JP7359458B2 - Adhesive body - Google Patents

Description

The present invention relates to an adhesive body in which the surface of an adhesive base material made of resin or rubber, which is difficult to adhere to, is treated to adhere and integrate with a different type of base material to be adhered.

Fluorine-containing polymer materials made of fluororesin or fluororubber, silicone materials made of silicone resin or silicone rubber, adhesive base materials made of rubber such as ethylene-propylene-diene copolymer, and polymers. Adhesive substrates made of different materials such as resin, natural rubber, synthetic rubber, cross-linked rubber, metal, glass, or ceramics may have significantly different physicochemical properties or may exhibit tackiness or adhesion. Therefore, adhesion or adhesion cannot be achieved simply by making contact. Even when bonding is performed using a fluid curable adhesive, the adhesive force is very weak due to intermolecular forces. Furthermore, since the appropriate adhesive changes depending on the material of the base material, selecting the most suitable adhesive has to be done through trial and error, which takes a lot of time and effort.

Among them, solid substrates made of fluorine-containing polymeric materials have extremely low dielectric constant, low surface tension, excellent chemical stability, low solvent absorption/water absorption, and excellent thermal stability. Because of this, it is commonly used alone as packing in places where chemical resistance and heat resistance are required, but due to its extremely low surface tension, it cannot be bonded, composited, or integrated with other materials. It is extremely difficult.

As a surface modification method for a solid base material that activates the surface to facilitate adhesion, printing, and painting, Patent Document 1 describes a modifier containing a silane atom, a titanium atom, or an aluminum atom and having a boiling point of 10 to 100°C. It has been disclosed that the surface of a solid material, which is a rubber such as silicone rubber, fluororubber, or natural rubber, is completely or partially sprayed with a flame of fuel gas containing a compound. However, simple adhesion, printing, and painting only rely on intermolecular forces on the surface, and not only do they fail to show sufficient adhesive strength between the solid base material and other base materials, but also the surface of the solid base material is exposed to flame. There are problems in that it deteriorates during processing and cannot be precisely processed.

Therefore, composites using vulcanization adhesives are mainly used. For example, Patent Document 2 discloses a rubber laminate in which a vulcanizable rubber composition consisting of fluororubber and a quaternary ammonium salt derivative of triazinethiol and a vulcanizable rubber composition other than fluororubber are vulcanized and bonded together. Disclosed. However, it has the disadvantages of not being able to adhere to members with low heat resistance, large dimensional variations, and eroding the fine structure of the surface.

Further, Patent Document 3 discloses a method for manufacturing a resin composite in which a silicone resin is bonded to a fluororesin, in which a surface treatment is applied to the adhesive surface of the fluororesin to the silicone resin, and the adhesive surface is treated with the silicone resin. , a method for producing a resin composite in which addition reaction-curing silicone resin compositions or condensation reaction-curing silicone resin compositions to which a reactive radical-generating compound or peroxide is added is laminated and crosslinked and bonded is disclosed. There is. However, since the composition is laminated and crosslinked, it does not adhere solid objects together, and therefore lacks versatility.

Japanese Patent Application Publication No. 2002-35921 Japanese Patent Application Publication No. 05-320453 Japanese Patent Application Publication No. 2005-66914

The present invention was made in order to solve the above-mentioned problem, and the surface of a solid adhesive base material made of resin or rubber, which is difficult to adhere to, is treated and bonded to a different solid base material to be easily integrated. The purpose is to provide a highly versatile adhesive body.

The adhesive according to the present invention is selected from fluororesin, fluororubber, silicone resin, silicone rubber, ethylene-propylene-diene rubber, ethylene-propylene-diene-methylene rubber, isobutylene-isoprene copolymer rubber, isoprene rubber, and natural rubber. The above-mentioned molecular adhesive is graft-copolymerized via active groups on the electron beam irradiation-treated surface or the γ-ray irradiation treated surface of a solid adhesive base material to which the molecular adhesive is attached. Through a covalent bond between a molecule and a functional group on the surface of a solid substrate made of one selected from polymer resins, natural rubber, synthetic rubber, crosslinked rubber, metals, glass, and ceramics, The adhesive base material and the adhered base material are bonded and integrated.
Specifically, the present invention provides fluororesin, fluororubber, silicone resin, silicone rubber, ethylene-propylene-diene rubber, ethylene-propylene-diene-methylene rubber, isobutylene-isoprene copolymer rubber, isoprene rubber, and natural rubber. A solid adhesive base formed of any selected material and attached with any molecular adhesive selected from silanol compounds, aluminate compounds, titanate compounds, triazine ring-containing compounds, thiol compounds, epoxy compounds, and amine compounds. Molecules of the molecular adhesive graft copolymerized via free radicals on the electron beam irradiation treated surface or γ ray irradiation treated surface of the material, polymer resin, natural rubber, synthetic rubber, crosslinked rubber, metal, glass, and A hydroxyl group as a functional group on at least one selected from a corona-treated surface, an ultraviolet-treated surface, an excimer-treated surface, and an intro-treated surface of a solid substrate to be adhered formed of any selected from ceramics, or The adhesive body is characterized in that the adhesive base material and the adhesive base material are bonded and integrated by a covalent bond with a functional group on the molecular adhesive-treated surface of the adhesive base material. .

This adhesive body may be one in which the free radicals are present and/or generated on the surface of the adhesive base material.

In this adhesive body, the adhesive base material is, for example, one selected from vinylidene fluoride polymer, tetrafluoroethylene-propylene copolymer, and tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer. A fluorine-containing adhesive base material made of fluororesin or fluororubber is used.

In this adhesive body, the molecular adhesive-treated surface of the substrate to be adhered is treated with any molecular adhesive selected from a silanol compound, an aluminate compound, a titanate compound, a triazine ring-containing compound, a thiol compound, an epoxy compound, and an amine compound. The surface is treated with a chemical agent .

In this adhesive body, the molecular adhesive is, for example, a vinyl group-containing alkoxysiloxane .

In this adhesive body, the adhesive base material is a flexible film shape, a non-flexible plate shape, or a solid three-dimensional shape, and the adhered base material is a flexible film shape, a non-flexible plate shape, or a solid three-dimensional shape. It is preferably in the form of a solid plate or a solid three-dimensional shape.

The adhesive of the present invention is selected from fluororesin, fluororubber, silicone resin, silicone rubber, ethylene-propylene-diene rubber, ethylene-propylene-diene-methylene rubber, isobutylene-isoprene copolymer rubber, isoprene rubber, and natural rubber. Molecular bonding made by graft copolymerization of an adhesion base material made of any one of them and a base material to be adhered made of any one selected from polymer resins, natural rubber, synthetic rubber, crosslinked rubber, metals, glass, and ceramics. They are attached by molecular adhesion, which is a covalent bond between the molecules of the agent. As a result, even without using a curable adhesive, these adhesive base materials can be directly bonded to the same or different type of adhered base material, regardless of their respective materials or physical properties, or the degree of surface unevenness. It is strongly cross-linked and bonded by covalent bonds.

This adhesive adheres the two base materials by covalent bonding much more strongly and reliably than the adhesion by the intermolecular force of the fluid curable adhesive.

The adhesive base material is made of resin or rubber that is difficult to adhere to, especially fluorine-containing polymeric materials such as fluororesins and fluororubbers that have low surface tension, or silicone polymeric materials such as silicone resins and silicone rubber. Even if it is ethylene-propylene-diene-methylene rubber, isobutylene-isoprene copolymer rubber, isoprene rubber, natural rubber, etc., which are difficult to cross-link and bond, it is possible to bond the substrate and the molecular adhesive through the molecules. Strong cross-linked adhesion is possible through covalent bonds.

In this adhesive body, a pre-formed adhesive base material and a bonded base material bind molecular adhesive molecules between an active group on the surface of the adhesive base material and a functional group on the surface of the bonded base material. They are attached by covalent bonds.

The bonded body shares the adhesive base material with the adhered base material selected from the same or different types of natural rubber, synthetic rubber, resin, metal, semimetal, alloy, glass, and ceramics through a chemical bond that is a covalent bond. Because it is strongly bonded, it will not peel off even if it is bent or subjected to severe temperature changes. In addition, since the adhesive body does not rely on a fluid curable adhesive and adheres only through direct bonding between the adhesive base material and the adhered base material, the mixture of them is bonded on the adhesive surface. There is no risk of the adhesive extruding or peeling off due to the cured layer. Moreover, even if the adhesive base material and the adhered base material are flat or have a complex three-dimensional shape with unevenness, they are evenly and firmly adhered without corroding the fine structure of the surface.

Therefore, since the adhesive interface is bonded only by direct covalent bonds, the adhesive interface has little thermal deterioration and has excellent heat resistance, and especially fluorine-containing materials such as fluororesins and fluororubbers that have low surface tension. Even polymeric materials will not peel or tear under tension.

Hereinafter, embodiments for carrying out the present invention will be described in detail, but the scope of the present invention is not limited to these embodiments.

In a preferred embodiment of the adhesive of the present invention, molecules of a molecular adhesive graft copolymerized via active groups on the surface of a fluororubber adhesive substrate and the surface of a metal substrate to be bonded are bonded to each other. The adhesive base material and the adhered base material are bonded and integrated by a covalent bond formed by the functional group.

The adhesive base material and the adhered base material are formed in advance, and are, for example, in the form of a flexible film.

This adhesive body is applied to the surface of an adhesive base material that has been coated, coated, sprayed, or dipped with a composition containing a molecular adhesive and then treated with an electron beam, or the adhesive base material is subjected to an electron beam treatment. The surface of the adhesive substrate that has been coated, coated, sprayed, or dipped in a composition containing a molecular adhesive is brought into contact with the surface of the adhesive substrate to be adhered, thereby forming a fluororubber adhesive base. The adhesive base material and the adhered base material are bonded together by the covalent bond between the molecular adhesive molecules graft-copolymerized to the active groups on the surface of the material and the functional groups on the surface of the metal base material. and are integrated.

A bonding substrate is brought into contact with the surface of the bonding substrate, which has been coated, coated, sprayed, or immersed with a composition containing a molecular adhesive and then treated with an electron beam. It is preferable that the materials are bonded and integrated. When a molecular adhesive is applied to the surface of an adhesive base material and then subjected to electron beam treatment, the unstable active groups generated by the electron beam treatment immediately react with molecules of the molecular adhesive and graft copolymerize, which reduces reaction efficiency and production. High efficiency.

Since the fluororubber used as the adhesive base material is chemically extremely stable, the surface of the adhesive base material cannot normally be activated due to insufficient energy even when subjected to corona discharge or excimer treatment. However, when fluororubber is subjected to electron beam treatment, it is estimated that the surface will be oxidized to produce hydroxyl groups, fluorine-carbon bonds will be cleaved and hydrogen fluoride will be released, and fluorine radicals will be released and free radicals will be produced. The reaction mechanism produces active groups on the surface of the adhesive substrate. The molecules of the molecular adhesive react with this active group and form a covalent bond. The molecules of the molecular adhesive chemically bonded to the adhesive substrate react with functional groups on the surface of the adhered substrate to form a covalent bond. As a result, the adhesive base material and the adhered base material are covalently bonded and adhered to each other via the molecules of the molecular adhesive. Such chemical bonding of molecules of the molecular adhesive to the adhesive substrate results in graft copolymerization, so one molecule of the molecular adhesive bonded to one group of each active group of the adhesive substrate , reacts with one of the functional groups of the adhesive base material, and the adhesive base material and the adhesive base material are bonded and integrated by a covalent bond.

Adhesives are created by molecular adhesive molecules forming on the surface of an adhesive substrate like a comb, forming a single covalent bond with one molecule of molecular adhesive, and forming a monomolecular film with many molecules of molecular adhesive. The adhesive base material and the adhered base material are bonded and integrated by forming a layer.

Although the example has been explained in which electron beam treatment is applied to perform graft copolymerization, γ-ray treatment may also be used as long as it activates the surface of the adhesive base material and makes it easier to bond molecules of the molecular adhesive. A plurality of any of these processes may be performed.

The surface of such a graft copolymerized adhesive base material may be subjected to corona treatment, ultraviolet treatment, excimer treatment, and/or intro treatment before and/or after graft copolymerization.

The functional groups of the substrate to be adhered may be newly generated or amplified by subjecting the surface of the substrate to corona treatment, ultraviolet treatment, excimer treatment, or intro treatment, and It may be derived from raw material components and originally exposed on the surface.

An example in which the adhesive base material is made of fluororubber and the adhered base material is made of metal is shown, but the adhesive base material may be vinylidene fluoride polymer, tetrafluoroethylene-propylene copolymer, or tetrafluoroethylene - Fluororesin or fluororubber such as perfluoroalkyl vinyl ether copolymer; T unit which is a monoorganosiloxy unit, Q unit which is the siloxy unit, R ₃ SiO _1/2 unit (organo group R is the same or different) , an alkyl group, a phenyl group, or a group derived from a crosslinkable functional group), and/or a diorganosiloxy unit consisting of an R ₂ SiO unit (R is the same as above). MQ resins/rubbers, MDQ resins/rubbers, MTQ resins/rubbers, MDTQ resins/rubbers, TD resins/rubbers, TQ resins/rubbers, and TDQ resins/rubbers that contain and have D units that are For example, silicone resins and silicone rubbers such as polydimethylsilicone, polydiphenylsilicone, and modified silicones thereof, and more specifically, vinylmethylsiloxane/polydimethylsiloxane copolymers synthesized in the presence of a Pt catalyst. (molecular weight: 500,000-900,000), vinyl-terminated polydimethylsiloxane (molecular weight: 10,000-200,000), vinyl-terminated diphenylsiloxane/polydimethylsiloxane copolymer (molecular weight: 10,000-100,000), vinyl-terminated diethylsiloxane/polymer Dimethylsiloxane copolymer (molecular weight: 10,000 to 50,000), vinyl-terminated trifluoropropylmethylsiloxane/polydimethylsiloxane copolymer (molecular weight: 10,000 to 100,000), vinyl-terminated polyphenylmethylsiloxane (molecular weight: 01,000 to 1 10,000), vinylmethylsiloxane/dimethylsiloxane copolymer, trimethylsiloxane-terminated dimethylsiloxane/vinylmethylsiloxane/diphenylsiloxane copolymer, trimethylsiloxane-terminated dimethylsiloxane/vinylmethylsiloxane/ditrifluoropropylmethylsiloxane copolymer, trimethylsiloxane-terminated polyvinylmethyl Vinyl group-containing polysiloxane such as siloxane, H-terminated polysiloxane (molecular weight: 0,050,000 to 100,000), methyl H-siloxane/dimethylsiloxane copolymer, polymethyl H-siloxane, polyethyl H-siloxane, H-terminated polyphenyl (dimethyl H-siloxane) ) siloxane, methyl H siloxane/phenylmethyl siloxane copolymer, methyl H siloxane/octyl methyl siloxane copolymer, and other H group-containing polysiloxane-containing compositions made of cured products; ethylene-propylene-diene rubber: ethylene-propylene-diene - Methylene rubber (EPDM); isobutylene-isoprene copolymer rubber; isoprene rubber; and natural rubber.

The substrate to be adhered may be any one selected from natural rubber, synthetic rubber, crosslinked rubber, polymer resin, metal, glass, and ceramics.

As natural rubber, synthetic rubber, crosslinked rubber, and polymer resin for the base material to be adhered,
Addition crosslinked silicones; silicones such as vinyl methyl silicone (VMQ), methylphenyl silicone (PVMQ), fluoromethyl silicone (FVMQ), and dimethyl silicone (MQ), peroxide crosslinked silicones, condensation crosslinked silicones, UV crosslinked silicone type silicone, silicone exemplified by electron beam cross-linked silicone rubber, and silicone-based polymer resins such as co-blends of these silicones and olefins;
Polyvinyl chloride, polystyrene, s-polystyrene, -butadiene-styrene copolymer; polyamide; polymethacryacrylonitrile methyl lunate; polyphenylene sulfide; polyethylene terephthalate, polybutylene terephthalate; polycarbonate, cycloolefin polymer, polyester (meth)acrylate, epoxy (meth)acrylic resins, epoxy resins, cellulose and derivatives thereof, such as (meth)acrylates, urethane (meth)acrylates, polyether (meth)acrylates, and silicone (meth)acrylates, and pentaerythritol tetra(meth)acrylate; Hydroxyethyl cellulose, starch, cellulose diacetate, surface saponified vinyl acetate resin, low density polyethylene, high density polyethylene, i-polypropylene, petroleum resin, coumaron/indene resin, terpene resin, styrene/divinylbenzene copolymer, ABS resin, Polymethyl acrylate, polyethyl acrylate, polyacrylonitrile, polymethyl methacrylate, polyethyl methacrylate, polycyanoacrylate, polyvinyl acetate, polyvinyl alcohol, polyvinyl formal, polyvinyl acetal, polyvinyl chloride, vinyl chloride/vinyl acetate Copolymer, vinyl chloride/ethylene copolymer, polyvinylidene fluoride, vinylidene fluoride/ethylene copolymer, vinylidene fluoride/propylene copolymer, 1,4-trans polybutadiene, polyoxymethylene, polyethylene glycol, polypropylene glycol , phenol/formalin resin, cresol/formalin resin, resorcinol resin, melamine resin, xylene resin, toluene resin, gliptal resin, modified gliptal resin, unsaturated polyester resin, allyl ester resin, 6-nylon, 6,6-nylon, 6,10-nylon, polyimide, polyamide, polybenzimidazole, polyamideimide, silicone resin, silicone rubber, silicone resin, furan resin, polyurethane resin, polyphenylene oxide, polydimethylphenylene oxide, polyphenylene oxide or polydimethylphenylene oxide and triallyl Isocyanuric blends, (polyphenylene oxide or polydimethylphenylene oxide, triallylisocyanuric, peroxide) blends, polyxylene, polyphenylene sulfide, polysulfone, polyether sulfone, polyether ether ketone, polyimide, polytetrafluoroethylene, liquid crystal resin , Kevlar fiber, carbon fiber, natural rubber, butadiene rubber, 1,4-cis-butadiene rubber, isoprene rubber, isobutylene-isoprene rubber, polychloroprene, styrene-butadiene copolymer rubber, hydrogenated styrene-butadiene copolymer rubber, acrylonitrile, Butadiene copolymer rubber, hydrogenated acrylonitrile-butadiene copolymer rubber, polybutene rubber, polyisobutylene rubber, ethylene-propylene rubber, ethylene-propylene-diene rubber, ethylene oxide-epichlorohydrin copolymer rubber, chlorinated polyethylene rubber, Chlor Sulfonated polyethylene rubber, alkylated chlorosulfonated polyethylene rubber, chloroprene rubber, acrylic rubber, chlorinated acrylic rubber, brominated acrylic rubber, vinylidene fluoride, tetrafluoroethylene-propylene, and tetrafluoroethylene-purple orovinyl ether. Homopolymer rubbers such as fluororubber, epichlorohydrin and its copolymer rubber, chlorinated ethylene propylene rubber, chlorinated butyl rubber, brominated butyl rubber, tetrafluoroethylene, hexafluoropropylene, vinylidene fluoride and tetrafluoroethylene; Binary and ternary copolymer rubber, ethylene/tetrafluoroethylene copolymer rubber, propylene/tetrafluoroethylene copolymer rubber, ethylene acrylic rubber, epoxy rubber, urethane rubber;
can be mentioned.

Metals and alloys for the base material to be adhered include ordinary metals, functional metals, amorphous metals, fiber-reinforced metal blocks, shape memory alloys, superelastic alloys, etc., and metal shape classifications include plates, Includes sheets, films, square bars, round bars, spheres, hemispheres, fibers, nets, mesh wire cloth, films, sheets, complex circuit shapes, punching and cutting products, and on the periodic table are beryllium, magnesium, Calcium, strontium, barium, radium, scandium, yttrium, titanium, zirconium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, iron, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, Zinc, cadmium, mercury, aluminum, germanium, tin, lead, antimony, bismuth, neodymium, and the alloy composition includes iron alloys (steel, carbon steel, cast iron), copper alloys (phosphor bronze, brass). , cupronickel, beryllium copper, titanium copper), aluminum alloys (copper, manganese, silicon, magnesium, zinc, nickel alloys, etc.), magnesium alloys (Mg/Zn alloys, Mg/Ca alloys, etc.), zinc alloys, tin and tin Alloys, nickel alloys, gold alloys, silver alloys, platinum alloys, palladium alloys, lead alloys, titanium alloys (α type, β type and α + β type alloys), cadmium, zirconium alloys, cobalt alloys, chromium alloys, molybdenum alloys, tungsten alloys , manganese alloys, ferritic stainless steels, martensitic stainless steels, austinitic stainless steels, precipitation-strengthened stainless steels, nickel-titanium alloys, iron-manganese-titanium alloys, and superelastic alloys (nickel-titanium alloys). .

A silicon plate is an example of the metalloid material of the base material to be adhered.

Examples of the glass material of the substrate to be adhered include quartz, borosilicate glass, and alkali-free glass.

Ceramics of the base material to be bonded include ceramics, glass, cement, plaster, and enamel, which are hardened at high temperatures, and the composition is elemental (diamond, C) or oxide-based (alumina, Al ₂ O ₃ ). , zirconia type, hydroxide type (hydroxyapatite), carbide type (silicon carbide, SiC), carbonate type, nitride type (silicon nitride) (7 Halide type (fluorite), phosphate type (apatite) Also includes barium titanate, Bi ₂ Sr ₂ Ca ₂ Cu ₃ O ₁₀ , high temperature superconducting ceramics, boron nitride, ferrite, lead zirconate titanate, silicon carbide, silicon nitride, steatite (MgOSiO ₂ ). , YBa ₂ Cu ₃ O _7-δ , high-temperature superconducting ceramics, zinc oxide, aluminum nitride (AlN), silicon carbide (SiC), silicon nitride (Si ₃ N ₄ ), forsterite (2MgO・SiO ₂ ), steatite (MgO・SiO ₂ ), cordierite (2MgO・2Al ₂ O ₃・5SiO ₂ ), sialon (Si ₃ N ₄・Al ₂ O ₃ ), machinable ceramics, zircon (ZrO ₂・SiO ₂ ), Examples include barium titanate (BaTiO ₃ ), lead zirconate titanate (Pb(Zr,Ti)O ₃ ), ferrite (M ₂ O・Fe ₂ O ₃ ), mullite (3Al ₂ O ₃・2SiO ₂ ), etc. , Mg, Ti, Be, Ca, Li, Al, Mn, Zn, Cr, Ga, Fe, Cd, In, Ta, Co, Ni, Sn, Sb, Bi, Pb, Cu, and Ag. It may be a sintered body of an oxide of a binary alloy of these metal materials, a sintered body of an oxide of a ternary alloy, a sintered body of an oxide of a multi-component alloy, and a block, plate, or sheet. It also includes shapes such as films, square bars, round bars, spheres, hemispheres, fibers, and nets, as well as composite materials such as fiber-reinforced ceramics and carbon fiber-reinforced carbon.

An example in which both the adhesive base material and the adhered base material are in the form of a flexible film has been shown, but the adhesive base material may be in the form of a flexible film, a non-flexible plate, or a solid tertiary material. The original structure is three-dimensional, and the substrate to be adhered may be a flexible film, a non-flexible plate, or a solid three-dimensional structure.

Examples of molecular adhesives include silanol compounds, aluminate compounds, titanate compounds, triazine ring-containing compounds, thiol compounds, epoxy compounds, and amine compounds.

Silanol compounds include vinyltrimethoxysilane, vinyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N -β(aminoethyl)-γ-aminopropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-chloropropyltrimethoxysilane and the like.

Examples of the aluminate compound include acetoalkoxyaluminum diisopropylate, aluminum diisoproboxymonoethyl acetoacetate, aluminum trisethyl acetoacetate, aluminum trisacetylacetonate, and the like.

Titanate compounds include isopropyl tristearoyl titanate, isopropyl tris(dioctyl pyrophosphate) titanate, isopropyl tri(N-aminoethyl aminoethyl) titanate, tetraoctyl bis(ditridecyl phosphate) titanate, and tetra(2-2-diallyl). Examples include oxymethyl-1-butyl)bis(ditridecyl)phosphate titanate, bis(dioctylpyrophosphate)oxyacetate titanate, and bis(dioctylpyrophosphate)ethylene titanate.

（式(Ｉ)中、Ｗは、スペーサ基、例えば置換基を有していてもよいアルキレン基、アミノアルキレン基であってもよく、直接結合であってもよい。Ｙは、水酸基又は加水分解や脱離により水酸基を生成する反応性官能基、例えばトリアルコキシアルキル基である。－Ｚは、－Ｎ_３又は－ＮＲ^１Ｒ^２である（但し、Ｒ^１，Ｒ^２は同一又は異なりＨ又はアルキル基、－Ｒ^３Ｓｉ（Ｒ^４）_ｍ（ＯＲ^５）_３－ｍ[Ｒ^３，Ｒ^４はアルキル基、Ｒ^５はＨ又はアルキル基、ｍは０～２]。なお、アルキレン基、アルコキシ、アルキル基は、置換基を有していてもよい炭素数１～１２の直鎖状、分岐鎖状及び／又は環状の炭化水素基である。）で表わされるトリアジン化合物、例えば２，６－ジアジド－４－｛３－（トリエトキシシリル）プロピルアミノ｝－１，３，５－トリアジン；
などが挙げられる。 Examples of triazine ring-containing compounds include amino group-containing compounds such as triethoxysilylpropylamino-1,3,5-triazine-2,4-dithiol (TES) and aminoethylaminopropyltrimethoxysilane; triethoxysilylpropylamino A triazine compound having a trialkoxysilylalkylamino group and a mercapto group or an azide group, such as the following chemical formula (I)

(In formula (I), W may be a spacer group, for example, an alkylene group or aminoalkylene group which may have a substituent, or may be a direct bond. Y is a hydroxyl group or a hydrolyzable -Z is -N ₃ or -NR ¹ R ² (provided that R ¹ and R ² are the same or different and H or Alkyl group, -R ³ Si(R ⁴ ) _m (OR ⁵ ) _3-m [R ³ , R ⁴ are alkyl group, R ⁵ is H or alkyl group, m is 0 to 2].Alkylene group, alkoxy , the alkyl group is a linear, branched and/or cyclic hydrocarbon group having 1 to 12 carbon atoms which may have a substituent.), for example, 2,6- Diazido-4-{3-(triethoxysilyl)propylamino}-1,3,5-triazine;
Examples include.

Examples of thiol compounds include 6-alkoxysilylpropylamino-1,3,5-triazine-2,4-dithiol monosodium, 6-bis(3-alkoxysilylpropyl)amino-1,3,5-triazine-2, 4-dithiol monosodium, 6-N-cyclohexyl-N-(3-(triethoxysilyl)propylamino)-1,3,5-triazine-2,4-dithiol monosodium, 2,4-bis(2 -aminoethylamino)-6-(3-triethoxysilylpropylamino)-1,3,5-triazine, 2,4-dihydrazino-6-(3-triethoxysilylpropylamino)-1,3,5- Triazine, 6-alkoxysilylpropylamino-1,3,5-triazine-2,4-dithiol, 3-mercaptopropyltrimethoxysilane, 5-(bicycloheptynyl)triethoxysilane, (3-cyclopentadiene) (propyl)triethoxysilane, etc.

Epoxy compounds include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane Examples include.

Examples of amino compounds include 6-alkoxysilylpropylamine, 6-N-cyclohexyl-N-(3-(triethoxysilyl)propylamine), 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 4- Aminobutyltriethoxysilane, m-aminophenyltriethoxysilane, 11-aminoundecyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropylmethyldiethoxysilane, amino Examples include propylsilane triol, N-(2-aminoethyl)-3-aminopropylsilane triol, and (3-cyclopentazidienepropyl)triethoxysilane.

The electron beam treatment applied to the adhesion side surface of the adhesive base material may be performed using any method, such as a scanning method or an area beam method, with an accelerating voltage of 300 to 5 MeV and a total absorbed dose of 20 to 300 kGy. will be carried out.

As the gamma ray treatment applied to the adhesive side surface of the adhesive base material, for example, a cobalt radiation source, an iridium radiation source, a cesium radiation source, etc. may be used, and the total absorbed dose is 20 to 300 kGy at a radiation source strength of 1 T to 200 PBq. It will be held at

As the corona discharge treatment applied to the adhesive side surface of the adhesive base material or the adhesive side surface of the adhered base material, for example, an atmospheric pressure corona surface modification device (manufactured by Shinko Electric Measurement Co., Ltd., product name: Corona Master) can be used. For example, the test is carried out under the following conditions: power source: AC 100 V, output voltage: 0 to 20 kV, oscillation frequency: 0 to 40 kHz, 0.1 to 60 seconds, and temperature of 0 to 60°C. Such corona discharge treatment may be performed in a wet state with water, alcohols, acetones, esters, etc.

The atmospheric pressure plasma treatment applied to the adhesion side surface of the adhesion base material or the adhesion side surface of the adhered base material is performed using, for example, an atmospheric pressure plasma generator (manufactured by Panasonic Corporation, product name: Aiplasma), For example, plasma processing speed: 10 to 100 mm/s, power source: 200 or 220 V AC (30 A), compressed air: 0.5 MPa (1 NL/min), 10 kHz/300 W to 5 GHz, power: 100 W to 400 W, irradiation time: 0. It is carried out for 1 to 60 seconds.

For ultraviolet irradiation treatment (general UV treatment or excimer UV treatment that generates ozone by UV irradiation) applied to the adhesive side surface of the adhesive base material or the adhesive side surface of the adhered substrate, an excimer lamp light source is used. (manufactured by Hamamatsu Photonics Co., Ltd., product name: L11751-01) at an integrated light amount of 50 to 1500 mJ/cm ² , for example.

The method for producing an adhesive body according to the present invention includes applying a molecular adhesive to the surface of the solid adhesive base material described above, and subjecting the surface to at least one selected from electron beam treatment and gamma ray treatment. A graft copolymerization step in which the molecular adhesive is graft-copolymerized once or multiple times to the active groups having and/or generated; and and/or a step of causing at least one selected from corona treatment, ultraviolet treatment, excimer treatment, intro treatment, and molecular adhesive treatment, and adhesion of a substrate to be adhered to the surface of the graft copolymerized adhesive substrate. a contact step of bringing the surfaces to be bonded into contact; and graft copolymerization of the adhesive base material and the adhered base material on the surface of the adhesive base material under at least one of conditions selected from standing still, loading, heating, and reduced pressure. an adhesion step in which the adhesive base material and the adhered base material are adhered and integrated by covalent bonding between the molecules of the molecular adhesive and the functional group on the surface of the adhered base material. There is.
Specifically, the procedure is as follows. First, a procedure of subjecting the surface of the adhesive base material to electron beam treatment and/or γ-ray treatment, and a procedure of graft copolymerizing a molecular adhesive to the active groups present and/or generated on the surface. (graft copolymerization step). In this step, the treatment procedure and the graft copolymerization procedure may be performed multiple times.

Next, the surface of the substrate to be bonded is brought into contact with the surface of the graft copolymerized adhesive substrate (contact step).

Thereafter, the adhesive base material and the adhered base material are left standing, subjected to a load of 10 to 200 kgf, heated to 10 to 100°C, and/or under reduced pressure conditions of 50 torr or less, more specifically, 50 to 10 torr, or less than 10 torr. , more specifically, under conditions of less than 10 torr to 1×10 ⁻³ torr, preferably less than 10 torr to 1×10 ⁻² torr, with the molecules of the molecular adhesive graft copolymerized on the surface of the adhesive substrate. , a covalent bond is formed with a functional group on the surface of the adhesive base material, whereby the adhesive base material and the adhesive base material are bonded and integrated (adhesion step).
Before this contact step, the surface of the graft copolymerized adhesive base material and/or the surface of the adhered base material may be subjected to any one of corona treatment, ultraviolet treatment, excimer treatment, and intro treatment. good.

Hereinafter, a comparative evaluation was made of Examples 1 and 2 in which samples of adhesive bodies to which the present invention is applied were prepared, and Comparative Examples 1 and 2 in which samples of adhesive bodies to which the present invention was not applied were prepared.

An adhesive sample of an adhesive body of an example to which the present invention is applied and an adhesive sample of an adhesive body of a comparative example to which the present invention is not applied were prepared as follows, and their physical properties were evaluated.

(Preparation of adhesive material)
As adhesive materials, we used a millable-type fluororubber (FKM) with internal vulcanizing agent added: SFM-70A (manufactured by 3M Japan Co., Ltd.) and a millable-type ethylene-propylene-diene copolymer (EPDM): EPT4045M (manufactured by Mitsui Chemicals Co., Ltd.). ) was used.
The vulcanizing agent internally added FKM was heated with an open roll, placed in a mold, and pressed at 170°C for 10 minutes to produce a sheet-like FKM molded body of 1 mm x 150 mm x 150 mm as an adhesive material. .
11 parts of an organic peroxide crosslinking agent: Percmil D-40 (manufactured by NOF Corporation, Perkmil is a registered trademark) was mixed with 100 parts of EPDM, mixed using an open roll, placed in a mold, and heated at 170°C. Pressing was carried out for 10 minutes to produce a sheet-like EPDM molded body of 1 mm x 150 mm x 150 mm as an adhesive material.

(Processing of adhesive material)
Atmospheric pressure corona discharge treatment machine (manufactured by Shinko Denki Keiso Co., Ltd.) under the following conditions: gap length: 1.0 mm, output voltage: 10 kV (surface voltage), moving speed: 4.2 m/ s , number of moves: 3 times. , corona discharge treatment was performed. Thereafter, as a molecular adhesive treatment, an ethanol solution in which a plurality of vinyl group-containing alkoxysiloxane and a vinyl group-containing alkoxysiloxane were each diluted by 0.1 wt % was applied, and heated in a heating oven at a temperature of 80 ° C. for a time of 10 minutes. Grafting was performed by irradiating electron beams with an electron beam irradiator of 2 MeV and a total irradiation dose of 20 to 200 kGy.
Then, using an atmospheric pressure corona discharge treatment machine (manufactured by Shinko Denki Keiso Co., Ltd.), the conditions were: gap length: 1.0 mm, output voltage: 10 kV (surface voltage), moving speed: 4.2 m/ s , number of moves: 3 times. Then, corona discharge treatment was performed. Thereafter, as a molecular adhesive treatment, an ethanol solution in which a plurality of vinyl group-containing alkoxysiloxane and a vinyl group-containing alkoxysiloxane were each diluted by 0.1 wt % was applied, and heated in a heating oven at a temperature of 80° C. for a time of 10 minutes. Thereafter, the treated surface was subjected to atmospheric pressure corona discharge treatment under the same conditions to obtain an adhesive material.

(Treatment of adhered base material)
SUS430:793423 (manufactured by Nilaco Co., Ltd.) was used as the material to be adhered.
SUS cut into 30×60 mm was washed with alkaline and alcohol. Then, using an atmospheric pressure corona discharge treatment machine (manufactured by Shinko Denki Keiso Co., Ltd.), the conditions were: gap length: 1.0 mm, output voltage: 10 kV (surface voltage), moving speed: 4.2 m/ s , number of moves: 3 times. Then, corona discharge treatment was performed. Thereafter, as a molecular adhesive treatment, an ethanol solution in which a plurality of vinyl group-containing alkoxysiloxane and a vinyl group-containing alkoxysiloxane were each diluted by 0.1 wt % was applied, and heated in a heating oven at a temperature of 80° C. for a time of 10 minutes. Thereafter, the treated surface was treated with an atmospheric pressure corona discharge treatment machine under the same conditions to obtain a material to be adhered.

(Examples 1-2)
After bonding the treated surfaces of the adhesive material and the bonded material that have undergone the above treatment so that no air enters, they are heated using a pressure and heat press at a temperature of 80°C, a time of 15 minutes, a pressure of 8.3 kgf/ A bonded body was produced in cm ² .

(Comparative example 1)
After bonding each of the molded bodies of the adhesive material and the surface of the adhered material that has not undergone surface treatment so as to prevent air from entering, they were heated using a pressurized heat press at a temperature of 80°C, a time of 15 minutes, and a pressure: An adhesive body was produced at 8.3 kgf/cm ² .

(Comparative example 2)
Each of the adhesive material molded bodies was treated with an atmospheric pressure corona discharge treatment machine (manufactured by Shinko Denki Keiso Co., Ltd.) with a gap length of 1.0 mm, an output voltage of 10 kV (surface voltage), and a moving speed of 4.2 m/ sec . Corona discharge treatment was performed under the conditions of number of movements: 3 times. Thereafter, as a molecular adhesive treatment, an ethanol solution in which a plurality of vinyl group-containing alkoxysiloxane and a vinyl group-containing alkoxysiloxane were each diluted by 0.1 wt % was applied, and heated in a heating oven at a temperature of 80° C. for a time of 10 minutes. Thereafter, the treated surface was subjected to atmospheric pressure corona discharge treatment under the same conditions. After that, the surface-treated adhesive material and the treated surfaces of the bonded material are pasted together to prevent air from entering, and then heated using a pressure press at a temperature of 80°C for 15 minutes and a pressure of 8.3 kgf. / ^cm2 .

The produced adhesive was subjected to a 90 degree peel test using a force gauge: ZP-200N (manufactured by Imada Co., Ltd.) at a speed of 50 mm/sec to measure the peel strength and observe the condition on the peeled surface. did. Peel tests were conducted on initial samples and samples immersed in boiling water for 1 hour. The results are shown in Table 1.

注）実施例１，比較例１：ＦＫＭ成形体、実施例２，比較例２：ＥＰＤＭ成形体

Note) Example 1, Comparative Example 1: FKM molded product, Example 2, Comparative Example 2: EPDM molded product

As is clear from Table 1, no adhesion occurred in Comparative Examples 1 and 2. On the other hand, in both Examples 1 and 2, the adhesive materials FKM and EPDM were destroyed, so it was found that the adhesive was firmly bonded. Furthermore, it was found that the adhesive material and the adhered material were firmly adhered because the adhesive material did not peel off even when boiled or immersed in alcohol.

Since the adhesive body of the present invention has high adhesive strength, it can be applied to industrial products and daily necessities that must not be peeled off, such as hoses, packing, oil seals, adhesives with metals, diaphragms, gaskets, large rubber rolls, rubber rolls for copying machines, etc. It is useful as a product in many fields, such as conveyor belts, reinforcing belts, medical rubber products, electrical and electronic parts products, construction products, computer products, automobile products, bus and truck products, and airplane products.

Claims (6)

Made of one selected from fluororesin, fluororubber, silicone resin, silicone rubber, ethylene-propylene-diene rubber, ethylene-propylene-diene-methylene rubber, isobutylene-isoprene copolymer rubber, isoprene rubber, and natural rubber , and Electron beam irradiation treatment surface or γ of a solid adhesive base material to which any molecular adhesive selected from silanol compounds, aluminate compounds, titanate compounds, triazine ring-containing compounds, thiol compounds, epoxy compounds, and amine compounds is attached. Molecules of the molecular adhesive graft copolymerized via free radicals on the radiation-treated surface;
Corona-treated surface, ultraviolet-treated surface, excimer-treated surface, and intro-treated surface of a solid adherend substrate made of one selected from polymer resin, natural rubber, synthetic rubber, crosslinked rubber, metal, glass, and ceramics. The adhesive base material and the adherend base material are bonded together by a covalent bond formed by a hydroxy group as a functional group on at least one selected from the surfaces or a functional group on the molecular adhesive-treated surface of the adherend base material. An adhesive body characterized in that these are bonded and integrated. The adhesive body according to claim 1, wherein the free radicals are present and/or generated on the surface of the adhesive base material. The adhesive base material is the fluororesin or fluororubber selected from vinylidene fluoride polymer, tetrafluoroethylene-propylene copolymer, and tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer. The adhesive body according to claim 1 or 2, wherein the adhesive body is a fluorine-containing adhesive base material. The surface treated with a molecular adhesive of the substrate to be adhered is a surface treated with any molecular adhesive selected from a silanol compound, an aluminate compound, a titanate compound, a triazine ring-containing compound, a thiol compound, an epoxy compound, and an amine compound. The adhesive body according to any one of claims 1 to 3 . The adhesive body according to any one of claims 1 to 4 , wherein the molecular adhesive is a vinyl group-containing alkoxysiloxane . The adhesive base material has a flexible film shape, a non-flexible plate shape, or a solid three-dimensional shape, and the adhesive base material has a flexible film shape, a non-flexible plate shape, The adhesive body according to any one of claims 1 to 5 , characterized in that the adhesive body has a solid three-dimensional shape.