本発明の一態様は、前記表面改質部材の表面改質層側の表面の少なくとも一部に塗膜を備えた塗装物である。 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.
　本発明の一態様は、前記表面改質部材の表面改質層側の表面の少なくとも一部に印刷を施した印刷物である。 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.
　本発明の一態様は、前記表面改質部材の表面改質層側の表面の少なくとも一部に接着剤を用いて物品を接合した接合体である。 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.
　本発明の一態様は、前記表面改質シートと、前記熱硬化性樹脂とを用いて成形した表面改質部材の製造方法であって、前記表面改質部材の成形工程中に前記熱硬化性樹脂の表面の少なくとも一部に前記表面改質層を設ける表面改質部材の製造方法である。 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.
　本発明の一態様において、表面改質部材の製造方法は、前記熱硬化性樹脂は、未硬化の熱硬化性樹脂であり、
　前記熱硬化性樹脂と反応する成分が、反応性を有する不飽和結合を有する基を含まないポリマー成分と過酸化物との混合物、または反応性を有する不飽和結合を有する基を含むポリマー成分を含むことが好ましい。 In one aspect of the present invention, in the method for producing a surface modifying member, the thermosetting resin 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.
　本発明の一態様において、前記表面改質部材の製造方法は、前記熱硬化性樹脂は、硬化した熱硬化性樹脂であり、
　前記熱硬化性樹脂と反応する成分が、反応性を有する不飽和結合を有する基を含まないポリマー成分と過酸化物との混合物、または硬化剤及び反応性を有する不飽和結合を有する基を含むポリマー成分を含むことが好ましい。 In one aspect of the present invention, in the method for producing the surface modifying member, the thermosetting resin 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.
　本発明の一態様において、前記表面改質部材の製造方法は、前記熱硬化性樹脂が、熱硬化性エラストマーであってもよい。 In one aspect of the present invention, in the method for producing the surface modifying member, the thermosetting resin may be a thermosetting elastomer.
　本発明の一態様において、前記表面改質部材の製造方法は、前記熱硬化性樹脂が、二重結合を含まない非ジエン系ゴムであってもよい。 In one aspect of the present invention, in the method for producing the surface modifying member, the thermosetting resin may be a non-diene rubber that does not contain a double bond.
　本発明の一態様において、前記表面改質部材の製造方法は、前記熱硬化性樹脂が、シリコーン系樹脂またはシリコーンゴムであってもよい。 In one aspect of the present invention, in the method for producing the surface modifying member, the thermosetting resin may be a silicone resin or a silicone rubber.
　本発明の一態様に係る表面改質シートは、熱硬化性樹脂との接着力に優れ、むら無く表面改質層を形成できる。
　また、表面改質部材の形成の際に表面改質層と熱硬化性樹脂と一体成形し得る表面改質シートを提供可能である。 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.
表面改質部材の一例を示す概略断面図である。It is a schematic sectional drawing which shows an example of a surface modification member. 表面改質シートの一例を示す概略断面図である。It is a schematic sectional drawing which shows an example of a surface modification sheet. 離型シートと表面改質層の積層体である表面改質シートの表面改質層側を熱可塑性樹脂の表面の少なくとも一部に載置する形態を示す概略断面図である。It is a schematic sectional drawing which shows the form which mounts the surface modification layer side of the surface modification sheet | seat which is a laminated body of a release sheet and a surface modification layer in at least one part of the surface of a thermoplastic resin. 塗装物の一例を示す概略断面図である。It is a schematic sectional drawing which shows an example of a coated material.
　本明細書において「熱硬化性樹脂の表面の少なくとも一部」とは、熱硬化性樹脂が有する全ての表面の中の少なくとも一部を意味する。例えば、熱硬化性樹脂が板状やシート状やフィルム状の場合は、その少なくとも一方の表面の一部や、その少なくとも一方の表面の全部などを意味する。 In this specification, “at least part of the surface of the thermosetting resin” means at least part of all the surfaces of the thermosetting resin. For example, when the 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.
　以下、本発明の実施形態について、詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail.
　本発明の実施形態に係る表面改質シートは離型シートと表面改質層とを備え、前記表面改質層は、熱硬化性樹脂と反応する成分を含有する。
　本発明の実施形態における表面改質シートは、表面改質層がシート状であるため部材等の表面に塗設するのではなく、載積することで積層体とすることや一体成形ができる。そのため、ハジキ発生等によるむらの発生を防ぎ部材等の表面に均一な厚みで表面改質層を形成することができる。また、部材の表面の一部に表面改質層を施す際には、はみだし等により歩留りが低下するのを抑制できる。 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.
　〔表面改質層〕
　本発明の実施形態における表面改質層は熱硬化性樹脂と反応する成分を含有する。表面改質層は熱硬化性樹脂と反応する成分を含有することにより、熱硬化性樹脂を含む部材等に用いると化学反応により化学結合を生じ、混合層を形成しやすくなる。それにより接着力に優れた表面改質層とすることができる。 [Surface modification layer]
The surface modification layer in the embodiment of the present invention contains a component that reacts with the thermosetting resin. When 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.
　（熱硬化性樹脂）
　熱硬化性樹脂としては、加熱することにより硬化反応する樹脂であれば特に制限はなく、例えば、熱硬化性エラストマー、フェノール系樹脂、アミノ系樹脂、不飽和ポリエステル系樹脂、エポキシ系樹脂、ポリウレタン系樹脂、シリコーン系樹脂、熱硬化性ポリイミド系樹脂等が挙げられる。 (Thermosetting resin)
The thermosetting resin is not particularly limited as long as it is a resin that cures when heated. For example, 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.
　熱硬化性樹脂は、熱硬化性エラストマーであってもよい。
　熱硬化性エラストマーとは、加熱硬化後、弾性変形する樹脂をいう。
　熱硬化性エラストマーとしては、硬化したものであっても未硬化のものであってもよく、例えば、二重結合を含むジエン系ゴム又は二重結合を含まない非ジエン系ゴムが挙げられる。
　熱硬化性エラストマーは、加熱により架橋するものであることが好ましく、熱硬化エラストマーの代表的な架橋方法としては、硫黄架橋、過酸化物架橋、樹脂架橋が挙げられる。 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.
　熱硬化性樹脂が、二重結合を含むジエン系ゴムであってもよい。
　熱硬化性樹脂が、二重結合を含むジエン系ゴムである場合、表面改質層が含有する熱硬化性樹脂と反応する成分は、ジエン系ゴムと硫黄架橋、過酸化物架橋、又は樹脂架橋する成分を含むことが好ましく、硬化剤を含むことがより好ましい。 The thermosetting resin may be a diene rubber containing a double bond.
When the thermosetting resin is 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.
　硫黄架橋や樹脂架橋では、硫黄ラジカルやハロゲン化物によってジエン系ゴムに含まれる二重結合の隣に位置する水素を引抜き、表面改質層が含有するポリマー成分中の二重結合と反応させることで、接着力が向上する。
　過酸化物架橋では過酸化物によって、ジエン系ゴムに含まれる二重結合部がラジカルとなり、表面改質層が含有するポリマー成分中の二重結合部位と反応することで接着力が向上する。 In sulfur crosslinking and resin crosslinking, hydrogen located next to the double bond contained in the diene rubber is extracted by sulfur radicals and halides, and reacted with the double bond in the polymer component contained in the surface modification layer. , Adhesion is improved.
In peroxide crosslinking, the double bond portion contained in the diene rubber becomes a radical due to the peroxide, and the adhesive force is improved by reacting with the double bond site in the polymer component contained in the surface modified layer.
　二重結合を含むジエン系ゴムとしては、例えば、天然ゴム（ＮＲ）、イソプレンゴム（ＩＲ）、ブタジエンゴム（ＢＲ）、スチレン－ブタジエンゴム（ＳＢＲ）、クロロプレンゴム（ＣＲ）、ニトリルゴム、ノルボルネンゴム（ＮＯＲ）、アクリロニトリルブタジエンゴム（ＮＢＲ）等が挙げられる。二重結合を含むジエン系ゴムとしては、ブタジエンゴムが好ましい。 Examples of the diene rubber containing a double bond 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. As the diene rubber containing a double bond, butadiene rubber is preferable.
　熱硬化性樹脂が、二重結合を含まない非ジエン系ゴムであってもよい。
　熱硬化性樹脂が、二重結合を含まない非ジエン系ゴムである場合、表面改質層が含有する熱硬化性樹脂と反応する成分は、非ジエン系ゴムと過酸化物架橋する基を含むことが好ましく、反応性を有する不飽和結合を有する基を含まないポリマー成分と過酸化物との混合物であることがより好ましい。
　過酸化物架橋では、過酸化物が熱分解によってラジカルが発生し、発生した過酸化物ラジカルによって、非ジエン系ゴムに含まれる炭素－炭素結合から水素を引き抜き、表面改質層が含有するポリマー成分中の二重結合部位と反応する。表面改質層が含有するポリマー成分が二重結合を含まないポリマー成分の場合、過酸化物によって非ジエン系ゴムとポリマー成分からも水素が引き抜かれるため、飽和結合間でも反応する。表面改質層が含有する熱硬化性樹脂と反応する成分が、非ジエン系ゴムと過酸化物架橋する基を含まない場合は、触媒を添加することで、シラノール縮合も可能である。 The thermosetting resin may be a non-diene rubber that does not contain a double bond.
When the thermosetting resin is 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.
In 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. In the case where 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. When 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.
　二重結合を含まない非ジエン系ゴムとしては、ニトリルゴム、エチレン・プロピレンゴム（ＥＰＭ）、エチレン・プロピレン・ジエンゴム（ＥＰＤＭ）、ブチルゴム（ＩＩＲ）、アクリルゴム（ＡＣＭ）、ウレタンゴム、塩素化ポリエチレン、多硫化ゴム、フッ素ゴム（ＦＫＭ）、シリコーンゴム、クロロスルホン化ポリエチレン、エピクロルヒドリンゴム（ＣＯ／ＥＣＯ）等が挙げられる。
　二重結合を含まない非ジエン系ゴムとしては、好ましくはシリコーンゴムである。 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.
　熱硬化性樹脂がシリコーン系樹脂またはシリコーンゴムであることが好ましい。
　例えば、熱硬化性樹脂がシリコーンゴムである場合、熱硬化性樹脂と反応する成分とシリコーンゴムとの反応は過酸化物架橋でありシリコーンゴムから水素を引きぬき発生したラジカルと熱硬化性樹脂と反応する成分の二重結合部位が反応する。また、表面改質層に二重結合部位が含まれてなくても、過酸化物によって表面改質層の炭素-炭素結合部位からも水素を引き抜き発生したラジカルとシリコーンゴムに発生したラジカルが反応する。 The thermosetting resin is preferably a silicone resin or silicone rubber.
For example, when the thermosetting resin is a 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.
　シリコーン系樹脂としては、本発明の効果を損なわない範囲で、任意の適切なシリコーン系樹脂を採用し得る。シリコーン系樹脂は、１種のみであっても良いし、２種以上であっても良い。このようなシリコーン系樹脂としては、常温で液状のシリコーン系樹脂であっても良いし、常温で固体状のシリコーン系樹脂であっても良い。また、このようなシリコーン系樹脂としては、縮合型のシリコーン系樹脂であっても良いし、付加型のシリコーン系樹脂であっても良く、付加型シリコーン系樹脂が好ましい。また、このようなシリコーン系樹脂としては、単独で乾燥させる１液型のシリコーン系樹脂（例えば、１液型の室温硬化性（ＲＴＶ）樹脂）であっても良いし、２液型のシリコーン系樹脂（例えば、２液型の室温硬化性（ＲＴＶ）樹脂）であっても良い。 As the silicone resin, 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. Such 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. Moreover, as such a silicone resin, a one-component silicone resin (for example, a one-component room temperature curable (RTV) resin) that is dried alone may be used, or a two-component silicone resin may be used. It may be a resin (for example, a two-component room temperature curable (RTV) resin).
　（熱硬化性樹脂と反応する成分）
　熱硬化性樹脂と反応する成分としては、熱硬化性樹脂と化学反応を起こす成分、または化学結合等の結合を生じる成分であれば特に限定されず、任意の成分を用いることが可能である。例えば、硬化剤、反応性を有する不飽和結合を有する基を含むポリマー成分、反応性を有する不飽和結合を有する基を含まないポリマー成分と過酸化物との混合物、ハロゲン化化合物等が挙げられ、硬化剤、反応性を有する不飽和結合を有する基を含むポリマー成分、または反応性を有する不飽和結合を有する基を含まないポリマー成分と過酸化物との混合物の少なくともいずれかを含むことがより好ましい。 (Component that reacts with thermosetting 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.
　表面改質層が熱硬化性樹脂と反応する成分を含有することにより、表面改質シートを、例えば表面改質部材に用いた際に、表面改質層中の熱硬化性樹脂と反応する成分と熱硬化性樹脂とが混合した混合層を形成して化学反応や化学結合を生じやすくなる。混合層は、熱硬化性樹脂の表面の少なくとも一部に表面改質層を設けて加熱溶着を行うことによって、表面改質層と熱硬化性樹脂の界面が溶融接触して溶着混合し、それによって得られる溶着混合部分の層である。
　また、更に硬化剤を含有することにより化学反応や化学結合がより生じやすくなる。 A component that reacts with the 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.
　熱硬化性樹脂が未硬化の熱硬化性樹脂である場合、熱硬化性樹脂と反応する成分が反応性を有する不飽和結合を有する基を含まないポリマー成分と過酸化物との混合物、硬化剤又は反応性を有する不飽和結合を有する基を含むポリマー成分を含むことが好ましく、反応性を有する不飽和結合を有する基を含むポリマー成分を含むことがより好ましく、硬化剤及び反応性を有する不飽和結合を有する基を含むポリマー成分を含むことが更に好ましい。未硬化の熱硬化性樹脂を加熱硬化する際に、熱硬化性樹脂と表面改質層の反応性を有する不飽和結合を有する基を含むポリマー成分、又は反応性を有する不飽和結合を有する基を含まないポリマー成分とが混合して化学反応や化学結合を生じやすくなるためである。 When the thermosetting resin is an uncured thermosetting resin, 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. Alternatively, it is preferable to include 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. It is further preferable to include a polymer component including a group having a saturated bond. 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.
　また、熱硬化性樹脂が硬化した熱硬化性樹脂である場合、熱硬化性樹脂と反応する成分が、反応性を有する不飽和結合を有する基を含まないポリマー成分と過酸化物との混合物、または硬化剤及び反応性を有する不飽和結合を有する基を含むポリマー成分を含むことが好ましく、硬化剤及び反応性を有する不飽和結合を有する基を含むポリマー成分を含むことがより好ましい。
　表面改質層に硬化剤及び反応性を有する不飽和結合を有する基を含むポリマー成分を含有させることで、硬化した熱硬化性樹脂と化学反応や化学結合させるためである。 In addition, when the thermosetting resin is a cured 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 group having an unsaturated bond, Alternatively, it is preferable to include a polymer component including a curing agent and a group having a reactive unsaturated bond, and it is more preferable to include a polymer component including a curing agent and a group having a reactive unsaturated bond.
This is because 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.
　熱硬化性樹脂と反応する成分が、反応性を有する不飽和結合を有する基を含むポリマー成分である場合、反応性を有する不飽和結合を有する基を含むポリマー成分は、バインダーとして作用することで表面改質シートを形成し易くなる。
　反応性を有する不飽和結合としては、例えば、エチレン性二重結合、非芳香族性二重結合等が挙げられ、エチレン性二重結合であることが好ましい。
　エチレン性二重結合を有する基を含むポリマー成分としては、熱硬化性樹脂と反応するものであれば特に限定はなく、側鎖にエチレン性二重結合を有するポリマー成分であることが好ましい。熱硬化性樹脂と、エチレン性二重結合を有する基を含むポリマー成分の二重結合部位が化学反応することで、接着力が向上するためである。 When 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.
Examples of 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.
　反応性を有する不飽和結合を有する基を含むポリマー成分としては、エチレン性二重結合を有する基を含むポリマー成分が好ましく、例えば、イソブチレン系ポリマー、ブタジエン系ポリマー、イソプレン系ポリマー及びこれらより選択される少なくとも一種を含む共重合体のいずれかを含むことが好ましく、イソブチレン系ポリマー、又はブタジエン系ポリマー及びこれらより選択される少なくとも一種を含む共重合体のいずれかを含むことがより好ましい。 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.
　例えば、エチレン性二重結合を有する基を含むポリマー成分がブタジエン系ポリマーである場合、熱硬化性エラストマーのメチル基から水素引きぬきによってラジカルが発生し、ブタジエン系ポリマー中の二重結合部位とが反応する。 For example, when the polymer component containing a group having an ethylenic double bond is a butadiene-based polymer, 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.
　イソブチレン系ポリマーとしては、イソブチレンのホモポリマー（ホモイソブチレン）であってもよく、イソブチレンを主モノマーとするコポリマーであってもよい。該コポリマーは、例えば、イソブチレンとノルマルブチレンとの共重合体、イソブチレンとイソプレンとの共重合体（レギュラーブチルゴム、塩素化ブチルゴム、臭素化ブチルゴム、部分架橋ブチルゴム等）、これらの加硫物や変性物（例えば、水酸基、カルボキシル基、アミノ基、エポキシ基等の官能基で変性したもの）等が挙げられる。 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).
　ブタジエン系ポリマーとしては、ブタジエンのホモポリマーであってもよく、ブタジエンを主モノマーとするコポリマーであってもよい。該コポリマーは、例えば、ブタジエンとスチレンとの共重合体、ブタジエンとアクリロニトリルとの共重合体等が挙げられる。 The butadiene-based polymer may be a butadiene homopolymer or a copolymer containing butadiene as a main monomer. Examples of the copolymer include a copolymer of butadiene and styrene, a copolymer of butadiene and acrylonitrile, and the like.
　イソプレン系ポリマーとしては、イソプレンのホモポリマーであってもよく、イソプレンを主モノマーとするコポリマーであってもよい。該コポリマーは、例えば、イソプレンとイソブチレンとの共重合体等が挙げられる。 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.
　共重合体としては、例えば、スチレン・ブタジエン共重合体（ＳＢ）、スチレン・イソプレン共重合体（ＳＩ）、等のスチレン系ＡＢ型ジブロック共重合体（ジブロック共重合体）；スチレン・ブタジエン・スチレン共重合体（ＳＢＳ）、スチレン・イソプレン・スチレン共重合体（ＳＩＳ）等のスチレン系ＡＢＡ型ブロック共重合体（トリブロック共重合体）；スチレン・ブタジエン・スチレン・ブタジエン共重合体（ＳＢＳＢ）、スチレン・イソプレン・スチレン・イソプレン共重合体（ＳＩＳＩ）等のスチレン系ＡＢＡＢ型ブロック共重合体（テトラブロック共重合体）；スチレン・ブタジエン・スチレン・ブタジエン・スチレン共重合体（ＳＢＳＢＳ）、スチレン・イソプレン・スチレン・イソプレン・スチレン共重合体（ＳＩＳＳＩＳ）等のスチレン系ＡＢＡＢＡ型ブロック共重合体（ペンタブロック共重合体）；これらの構成単位を有するマルチブロック共重合体；スチレン・ブタジエン共重合体；スチレン・イソプレンランダム共重合体などを主剤としたものが挙げられ、スチレン・イソプレン・スチレン共重合体（ＳＩＳ）が好ましい。 Examples of the copolymer 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 (SISI); styrene / butadiene / styrene / butadiene / styrene copolymer (SBSBS), styrene・ Isoprene, styrene, isoprene, styrene copolymer (SIS IS) and other styrene-based ABABA block copolymers (pentablock copolymers); multiblock copolymers having these structural units; styrene / butadiene copolymers; styrene / isoprene random copolymers and the like as main ingredients Styrene / isoprene / styrene copolymer (SIS) is preferable.
　熱硬化性樹脂と反応する成分が、反応性を有する不飽和結合を有する基を含まないポリマー成分と過酸化物との混合物である場合は、過酸化物によって反応性を有する不飽和結合を有する基を含まないポリマー成分からも水素が引きぬかれるため、熱硬化性樹脂がシリコーンゴムである場合、シリコーンゴムと反応性を有する不飽和結合を有する基を含まないポリマー成分とが反応する。 When 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.
　過酸化物としては、例えば、有機過酸化物が挙げられる。有機過酸化物は、分子中に酸素－酸素（－Ｏ－Ｏ－）結合を有する化合物であり、この酸素－酸素（－Ｏ－Ｏ－）結合は熱により比較的容易に切断されて、反応性に富むラジカルが生成する。有機過酸化物として具体的には、ハイドロパーオキサイド、ジアルキルパーオキサイド、パーオキシエステル、ジアシルパーオキサイド、パーオキシジカーボネート、パーオキシモノカーボネート、パーオキシケタール、アルキルパーオキシエステル又はケトンパーオキサイド等が挙げられる。 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.
　反応性を有する不飽和結合を有する基を含まないポリマー成分としては、例えば、スチレン系ポリマー、ポリウレタン系ポリマー、ポリエステル系ポリマー、ポリアミド系ポリマー、（メタ）アクリル系ポリマーから選ばれる少なくとも１種であることが好ましい。 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.
　スチレン系ポリマーとしては、スチレン・ブチレン共重合体等のスチレン系ＡＢ型ジブロック共重合体（ジブロック共重合体）；スチレン・ブチレン・スチレン共重合体等のスチレン系ＡＢＡ型ブロック共重合体（トリブロック共重合体）；スチレン－エチレン－ブチレン－スチレンブロック共重合体（ＳＥＢＳ）、スチレン－エチレン－プロピレン－スチレンブロック共重合体（ＳＥＰＳ）等が挙げられる。 Examples of 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 copolymer); styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (SEPS), and the like.
　ポリウレタン系ポリマーとしては、ポリエステル又はポリエーテルとイソシアナートを主剤としたものが挙げられる。 Examples of polyurethane-based polymers include those based on polyester or polyether and isocyanate.
　ポリエステル系ポリマーとしては、例えば、飽和ポリエステル（例えば、ポリエチレンテレフタレート、ポリブチレンテレフタレートなど）と、変性ポリオレフィン（例えば、アクリル酸変性ポリエチレン、アクリル酸変性ポリプロピレンなどの酸変性ポリオレフィン；エポキシ変性ポリオレフィンなど）またはゴム系ポリマー（例えば、エチレン－プロピレンゴム、ポリエステルエラストマー、エチレン－アクリルゴムなどの熱可塑性エラストマーなど）とのブレンド；ポリエチレンナフタレートを主剤としたものが挙げられる。 Examples of the polyester polymer 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 rubber, polyester elastomer, ethylene-acrylic rubber); those based on polyethylene naphthalate.
　ポリアミド系ポリマーとしては、アミノ酸、ラクタムあるいはジアミンとジカルボン酸を主剤としたものが挙げられる。例えば、ナイロン６やナイロン６６などが挙げられる。 Examples of polyamide polymers include those based on amino acids, lactams or diamines and dicarboxylic acids. Examples include nylon 6 and nylon 66.
　（メタ）アクリル系ポリマーとしては、アクリル酸エチル、アクリル酸ブチル、アクリル酸２－エチルヘキシル、アクリル酸イソオクチル、アクリル酸イソノニルなどの（メタ）アクリル酸アルキルエステルを主成分とし、これらに必要によりアクリロニトリル、酢酸ビニル、スチレン、メタクリル酸メチル、アクリル酸、無水マレイン酸、ビニルピロリドン、グリシジルメタクリレート、ジメチルアミノエチルメタクリレート、ヒドロキシエチルアクリレート、アクリルアミドなどの改質用単量体を加えてなる単量体の重合体を主剤としたものが挙げられる。 As the (meth) acrylic polymer, 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.
　主剤とは、含有成分中で最も大きな質量割合を占める成分とする。 The main agent is a component that occupies the largest mass ratio among the contained components.
　硬化剤としては、熱硬化性樹脂と反応するものであっても、熱硬化性樹脂と反応性を有する不飽和結合を有する基を含むポリマー成分との反応を促進するものであってもよく、特に制限は無いが、シラン系硬化剤、有機チタン系硬化剤、アミン系硬化剤、イミダゾール系硬化剤、酸無水物系硬化剤から選ばれる少なくとも１種であることが好ましい。中でも、シラン系硬化剤、又は有機チタン系硬化剤であることがより好ましく、有機チタン系硬化剤であることが更に好ましい。二種以上の硬化剤を組み合わせて使用してもよく、シラン系硬化剤及び有機チタン系硬化剤を併用することが好ましい。 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 | limiting in particular, It is preferable that it is at least 1 sort (s) chosen from a silane type hardening | curing agent, an organic titanium type hardening | curing agent, an amine type hardening | curing agent, an imidazole type hardening | curing agent, and an acid anhydride type hardening | curing agent. Among these, 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.
　シラン系硬化剤としては、シリコーンアルコキシオリゴマー、アルコキシシラン等が挙げられる。
　有機チタン系硬化剤としては、テトラブチルチタネート、テトラエチルチタネート、テトライソプロピルチタネート、テトラフェニルチタネート等が挙げられる。
　アミン系硬化剤としては、３級アミン化合物としてポリエチレンイミンとして「エポミン」（登録商標）シリーズ（株式会社日本触媒製）等が挙げられる。
　イミダゾール系硬化剤としては、「キュアゾール」シリーズ（イミダゾール系エポキシ樹脂硬化剤、四国化成工業株式会社）等が挙げられる。
　酸無水物系硬化剤としては、メチルテトラヒドロ無水フタル酸や（メチル）ヘキサヒドロ無水フタル酸等が挙げられる。 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.
　表面改質層における上記硬化剤の含有量としては、特に限定されないが、反応性を有する不飽和結合を有する基を含むポリマー成分１００質量部に対して、転写性の観点から、好ましくは１０質量部以上であり、より好ましくは５０質量部以上、更に好ましくは７０質量部以上である。また、接着力のため、好ましくは１０００質量部以下であり、より好ましくは５００質量部以下、更に好ましくは４００質量部以下、特に好ましくは２００質量部以下である。
　二種以上の硬化剤を組み合わせて使用する場合は、硬化剤の合計量が上記の範囲となればよい。 Although it does not specifically limit as content of the said hardening | curing agent in a surface modification layer, From a transferable viewpoint, Preferably it is 10 mass with respect to 100 mass parts of polymer components containing the group which has a reactive unsaturated bond. Part or more, more preferably 50 parts by weight or more, and still more preferably 70 parts by weight or more. Moreover, for adhesive force, Preferably it is 1000 mass parts or less, More preferably, it is 500 mass parts or less, More preferably, it is 400 mass parts or less, Most preferably, it is 200 mass parts or less.
When using combining 2 or more types of hardening | curing agents, the total amount of a hardening | curing agent should just become said range.
　表面改質層は、熱硬化性樹脂と反応する成分として、ハロゲン化化合物を含有してもよい。ハロゲン化化合物としては、例えば、塩素系化合物が挙げられ、塩素系ポリマーであることが好ましく、塩素化ポリプロピレンであることがより好ましい。 The surface modification layer may contain a halogenated compound as a component that reacts with the thermosetting resin. Examples of the halogenated compound include chlorinated compounds, which are preferably chlorinated polymers, and more preferably chlorinated polypropylene.
　例えば、塩素系化合物を含有する表面改質層を、熱硬化性樹脂を含む部材等に用いる際は、後述する表面改質組成物を熱硬化性樹脂を含む部材等に塗布してもよく、シート化した表面改質層を熱硬化性樹脂を含む部材等に熱転写してもよく、熱転写することが好ましい。特に、熱硬化性樹脂が二重結合を含むジエン系ゴムである場合、熱転写することが好ましい。
　塩素系化合物を含有する表面改質層をシート化して熱転写することで、ハジキやはみだしの発生を抑制し、熱硬化樹脂部材に塩素系化合物を含有する表面改質層を均一に形成することが可能であり、安定した接着力を発現することができる。 For example, 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. In particular, when the thermosetting resin is a diene rubber containing a double bond, it is preferable to perform thermal transfer.
By forming a surface modified layer containing a chlorine-based compound into a sheet and performing thermal transfer, it is possible to suppress the occurrence of repellency and protrusion and uniformly form a surface modified layer containing a chlorine-based compound on a thermosetting resin member. It is possible and can express the stable adhesive force.
　表面改質層は後述する表面改質組成物を用いて形成することができる。
　表面改質組成物としては、表面改質層を構成する成分を溶剤に溶解した溶液が挙げられる。例えば、上記反応性を有する不飽和結合を有する基を含むポリマー成分又は反応性を有する不飽和結合を有する基を含まないポリマー成分を主成分とし、必要に応じて硬化剤又は過酸化物を含む混合物を慣用の方法により溶液に浸漬して、熱攪拌することでポリマー溶液を得て、これに必要に応じて架橋剤等を添加することにより調製してもよい。 The surface modification layer can be formed using a surface modification composition described later.
As a surface modification composition, the solution which melt | dissolved the component which comprises a surface modification layer in the solvent is mentioned. For example, 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.
　表面改質層は、必要に応じて、更に、任意の適切な添加剤を含み得る。該添加剤としては、例えば、開始剤、架橋剤、粘着付与剤、可塑剤、顔料、染料、充填剤、老化防止剤、導電材、帯電防止剤、紫外線吸収剤、光安定剤、剥離調整剤、軟化剤、界面活性剤、難燃剤、酸化防止剤等が挙げられる。 The surface modification layer may further contain any appropriate additive as required. Examples of 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.
　表面改質層の厚みは、接着力の観点から、好ましくは０．００１μｍ以上であり、より好ましくは０．０１μｍ以上であり、さらに好ましくは０．０５μｍ以上である。また、接着力の観点から好ましくは１００μｍ以下であり、より好ましくは３０μｍ以下であり、さらに好ましくは１０μｍ以下である。 The thickness of the surface modification layer is preferably 0.001 μm or more, more preferably 0.01 μm or more, and further preferably 0.05 μm or more from the viewpoint of adhesive strength. Further, from the viewpoint of adhesive strength, it is preferably 100 μm or less, more preferably 30 μm or less, and further preferably 10 μm or less.
　〔離型シート〕
　離型シートとしては、特に限定されないが、耐熱性が１００℃以上であることが好ましく、１００℃における引張弾性率が１ＧＰａ以下であることが好ましい。また、非シリコン系の樹脂シートであることが好ましく、例えば、フッ素樹脂シートフィルム（日東電工製、ニトフロン）、ポリエステル樹脂シート、ポリメチルペンテン樹脂シート（三井化学東セロ製、オピュラン（登録商標））、ポリスチレン樹脂シート（クラボウ製、オイディス（登録商標））などが挙げられる。
　離型シートの厚みは、形状追従性の観点から、好ましくは１μｍ～１０００μｍであり、より好ましくは１０μｍ～５００μｍであり、さらに好ましくは１０μｍ～３００μｍであり、特に好ましくは５μｍ～２００μｍである。 [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 μm to 1000 μm, more preferably 10 μm to 500 μm, still more preferably 10 μm to 300 μm, and particularly preferably 5 μm to 200 μm from the viewpoint of shape followability.
〔表面改質シートの製造〕
　表面改質シートは、任意の適切な方法によって製造し得る。例えば、表面改質層の材料と溶剤を含む溶液（表面改質組成物）への離型シートのディッピングの後に必要に応じて乾燥する方法、離型シートの表面への表面改質組成物の刷毛塗りの後に必要に応じて乾燥する方法、離型シートの表面への表面改質組成物の各種コーターによる塗布の後に必要に応じて乾燥する方法、離型シートの表面への表面改質組成物のスプレー塗布の後に必要に応じて乾燥する方法などが挙げられる。 [Production of surface modified sheet]
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.
　表面改質組成物としては、表面改質層を構成する材料を、溶剤に溶解した溶液が挙げられる。
　溶剤としては、例えば、メタノール、エタノール、イソプロピルアルコールなどのアルコール類；メチルエチルケトンなどのケトン類；エステル；脂肪族、脂環族、並びに芳香族炭化水素；ハロゲン化炭化水素；ジメチルホルムアミドなどのアミド類；ジメチルスルホキシドなどのスルホキシド類；ジメチルエーテル、テトラヒドロフランなどのエーテル類；などが挙げられる。溶剤は、１種のみであってもよいし、２種以上であってもよい。 As a surface modification composition, the solution which melt | dissolved the material which comprises a surface modification layer in the solvent is mentioned.
Examples of 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.
　表面改質組成物における固形分濃度は、目的に応じて適宜設定し得る。取り扱い性の簡便さ等の観点から、質量割合として、好ましくは０．０１質量％～８０質量％であり、より好ましくは０．０５質量％～６０質量％であり、さらに好ましくは０．１質量％～５０質量％である。 The solid content concentration in the surface modifying composition can be appropriately set according to the purpose. From the viewpoint of ease of handling and the like, 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.
　表面改質組成物には、必要に応じて、ｐＨ調整剤、架橋剤、粘度調整剤（増粘剤等）、レベリング剤、剥離調整剤、可塑剤、軟化剤、充填剤、着色剤（顔料、染料等）、界面活性剤、帯電防止剤、防腐剤、老化防止剤、紫外線吸収剤、酸化防止剤、光安定剤等の各種の添加剤を含有してもよい。 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.
〔積層体〕
　本発明の実施形態に係る積層体は、熱硬化性樹脂の表面に表面改質層が積層された積層体であって、熱硬化性樹脂と表面改質層との間に、該熱硬化性樹脂と該表面改質層とが混合した混合層を備えることが好ましい。
　積層体は、更に他の樹脂成分を含む層を有していても良く、他の樹脂成分は熱可塑性樹脂でもあってもよく、熱硬化性樹脂であってもよい。 [Laminate]
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.
〔表面改質部材〕
　本発明の実施形態に係る表面改質部材は、熱硬化性樹脂の表面に表面改質層が積層された表面改質部材であって、前記表面改質層は、前記熱硬化性樹脂と反応する成分を含有し、前記熱硬化性樹脂と、前記表面改質層とが化学反応により結合したものである。
　表面改質部材は、熱硬化性樹脂と表面改質層との間に、該熱硬化性樹脂と該表面改質層とが混合した混合層を備えることが好ましく、混合層において熱硬化性樹脂と、前記表面改質層とが化学反応により結合することが好ましい。 [Surface modification material]
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.
　熱硬化性樹脂、熱硬化性エラストマー及び表面改質層としては、上述の説明をそのまま援用し得る。 As the thermosetting resin, the thermosetting elastomer, and the surface modification layer, the above description can be used as it is.
　混合層は、熱硬化性樹脂と該表面改質層とが混合した層であり、熱硬化性樹脂の表面の少なくとも一部に表面改質層を設けて加熱溶着を行うことによって、表面改質層と熱硬化性樹脂の界面が溶融接触して溶着混合し、それによって得られる溶着混合部分の層である。 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.
　混合層の厚みは、加熱溶着の条件や、熱硬化性樹脂や表面改質層の種類に応じて、適宜決定し得る。混合層の厚みは、好ましくは１．５ｎｍ以上であり、より好ましくは２．０ｎｍ以上である。 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.
　本発明の実施形態に係る表面改質部材において、熱硬化性樹脂の厚みとしては、例えば、０．００１ｍｍ～１００ｍｍである。 In the surface modifying member according to the embodiment of the present invention, the thickness of the thermosetting resin is, for example, 0.001 mm to 100 mm.
　本発明の実施形態に係る表面改質部材において、表面改質層の厚みは、特に制限は無く、好ましくは０．００１μｍ～１００μｍであり、より好ましくは０．０１μｍ～１０μｍであり、さらに好ましくは０．０５μｍ～５μｍであり、特に好ましくは０．１μｍ～３μｍである。 In the surface modified member according to the embodiment of the present invention, the thickness of the surface modified layer is not particularly limited, is preferably 0.001 μm to 100 μm, more preferably 0.01 μm to 10 μm, and still more preferably. The thickness is 0.05 to 5 μm, particularly preferably 0.1 to 3 μm.
　本発明の実施形態に係る表面改質部材は、好ましくは、本発明の表面改質部材の製造方法によって得られる。 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.
　本発明の実施形態に係る塗装物は、表面改質部材の表面改質層側の表面の少なくとも一部に塗膜を備えたものである。
　表面改質層がシート状に形成された表面改質シートを用いて形成されているため、部材の表面に塗布では発生していたハジキ等によるむらの発生を防ぐことができる。また、表面改質層がシート状になっているため、部材の表面に均一な厚みで形成することができる。
　塗膜としては、特に制限されず、例えば、ポリエステル・メラミン系、アルキド・メラミン系、アクリル・メラミン系、アクリル・ウレタン系、アクリル・多酸硬化剤系、メッキ処理などの各種塗膜が挙げられる。
　塗膜の塗装方法に特に制限は無く、刷毛塗り、ローラー塗装、スプレー塗装、各種コーター塗装などの一般的な方法を用いることができ、その塗布量は特に限定されるものではない。また、塗膜を加熱する時間や温度等も、用いる塗料、塗布量等によって適宜決定することができる。 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. .
There is no particular limitation on the 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. Moreover, the time, temperature, etc. which heat a coating film can be suitably determined with the coating material to be used, the application quantity, etc.
　本発明の実施形態に係る印刷物は、表面改質部材の表面改質層側の表面の少なくとも一部に印刷を施したものである。
　表面改質層はシート状の表面改質シートを用いて形成されるため、非印刷媒体の表面にむら無く形成することができる。また、３次元的な形状にも表面改質層をむら無く形成できるため、均一な膜厚の印刷物とすることができる。
　印刷としては、例えば、インクジェット印刷が挙げられる。 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.
　本発明の実施形態に係る接合体は、表面改質部材の表面改質層側の表面の少なくとも一部に接着剤を用いて物品を接合したものである。接合し得る物品としては、例えば、電子部品、自動車の外装部品（特にウェザーストリップなどの柔軟なゴム製中空部材など）、ボディーの保護用部品や装飾部品等が挙げられる。
　接着剤としては、特に制限されず、例えば、ゴム系接着剤、ウレタン系接着剤（アクリルウレタン系接着剤）、アクリル系接着剤、シリコーン系接着剤、ポリエステル系接着剤、ポリアミド系接着剤、エポキシ系接着剤、ビニルアルキルエーテル系接着剤、フッ素系接着剤などの公知の接着剤を用いることができる。上記の中でも、ゴム系接着剤、ウレタン（アクリルウレタン）系接着剤が特に好ましい。また、上記接着剤は単独でもよいし、２種以上の組み合わせでもよい。 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. Examples of 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. Moreover, the said adhesive agent may be individual, and 2 or more types of combinations may be sufficient as it.
＜表面改質部材の製造方法＞
　本発明の実施形態に係る表面改質部材の製造方法は、表面改質シートと、熱硬化性樹脂とを用いて成形した表面改質部材の製造方法であって、表面改質部材の成形工程中に熱硬化性樹脂の表面の少なくとも一部に表面改質層を設ける方法である。
　熱硬化性樹脂は、未硬化の熱硬化性樹脂である場合、熱硬化性樹脂と反応する成分が、反応性を有する不飽和結合を有する基を含まないポリマー成分と過酸化物との混合物、または反応性を有する不飽和結合を有する基を含むポリマー成分を含むことが好ましい。また、反応性を有する不飽和結合を有する基を含まないポリマー成分が、スチレン系ポリマー、ポリウレタン系ポリマー、ポリエステル系ポリマー、ポリアミド系ポリマー、（メタ）アクリル系ポリマーから選ばれる少なくとも１種であり、反応性を有する不飽和結合を有する基を含むポリマー成分が、イソブチレン系ポリマー、ブタジエン系ポリマー、イソプレン系ポリマー、及びこれらより選択される少なくとも一種を含む共重合体のいずれかを含むことが好ましい。 <Method for producing surface modified member>
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 In this method, a surface modification layer is provided on at least a part of the surface of the thermosetting resin.
When the thermosetting resin 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 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. Further, 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.
　熱硬化性樹脂が、硬化した熱硬化性樹脂である場合、熱硬化性樹脂と反応する成分が、反応性を有する不飽和結合を有する基を含まないポリマー成分と過酸化物との混合物、または硬化剤及び反応性を有する不飽和結合を有する基を含むポリマー成分を含むことが好ましい。また、エチレン性二重結合を有する基を含まないポリマー成分が、スチレン系ポリマー、ポリウレタン系ポリマー、ポリエステル系ポリマー、ポリアミド系ポリマー、（メタ）アクリル系ポリマーから選ばれる少なくとも１種であり、反応性を有する不飽和結合を有する基を含むポリマー成分が、イソブチレン系ポリマー、ブタジエン系ポリマー、イソプレン系ポリマー、及びこれらより選択される少なくとも一種を含む共重合体のいずれかを含み、硬化剤が、シラン系硬化剤、有機チタン系硬化剤、アミン系硬化剤、イミダゾール系硬化剤、酸無水物系硬化剤から選ばれる少なくとも１種であることが好ましい。 When the thermosetting resin is a cured thermosetting resin, 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. In addition, 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.
　熱硬化性樹脂、熱硬化性エラストマー、表面改質層、硬化剤、反応性を有する不飽和結合を有する基を含むポリマー成分、または反応性を有する不飽和結合を有する基を含まないポリマー成分と過酸化物との混合物としては、上述の説明をそのまま援用し得る。 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; As the mixture with the peroxide, the above description can be used as it is.
　本発明の実施形態に係る表面改質部材の製造方法においては、表面改質部材の成形工程中に熱硬化性樹脂の表面の少なくとも一部に前記表面改質層を設ける。
　成形方法としては、プレス成形、射出成形、ブロー成形等の公知の方法を適宜利用することができる。
　成形装置としては、熱プレス装置や射出成形装置、ダブルベルト型プレス成形装置を用いることができる。
　加熱方法としては、例えば、オーブン加熱、赤外線加熱、高周波加熱などが挙げられる。 In the method for producing a surface modified member according to the embodiment of the present invention, 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.
As a molding method, a known method such as press molding, injection molding, blow molding or the like can be appropriately used.
As the molding apparatus, 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.
　例えば、表面改質シートを予め金型内に固定した後、熱硬化性樹脂を金型内に充填し射出成形にて一体成形することにより、表面改質シートを成形工程中に熱硬化性樹脂の片面または両面に貼り合せ、熱硬化性樹脂の表面の少なくとも一部に前記表面改質層を設けることができる。
　また、板状またはフィルム状の熱硬化性樹脂に表面改質シートの表面改質層側が接するように載置して金型に配置する。そして、プレス成形にて一体成形して、表面改質シートを成形工程中に熱硬化性樹脂の片面または両面に貼り合せ、熱硬化性樹脂の表面の少なくとも一部に前記表面改質層を設けることができる。プレス成形によれば、熱硬化性樹脂の表面改質処理とともに、熱硬化性樹脂の成形加工も同時に行うことができるため、高い生産性と低コストを提供できる。 For example, after fixing the surface modified sheet in the mold in advance, 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 | places and arrange | positions in a metal mold | die so that the surface modification layer side of a surface modification sheet may contact plate-shaped or film-shaped thermosetting resin. Then, it is integrally formed by press molding, and the surface modified sheet is bonded to one or both sides of the thermosetting resin during the molding process, and the surface modified layer is provided on at least a part of the surface of the thermosetting resin. be able to. According to the press molding, since the thermosetting resin can be molded simultaneously with the surface modification treatment of the thermosetting resin, high productivity and low cost can be provided.
　成形時の加熱温度は、熱硬化性樹脂の種類および表面改質シートに使用する樹脂の種類によっても異なるため、適宜選択できるが、好ましくは４００℃以下である。 Since 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.
　成形時の圧力は、特に限定するものではなく、表面改質部材の形状や物性等を考慮して適宜決定することが好ましく、０～１０ＭＰａが好ましい。 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.
　表面改質シートと、熱硬化性樹脂とを一体成形した後に、離型シートを引き剥がすことにより、表面改質層が熱硬化性樹脂の表面に転写された状態になり、表面が改質された表面改質部材が得られる。離型シートは成形工程の前に剥離してもよいし、成形工程のいずれかの時点または成形工程後に剥離してもよい。
　このようにして、表面改質層と熱硬化性樹脂との接着性が良好で表面改質層の厚みが均一な表面改質部材を容易に得ることができる。 After the surface-modified sheet and the thermosetting resin are integrally formed, 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.
　上記の製造方法により、図１に示すように、樹脂１００の表面に表面改質層１０が設けられ、表面改質部材が得られる。ここでの樹脂１００は熱硬化性樹脂である。なお、図１においては、樹脂１００の表面に表面改質層１０が積層されているが、好ましくは、樹脂１００と表面改質層１０との間に、該樹脂（熱硬化性樹脂）と該表面改質層とが混合した混合層（図示せず）を備える。 By the above manufacturing method, as shown in FIG. 1, 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. In FIG. 1, 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.
　離型シートと表面改質層の積層体である表面改質シートは、図２に示すように、離型シート２０と表面改質層１０の積層体である表面改質シート２００である。 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.
　本発明の実施形態に係る表面改質部材の製造方法において、離型シートと表面改質層の積層体である表面改質シートの該表面改質層側を該樹脂（熱硬化性樹脂）の表面の少なくとも一部に載置する形態は、図３に示すように、表面改質シート２００を、該表面改質シート２００の表面改質層１０側が樹脂１００の表面側になるように該表面改質シート２００を該樹脂１００の表面に載置させた形態である。
　また、本発明の実施形態に係る塗装物の一例として、図４に樹脂１００の表面に表面改質層１０が設けられた表面改質部材の、表面改質層側の表面に塗膜３０を備えた塗装物３００を示す。 In the method for producing a surface modified member according to the embodiment of the present invention, 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). As shown in FIG. 3, 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. In this embodiment, the modified sheet 200 is placed on the surface of the resin 100.
Moreover, as an example of the coated material according to the embodiment of the present invention, 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.
　本発明の実施形態に係る表面改質部材は熱硬化性樹脂の表面の少なくとも一部が表面改質層により改質されているため、他の樹脂成分との接着力に優れ、熱可塑性樹脂にも優れた接着力を発揮する。表面改質部材に塗膜、印刷、物品の接合を施す際は、予め加熱する処理、コロナ放電処理、電子照射処理、紫外線照射処理、フレームプラズマ処理、大気圧プラズマ処理または低圧プラズマ処理等の前処理を施してもよいが、前処理を施さなくても充分な接着強度を有する塗装物、印刷物、及び接合体が得られる。 Since 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. When applying coatings, printing, and bonding of articles to the surface-modified member, 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.
　以下、実施例により本発明を具体的に説明するが、本発明はこれら実施例になんら限定されるものではない。 Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples.
〔評価〕
（接着力試験（１８０度ピール））
　引張試験機（装置名：オートグラフ　ＡＧ－ＩＳ、（株）島津製作所製）を用い、ＪＩＳ　Ｚ　０２３７：２００９に準拠して、引張速度３００ｍｍ／分、剥離角度１８０°の条件で、下記実施例１～７、比較例１～３、参考例、実施例１２、及び実施例１３で得られた接合体からＶＲ５３００を引きはがし、接着力（Ｎ／２０ｍｍ）を測定した。 [Evaluation]
(Adhesion test (180 degree peel))
Using a tensile tester (device name: Autograph AG-IS, manufactured by Shimadzu Corporation), in accordance with JIS Z 0237: 2009, under the conditions of a tensile speed of 300 mm / min and a peeling angle of 180 °, the following examples VR5300 was peeled off from the joined bodies obtained in 1 to 7, Comparative Examples 1 to 3, Reference Example, Example 12 and Example 13, and the adhesive strength (N / 20 mm) was measured.
＜接着力試験（Ｔ字ピール）＞
　引張試験機（装置名：オートグラフ　ＡＧ－ＩＳ、（株）島津製作所製）を用い、引張速度３００ｍｍ／分で、下記実施例８～１１、比較例４～６で得られた接合体を引きはがし、接着力（Ｎ／２０ｍｍ）を測定した。 <Adhesion test (T-peel)>
Using a tensile tester (device name: Autograph AG-IS, manufactured by Shimadzu Corporation), the joined bodies obtained in Examples 8 to 11 and Comparative Examples 4 to 6 below were drawn at a tensile speed of 300 mm / min. It peeled off and the adhesive force (N / 20mm) was measured.
〔実施例１〕
　下記表面改質層成分を配合した表面改質組成物（２０質量％トルエン溶液）を離型シート（Ｎｏ．９００ＵＬ、５０μｍ、日東電工株式会社製）に塗布乾燥（１２０℃×３ｍｉｎ）させて、厚み１μｍの表面改質層を備えた表面改質シートを作製した。
　作製した表面改質シートを、表面改質層側が内側になるように硬化型シリコーンゴム（品番：Ｋ－１２５、株式会社十川ゴム製）に載せ、プレス成形により熱転写（１６５℃×７ｍｉｎ）させ表面改質部材を作製した。プレス成形の熱処理で硬化型シリコーンゴム中に含まれる過酸化物によってシリコーンゴムと表面改質層が架橋される。
　その後、作製した表面改質部材の離型シートを剥がし、８０ｍｍ×２０ｍｍのＶＲ５３００（日東電工株式会社製、ＳＩＳ系粘着テープ（ＳＩＳブロックポリマー含有））を貼付し接合体を作製した。 [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 μm, 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 μm 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. 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.
　表面改質層成分：
　ＴＡ－２１（マツモトファインケミカル株式会社製、テトラブチルチタネート）　１００質量部
　ＯＦＳ－６６９７（ダウコーニング社製、シラン化合物）　　　　　　２００質量部
　ＱＴＣ３５２０（日本ゼオン株式会社製、ＳＩＳブロックポリマー）　１００質量部 Surface modification layer components:
TA-21 (manufactured by Matsumoto Fine Chemical Co., Ltd., tetrabutyl titanate) 100 parts by mass OFS-6597 (manufactured by Dow Corning, silane compound) 200 parts by mass QTC3520 (manufactured by Nippon Zeon Co., Ltd., SIS block polymer) 100 parts by mass
〔実施例２～７〕
　表面改質層の組成を表１のように変更した以外は、実施例１と同様にして表面改質シートを作製した。作製した表面改質シートを用いて実施例１と同様にして表面改質部材及び接合体を作製した。作製した接合体の評価結果を表１に示した。 [Examples 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.
〔比較例１〕
　硬化型シリコーンゴム（品番：Ｋ－１２５、株式会社十川ゴム製）に８０ｍｍ×２０ｍｍのＶＲ５３００（日東電工株式会社製、ＳＩＳ系粘着テープ（ＳＩＳブロックポリマー含有））を貼付し接合体を作製した。 [Comparative Example 1]
80 mm × 20 mm VR5300 (manufactured by Nitto Denko Corporation, SIS-based adhesive tape (containing SIS block polymer)) was attached to a curable silicone rubber (product number: K-125, manufactured by Togawa Rubber Co., Ltd.) to prepare a joined body.
〔比較例２〕
　下記表面改質層成分を配合した表面改質組成物（２０質量％トルエン溶液）を離型シート（Ｎｏ．９００ＵＬ、５０μｍ、日東電工株式会社製）に塗布乾燥（１２０℃×３ｍｉｎ）させて、厚み１μｍの表面改質層を備えた表面改質シートを作製した。
　作製した表面改質シートを、表面改質層側が内側になるように硬化型シリコーンゴム（品番：Ｋ－１２５、株式会社十川ゴム製）に載せ、プレス成形により熱転写（１６５℃×７ｍｉｎ）させ表面改質部材を作製した。
　その後、作製した表面改質部材の離型シートを剥がし、８０ｍｍ×２０ｍｍのＶＲ５３００（日東電工株式会社製、ＳＩＳ系粘着テープ（ＳＩＳブロックポリマー含有））を貼付し接合体を作製した。 [Comparative Example 2]
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 μm, 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 μm 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.
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.
　表面改質層成分：
　ＴＡ－２１（マツモトファインケミカル株式会社製、テトラブチルチタネート）　１００質量部
　ＯＦＳ－６６９７（ダウコーニング社製、シラン化合物）　　　　　　　　２００質量部 Surface modification layer components:
TA-21 (manufactured by Matsumoto Fine Chemical Co., Ltd., tetrabutyl titanate) 100 parts by mass OFS-6697 (manufactured by Dow Corning, silane compound) 200 parts by mass
［比較例３］
　未硬化のシリコーンゴム（ＫＥ９４９０－Ｕ（信越化学工業株式会社製）、Ｃ－８（信越化学工業株式会社製）の混合物（組成：ＫＥ９４９０－Ｕ（１００質量部）に対して、Ｃ－８（２質量部）を配合したシリコーンゴム））を加熱硬化（１６５℃×７ｍｉｎ）させた後、８０ｍｍ×２０ｍｍのＶＲ５３００（日東電工株式会社製、ＳＩＳ系粘着テープ（ＳＩＳブロックポリマー含有））を貼付し接合体を作製した。 [Comparative Example 3]
With respect to a mixture of 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)), C-8 ( 2 parts by mass))) is heated and cured (165 ° C. × 7 min), and then VR5300 of 80 mm × 20 mm (manufactured by Nitto Denko Corporation, SIS adhesive tape (containing SIS block polymer)) is applied. A joined body was produced.
〔参考例〕
　硬化型のシリコーンゴム（品番：Ｋ－１２５、株式会社十川ゴム製）に表面改質処理をせずにＮｏ．５３０３Ｗ（シリコーン系粘着テープ、日東電工株式会社製）を貼付させ接合体を作製した。 [Reference example]
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.
　実施例１～７、比較例１～３、及び参考例で作製した接合体の評価結果を、表１に示した。 Table 1 shows the evaluation results of the joined bodies produced in Examples 1 to 7, Comparative Examples 1 to 3, and Reference Example.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
（表面改質層成分）
　ＯＦＳ－６６９７（ダウコーニング株式会社製、シラン化合物）
　ＫＲ－５１３（信越化学工業株式会社製、シリコーンアルコキシオリゴマー）
　Ｘ－４１－１８０５（信越化学工業株式会社製、シリコーンアルコキシオリゴマー）
　ＴＡ－２１（マツモトファインケミカル株式会社製、テトラブチルチタネート）
　ＱＴＣ３５２０（日本ゼオン株式会社製、ＳＩＳブロックポリマー）
（熱硬化性樹脂）
　硬化：硬化型シリコーンゴム　Ｋ－１２５（株式会社十川ゴム製、シリコーンゴム）
　未硬化：未硬化型シリコーンゴム　ＫＥ９４９０－Ｕ（信越化学工業株式会社製）、Ｃ－８（信越化学工業株式会社製）の混合物（組成：ＫＥ９４９０－Ｕ（１００質量部）に対して、Ｃ－８（２質量部）を配合したシリコーンゴム） (Surface modification layer component)
OFS-6697 (manufactured by Dow Corning Co., Ltd., silane compound)
KR-513 (Shin-Etsu Chemical Co., Ltd., silicone alkoxy oligomer)
X-41-1805 (manufactured by Shin-Etsu Chemical Co., Ltd., silicone alkoxy oligomer)
TA-21 (Matsumoto Fine Chemical Co., Ltd., tetrabutyl titanate)
QTC3520 (Zeon Corporation, SIS block polymer)
(Thermosetting resin)
Curing: Curable silicone rubber K-125 (made by Togawa Rubber Co., Ltd., silicone rubber)
Uncured: Uncured silicone rubber KE9490-U (manufactured by Shin-Etsu Chemical Co., Ltd.), C-8 (manufactured by Shin-Etsu Chemical Co., Ltd.) (composition: KE9490-U (100 parts by mass), C- 8 (2 parts by mass) silicone rubber)
　ポリマー成分及び硬化剤を含有する実施例１～６に係る表面改質シートは、硬化型のシリコーンゴム及び未硬化型のシリコーンゴムのどちらに適用しても、ＳＩＳ系粘着テープに対し優れた接着力を発現した。その接着力は、シリコーン系粘着テープを接着した参考例と遜色ないものであった。
　実施例３～５に係る表面改質シートは、実施例６に係る表面改質シートよりも接着力が優れ、チタン系硬化剤とシリコーン硬化剤を併用することで、より優れた接着力が発現することが示された。
　硬化剤を含まない実施例７に係る表面改質シートは、未硬化のシリコーンゴムに適用した場合は優れた接着力を発揮した。
　一方、比較例２に係る表面改質シートは接着力が低く、表面改質シートを用いない比較例１及び３と同程度の接着力であった。 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.
On the other hand, 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.
（実施例８）
　表２に示す表面改質組成物を離型シート（Ｎｏ．９００ＵＬ、５０μｍ、日東電工株式会社製）に塗布乾燥（１２０℃×３ｍｉｎ）させて、厚み５μｍの表面改質層を備えた表面改質シートを作製した。作製した表面改質シートを、表面改質層側が内側になるようにブタジエンゴム（株式会社スタンダードテストピース製）に載せ、プレス成形により熱転写（１６０℃×５ｍｉｎ、圧力２ＭＰａ）させ表面改質部材（Ａ）を作製した。
　その後、表面改質部材（Ａ）の表面改質層側にポリウレタン（ＰＵ）接着剤を塗布乾燥（６０℃×５ｍｉｎ）させて、接着剤層を備えた表面改質部材（Ｂ）を作製した。そして、２枚の表面改質部材（Ｂ）の接着剤面同士を貼付させて、荷重約２０ｋｇ／ｍ２をかけて加熱保存（４０℃×２４ｈｒ）させて接合体を作製した。 (Example 8)
The surface modification composition shown in Table 2 was applied to a release sheet (No. 900UL, 50 μm, manufactured by Nitto Denko Corporation) and dried (120 ° C. × 3 min) to provide a surface modification layer having a 5 μm 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. × 5 min) on the surface modified layer side of the surface modified member (A) to produce a surface modified member (B) having an adhesive layer. . Then, the adhesive surfaces of the two surface modified members (B) were pasted together and heated and stored (40 ° C. × 24 hr) under a load of about 20 kg / m 2 to produce a joined body.
（実施例９～１３）
　表面改質層の組成、熱硬化性樹脂、及び接着剤を表２のように変更した以外は実施例８と同様にして表面改質部材及び接合体を作製した。 (Examples 9 to 13)
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.
（比較例４）
　熱硬化性樹脂としてブタジエンゴムにポリウレタン接着剤を塗布乾燥（６０℃×５ｍｉｎ）させて接着剤層を備えた熱硬化性樹脂体を作製した。そして、２枚の接着剤層を備えた熱硬化性樹脂体の接着剤面同士を貼付させて、荷重約２０ｋｇ／ｍ２をかけて加熱保存（４０℃×２４ｈｒ）させて接合体を作製した。 (Comparative Example 4)
A polyurethane adhesive was applied to butadiene rubber as a thermosetting resin and dried (60 ° C. × 5 min) to prepare a 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. .
（比較例５～６）
　熱硬化性樹脂や接着剤を表２のように変更した以外は比較例４と同様にして接合体を作製した。 (Comparative Examples 5 to 6)
A joined body was produced in the same manner as in Comparative Example 4 except that the thermosetting resin and the adhesive were changed as shown in Table 2.
　実施例８～１３、比較例４～６で作製した接合体の評価結果を、表２に示した。 Table 2 shows the evaluation results of the joined bodies produced in Examples 8 to 13 and Comparative Examples 4 to 6.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
（表面改質層成分）
　Ｐ７４０ＮＴ（ノーテープ工業株式会社製、クロロプレンゴム系接着剤）
　ＵＨ２１７０（東亜合成製、水酸基含有アクリルポリマー）
　ＲＣ－１０２８Ｋ（ロード・ジャパンインク製、塩素化ポリプロピレン）
　ＰＨＣＥＢ１４：アクリル系ポリマー（モノマー組成 ： ブチルアクリレート／エチルアクリレート／メタクリロイル基含有モノマー＝５０／５０／１７．６）
　ＵＣＥＣＯＡＴ７８５０：ダイセル・オルネクス株式会社製
（熱硬化性樹脂）
　ＢＲ：ブタジエンゴム（株式会社スタンダードテストピース製）
　ＩＩＲ：ブチルゴム（亜木津工業株式会社製）
　ＳＩＲ：シリコーンゴム（未硬化型シリコーンゴム　ＫＥ９４９０－Ｕ（信越化学工業株式会社製）、Ｃ－８（信越化学工業株式会社製）の混合物（組成：ＫＥ９４９０－Ｕ（１００質量部）に対して、Ｃ－８（２質量部）を配合したシリコーンゴム）
（接着剤）
　ポリウレタンゴム（ＰＵ）接着剤：ＡＳ－５６０（ノーテープ工業株式会社製、ポリウレタン樹脂）の固形分１００質量部に対して、硬化剤ＵＦＥ（ノーテープ工業株式会社製、イソシアネート化合物）を固形分で５質量部添加、攪拌して接着剤とした。
　クロロプレンゴム（ＣＲ）接着剤：９０００ＮＴ（ノーテープ工業株式会社製、クロロプレンゴム）の固形分１００質量部に対して、硬化剤ＵＦＥ（ノーテープ工業株式会社製、イソシアネート化合物）を固形分で３質量部添加、攪拌して接着剤とした。
（接着テープ）
　ＶＲ５３００：日東電工株式会社製、ＳＩＳ系粘着テープ
　Ｈ７００８：日東電工株式会社製、アクリルフォーム粘着テープ (Surface modification layer component)
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)
PHCEB14: acrylic polymer (monomer composition: butyl acrylate / ethyl acrylate / methacryloyl group-containing monomer = 50/50 / 17.6)
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
　ポリマー成分としてクロロプレンゴムを含有する実施例８及び１０に係る表面改質シートは、硬化型のブタジエンゴムに適用した場合、表面改質シートを用いなかった比較例４及び５に比べ、ＰＵ接着剤とＣＲ接着剤のどちらに対しても優れた接着力を発現した。
　ポリマー成分としてクロロプレンゴム及びＯＨ基含有ポリマーを含む実施例９は、実施例８に比べ更に優れた接着力を発現した。
　ポリマー成分として塩素化ポリプロピレンを含有する実施例１１に係る表面改質シートは、硬化型のブチルゴムに適用した場合、表面改質シートを用いなかった比較例６に比べ、アクリルフォーム対して優れた接着力を発現した。 When the surface modified sheet according to Examples 8 and 10 containing chloroprene rubber as a polymer component is applied to a curable butadiene rubber, the PU adhesive is compared with Comparative Examples 4 and 5 in which the surface modified sheet is not used. Excellent adhesion to both CR and CR adhesives.
Example 9 containing chloroprene rubber and an OH group-containing polymer as a polymer component exhibited a better adhesive force than Example 8.
When the surface modified sheet according to Example 11 containing chlorinated polypropylene as a polymer component was applied to a curable butyl rubber, the surface modified sheet was superior in adhesion to acrylic foam compared to Comparative Example 6 in which no surface modified sheet was used. Expressed power.
　以上、本発明の好ましい実施の形態について説明したが、本発明は、上述した実施の形態に制限されるものではなく、本発明の範囲を逸脱しない範囲において、上述した実施の形態に種々の変形及び置換を加えることができる。
　なお、本出願は、２０１８年４月２６日出願の日本特許出願（特願２０１８－０８５６７０）および２０１９年４月２４日出願の日本特許出願（特願２０１９－０８２９６０）に基づくものであり、その内容は本出願の中に参照として援用される。 The preferred embodiments of the present invention have been described above. However, the present invention is not limited to the above-described embodiments, and various modifications may be made to the above-described embodiments without departing from the scope of the present invention. And substitutions can be added.
This application is based on a Japanese patent application filed on April 26, 2018 (Japanese Patent Application No. 2018-085670) and a Japanese patent application filed on April 24, 2019 (Japanese Patent Application No. 2019-082960). The contents are incorporated by reference into this application.
１０　　　表面改質層
２０　　　離型シート
３０　　　塗膜
１００　　樹脂
２００　　表面改質シート
３００　　塗装物 DESCRIPTION OF SYMBOLS 10 Surface modification layer 20 Release sheet 30 Coating film 100 Resin 200 Surface modification sheet 300 Painted material

Claims (19)

  1. 　離型シートと表面改質層とを備え、
    　前記表面改質層は、熱硬化性樹脂と反応する成分を含有する表面改質シート。     With a release sheet and a surface modification layer,
    The surface modification layer is a surface modification sheet containing a component that reacts with a thermosetting resin.
  2. 　前記熱硬化性樹脂と反応する成分が、硬化剤、反応性を有する不飽和結合を有する基を含むポリマー成分、または反応性を有する不飽和結合を有する基を含まないポリマー成分と過酸化物との混合物の少なくともいずれかを含む、請求項１に記載の表面改質シート。 The component that reacts with the thermosetting resin is a curing agent, a polymer component containing a group having a reactive unsaturated bond, or a polymer component not containing a group having a reactive unsaturated bond and a peroxide. The surface-modified sheet according to claim 1, comprising at least one of the following mixtures.
  3. 　前記熱硬化性樹脂が、熱硬化性エラストマーである請求項１又は２に記載の表面改質シート。 The surface-modified sheet according to claim 1 or 2, wherein the thermosetting resin is a thermosetting elastomer.
  4. 　前記熱硬化性樹脂が、二重結合を含まない非ジエン系ゴムである請求項１又は２に記載の表面改質シート。 The surface-modified sheet according to claim 1 or 2, wherein the thermosetting resin is a non-diene rubber not containing a double bond.
  5. 　前記熱硬化性樹脂が、シリコーン系樹脂またはシリコーンゴムである請求項１又は２に記載の表面改質シート。 The surface-modified sheet according to claim 1 or 2, wherein the thermosetting resin is a silicone resin or silicone rubber.
  6. 　熱硬化性樹脂の表面に表面改質層が積層された表面改質部材であって、
    　前記表面改質層は、前記熱硬化性樹脂と反応する成分を含有し、
    　前記熱硬化性樹脂と、前記表面改質層とが化学反応により結合した表面改質部材。     A surface modification member in which a surface modification layer is laminated on the surface of a thermosetting resin,
    The surface modification layer contains a component that reacts with the thermosetting resin,
    A surface modification member in which the thermosetting resin and the surface modification layer are bonded by a chemical reaction.
  7. 　前記熱硬化性樹脂と反応する成分が、硬化剤、反応性を有する不飽和結合を有する基を含むポリマー成分、または反応性を有する不飽和結合を有する基を含まないポリマー成分と過酸化物との混合物の少なくともいずれかを含む、請求項６に記載の表面改質部材。 The component that reacts with the thermosetting resin is a curing agent, a polymer component containing a group having a reactive unsaturated bond, or a polymer component not containing a group having a reactive unsaturated bond and a peroxide. The surface modification member according to claim 6, comprising at least one of the following mixtures.
  8. 　前記熱硬化性樹脂が、熱硬化性エラストマーである請求項６又は７に記載の表面改質部材。 The surface modifying member according to claim 6 or 7, wherein the thermosetting resin is a thermosetting elastomer.
  9. 　前記熱硬化性樹脂が、二重結合を含まない非ジエン系ゴムである請求項６又は７に記載の表面改質部材。 The surface modifying member according to claim 6 or 7, wherein the thermosetting resin is a non-diene rubber containing no double bond.
  10. 　前記熱硬化性樹脂が、シリコーン系樹脂またはシリコーンゴムである請求項６に記載の表面改質部材。 The surface modifying member according to claim 6, wherein the thermosetting resin is a silicone resin or silicone rubber.
  11. 　請求項６～１０のいずれか１項に記載の表面改質部材の表面改質層側の表面の少なくとも一部に塗膜を備えた塗装物。 A coated article provided with a coating film on at least a part of the surface of the surface modifying member according to any one of claims 6 to 10 on the surface modifying layer side.
  12. 　請求項６～１０のいずれか１項に記載の表面改質部材の表面改質層側の表面の少なくとも一部に印刷を施した印刷物。 A printed matter obtained by printing on at least part of the surface of the surface modifying member according to any one of claims 6 to 10 on the surface modifying layer side.
  13. 　請求項６～１０のいずれか１項に記載の表面改質部材の表面改質層側の表面の少なくとも一部に接着剤を用いて物品を接合した接合体。 11. A joined body in which an article is joined to at least a part of the surface of the surface modifying member according to any one of claims 6 to 10 on the surface modifying layer side.
  14. 　請求項１～５のいずれか１項に記載の表面改質シートと、前記熱硬化性樹脂とを用いて成形した表面改質部材の製造方法であって、
    　前記表面改質部材の成形工程中に前記熱硬化性樹脂の表面の少なくとも一部に前記表面改質層を設ける表面改質部材の製造方法。     A method for producing a surface-modified member formed by using the surface-modified sheet according to any one of claims 1 to 5 and the thermosetting resin,
    A method for producing a surface modifying member, wherein the surface modifying layer is provided on at least a part of the surface of the thermosetting resin during the molding step of the surface modifying member.
  15. 　前記熱硬化性樹脂は、未硬化の熱硬化性樹脂であり、
    　前記熱硬化性樹脂と反応する成分が、反応性を有する不飽和結合を有する基を含まないポリマー成分と過酸化物との混合物、または反応性を有する不飽和結合を有する基を含むポリマー成分を含む請求項１４に記載の表面改質部材の製造方法。     The thermosetting resin 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. The manufacturing method of the surface modification member of Claim 14 containing.
  16. 　前記熱硬化性樹脂は、硬化した熱硬化性樹脂であり、
    　前記熱硬化性樹脂と反応する成分が、反応性を有する不飽和結合を有する基を含まないポリマー成分と過酸化物との混合物、または硬化剤及び反応性を有する不飽和結合を有する基を含むポリマー成分を含む請求項１４に記載の表面改質部材の製造方法。     The thermosetting resin 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. The manufacturing method of the surface modification member of Claim 14 containing a polymer component.
  17. 　前記熱硬化性樹脂が、熱硬化性エラストマーである請求項１４～１６のいずれか１項に記載の表面改質部材の製造方法。 The method for producing a surface modifying member according to any one of claims 14 to 16, wherein the thermosetting resin is a thermosetting elastomer.
  18. 　前記熱硬化性樹脂が、二重結合を含まない非ジエン系ゴムである請求項１４～１６のいずれか１項に記載の表面改質部材の製造方法。 The method for producing a surface modifying member according to any one of claims 14 to 16, wherein the thermosetting resin is a non-diene rubber containing no double bond.
  19. 　前記熱硬化性樹脂が、シリコーン系樹脂またはシリコーンゴムである請求項１４～１６のいずれか１項に記載の表面改質部材の製造方法。 The method for producing a surface modifying member according to any one of claims 14 to 16, wherein the thermosetting resin is a silicone resin or silicone rubber.
PCT/JP2019/017524 2018-04-26 2019-04-24 Surface-modified sheet, surface-modified member, coated article, printed article, joined body, and method for manufacturing surface-modified member WO2019208665A1 (en)

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US11345136B2 (en) * 2019-08-23 2022-05-31 Honda Motor Co., Ltd. Resin molded article and manufacturing method therefor
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