JP6940129B2 - Joined body - Google Patents

Description

The present invention relates to a bonded body in which a bonded base material formed of metal, polymer resin, crosslinked rubber, glass or ceramics and a base material to be bonded of the same type or different types are chemically bonded by a silane compound. Is.

A first bonded substrate made of metal, polymer resin, crosslinked rubber, glass or ceramics, and a second bonded substrate formed of dissimilar metals, polymer resins, crosslinked rubber, glass or ceramics. Has very different physicochemical properties and does not have adhesiveness or adhesiveness. Therefore, they cannot be adhered or adhered by simply contacting them. Even when bonded using a fluid curable adhesive, the adhesive force is very weak due to the intermolecular force. Since the appropriate adhesive changes when the material of the base material changes, the selection of the optimum adhesive must be performed by trial and error, which requires a great deal of time and effort.

Since the wettability between the adhesive and both base materials is the most important factor in ensuring that both base materials are adhered with an adhesive, the two base materials are pressed against each other via a fluid curable adhesive. This is done by contacting and then curing the adhesive.

Since the intermolecular force is strongly influenced by the environment such as temperature, humidity, and light, the adhesive force of the adhesive gradually decreases or disappears due to changes in the environment. In addition, there is no reproducibility of adhesion with an adhesive and an adhesive with the same characteristics cannot be obtained, the quality of the adhesive varies depending on the experience and ability of an adhesive engineer, and various factors in the drying and curing processes, etc. There is a problem that productivity is poor because it is difficult to control the product and it is not suitable for mass production.

Adhesion using such a fluid curable adhesive causes the adhesive to squeeze out from the edge of the base material to be adhered, and it is difficult to strictly control the thickness of the adhesive layer and sufficient adhesive strength. There was a problem. Such a problem causes a frequent occurrence of fatal defective products of precision equipment, particularly in the production of precision equipment requiring microfabrication, and thus reduces the yield.

Furthermore, in the case of bonding using a fluid curable adhesive, it is difficult to homogenize in the bonding process due to the non-uniformity of the surface of each base material for each lot, and the defective product occurrence rate and productivity are manufactured. Because it depends on the experience and ability of the person in charge, it is not possible to produce high quality products in large quantities with good yield.

Moreover, in the case of adhesion using a fluid curable adhesive, the wettability to the adherend greatly affects the adhesive strength, so that it is appropriate to have an appropriate coatability every time the material or physical properties of the base material are changed. It is troublesome to reselect the adhesive.

In Patent Document 1, a three-dimensional silicone rubber elastic base material having a hydroxyl group on the surface and a base material to be adhered having a hydroxyl group on the surface are bonded to the hydroxyl group of the elastic base material and the hydroxyl group of the base material to be adhered. Described are silicone rubber adhesives that are covalently bonded and laminated via polysiloxane.

International Publication No. 2010/032728

A bonded base material formed of metal, polymer resin, crosslinked rubber, glass or ceramics and a bonded base material formed of the same or different metal, polymer resin, crosslinked rubber, glass or ceramics are covalently bonded. A bonded body that can be firmly bonded by molecular bonding with, has excellent light resistance, weather resistance, heat resistance, chemical resistance, water resistance, and durability, does not deteriorate due to environmental changes, and is chemically and mechanically stable. The purpose is to provide.

The bonded body made to achieve the above object has a surface of at least one of a bonded base material made of metal, a polymer resin, a crosslinked rubber, glass or ceramics and a base material to be bonded. unsaturated groups attached to the surface exposed reactive group, an epoxy group, a ureido group, a mercapto group, a sulfide group, an isocyanate group, a plurality of alkoxysilyl group, an amino group, and nitrile group or al selected at least one functional group Amplified at the modified site by the second layer of the plurality of vinyl group-containing alkoxysilanes bonded to the modified site surface-modified with the surface-exposed reactive group by the first layer of the reactive functional group-containing alkoxysilane containing It is a heat-pressed bonded body that is bonded to the surface of the other base material via the amplified site by having the amplified site.

Conjugate, and the bonding substrate and the object to be bonded substrate, by the amplification and the surface modification by the plurality vinyl group-containing alkoxy silane and the reactive functional group-containing alkoxy silane and are joined, preferably.

Conjugate, and the bonding substrate and the object to be bonded substrate, the surface-exposed reactive group on the surface of mutual joining side, sharing of the reactive functional group-containing alkoxy silane and the plurality vinyl group-containing alkoxy silane It may be joined via a bond.

In the bonded body, for example, the plurality of vinyl group-containing alkoxysilanes have the following chemical formula.
R ² (OR ^1- ) ₂ -Si-O-[(CH ₂ = CH-) (OR ^1- ) Si-O] _n -Si (-OR ¹ ) ₂ R ³
(In the equation, n is a number from ¹ to 20, R 1 is C _a H _{2a + 1} , and a is a number from 1 to 3, and R ² and R ³ are CH ₃ or CH ₂ = CH). It is a thing.

In the conjugate, for example, the reactive functional group-containing alkoxysilane is a silane coupling agent.

In the conjugate, for example, the reactive functional group-containing alkoxysilane is an amino group- and alkoxy group-containing silane compound; a vinyl group and an alkoxy group-containing silane compound; an epoxy group and an alkoxy group-containing silane compound, and a styryl group and an alkoxy group-containing silane compound. (Meta) acrylic group and alkoxy group-containing silane compound; ureido group and alkoxy-containing silane compound; mercapto group and alkoxy-containing silane compound; sulfide group and alkoxy-containing silane compound; isocyanate group and alkoxy-containing silane compound, allyl group and alkoxy-containing Silane compound; alkyl group and alkoxy group-containing silane compound; aryl group and alkoxy group-containing silane compound; alkyl group and chlorosilane group-containing silane compound; tetraalkoxysilane compound.

Conjugates, the reactive functional group-containing alkoxy silane, is that aminoalkyl trialkoxysilanes, or the amino group and aminoalkyl aminoalkyl trialkoxysilane and alkoxy group-containing silane compound.

Conjugates, wherein the aminoalkyl aminoalkyl trialkoxysilanes, and more _{specifically, H 2 N- (C p H} 2p) -NH- (C q H 2q) -Si (-OC r H 2r + 1) _{It is 3} (p, q, r are independently numbers 1 to 6).

The bonded body is at least one of the exposed surface of the bonded substrate, the surface of the modified portion thereof, and the surface of the amplified portion thereof, and / or the exposed surface of the substrate to be bonded and the modification thereof. It is preferable that at least one of the surface of the quality portion and the surface of the amplification portion thereof is a corona discharge-treated surface, a plasma-treated surface, an ultraviolet-treated surface, and / or an excimer-treated surface.

In the bonded body, the surface on the bonding side between the bonding substrate and the substrate to be bonded has the modification site and the amplification site on the one hand, and the silanepropyltriethoxysilane compound-treated surface on the other hand. It may be a titanate compound-treated surface, an aluminate compound-treated surface, a thiol compound-treated surface, an azide compound-treated surface, a corona discharge-treated surface, a plasma-treated surface, an ultraviolet-treated surface, and / or an excimer-treated surface.

The method for producing a bonded body of the present invention comprises a bonding base material formed of metal, polymer resin, crosslinked rubber, glass or ceramics, and a group to be bonded formed of metal, polymer resin, crosslinked rubber, glass or ceramics. at least the surface of one substrate of a wood, unsaturated group, an epoxy group, a ureido group, a mercapto group, a sulfide group, an isocyanate group, a plurality of alkoxysilyl group, an amino group, and nitrile or al least one selected group by sequentially processing by reactive functional group-containing alkoxy silane and a plurality vinyl group-containing alkoxy silanes containing functional groups, the surface of the bonding side of at least one of the substrate and the object to be bonded substrate and the bonded substrate the reactive functional group-containing alkoxy silane surface-exposed reactive groups reacted of surface modification in the surface-exposed reactive group reformed region is formed as a first layer by the reactive functional group-containing alkoxy silane and then, forming an amplification region is amplified by the reforming portion by the plurality vinyl group-containing alkoxy silane to the modified site as a second layer by said plurality vinyl group-containing alkoxy silanes, their two substrates It includes a step of joining the surfaces on the joining side to each other and heat-pressing to obtain a heat-pressed joint body.

The bonded body of the present invention is a bonded base material formed of a metal, a polymer resin, a crosslinked rubber, glass or ceramics, and a bonded body formed of the same or different metals, a polymer resin, a crosslinked rubber, glass or ceramics. The base material is firmly crosslinked and bonded to the base material regardless of the material and physical properties of each material, without using a fluid curable adhesive. The conjugate by a reactive functional group-containing alkoxy silane and a plurality vinyl group-containing alkoxy silane, they are sequentially reacted with the substrate surface, and the reforming site that was surface modified by a reactive functional group-containing alkoxy silanes, modified to form an amplification region amplified by the plurality vinyl group-containing alkoxy silane quality sites, respectively, by covalent coupling via amplification sites are those that are joined with high joint strength.

This bonded body is a bonding base material formed of metal, polymer resin, crosslinked rubber, glass or ceramics, and a base material to be bonded formed of the same or different metals, polymer resin, crosslinked rubber, glass or ceramics. the surface exposed reactive group exposed to at least one of joint side on the surface of the reaction easily reactive functional group-containing alkoxy silane is bound first react to form a surface modified modified site , then its modified site react more vinyl group-containing alkoxy silane bonded to form an amplified amplification site of a number of vinyl groups, necessary functional groups such as to oxidatively dissociate the vinyl group transformation according to It is bonded to the surface of the other base material via the amplification site.

By covalent bond by the reaction functional group-containing alkoxy silane and a plurality vinyl group-containing alkoxy silane, metal, polymer resin, crosslinked rubber, glass or ceramics formed bonded substrate and the same or different metal, polymer resin Since it is firmly bonded to the base material to be bonded formed of crosslinked rubber, glass or ceramics, this bonded body is unlikely to be mechanically or chemically peeled off. Further, the bonded body does not depend on the fluid curable adhesive, but is thinly interposed between the bonded base material and the base material to be bonded via a reactive functional group-containing alkoxysilane and a plurality of vinyl group-containing alkoxysilanes , for example. Since the molecular film and the monomolecular film are formed and bonded, there is no risk that they will protrude at the bonding surface or peel off at the cured product layer thereof.

This bonded body is much stronger than the covalent bond between the reactive functional group-containing alkoxysilane and the multiple vinyl group-containing alkoxysilane and the bonding by the intermolecular force of the adhesive. However, it is a bonded product. It is stable to solutes such as water, especially hot water, and liquid chemicals, especially alcohol.

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.

A preferred form of the bonded body of the present invention is that the bonded base material formed of metal, polymer resin, crosslinked rubber, glass or ceramics and the bonded base material face each other on the bonding surface side, and contain a reactive functional group. by covalent bonds derived therefrom et using alkoxy silane and a plurality vinyl group-containing alkoxy silanes are those that are joined.

The conjugates modified sites both surfaces of the surface of the bonding side of the bonding substrate and the bonded substrate, surface modified by a reactive functional group-containing alkoxy silane bonded thereto surface-exposed reactive group by having an amplification region amplified by the plurality vinyl group-containing alkoxy silane bonded to, via the amplifier site on the surface of the other substrate it is bonded.

For example, the surface on the bonding side between the bonding base material and the base material to be bonded is previously subjected to surface activation treatment such as corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, or excima treatment to join the base materials to be bonded. The side surfaces are preliminarily subjected to surface activation treatments such as corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, or excima treatment, so that the surfaces thereof are treated with, for example, hydroxyl groups, carboxyl groups and, for example, as surface exposure reactive groups. / Or a new carbonyl group has been created.

In this way, a hydroxyl group, a carboxyl group, or a carbonyl group, which is a surface-exposed reactive group having a sufficient concentration, is generated on the surface of the bonding substrate or the substrate to be bonded on the bonding side, or a slightly generated surface of the hydroxyl group or the like. It is necessary to use the exposure-reactive group to amplify the concentration of the reactive group with the other surface-exposure-reactive group. In particular, it is preferable that a surface exposure-reactive group is newly introduced into both the bonding base material and the base material to be bonded.

In order to generate a sufficient concentration of surface-exposed reactive groups on the bonded surface of the bonded or bonded substrate, for example, on at least one of those bonded or bonded substrates to be bonded. When a surface activation treatment such as corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, or excimation treatment is performed, a highly reactive surface-exposed reactive group, for example, a hydroxyl group, is applied on the organic or inorganic material on the surface on the bonding side. , A carboxyl group or a carbonyl group is generated, and the joint surface has a scattered surface-exposed reactive group in which the originally formed hydroxyl group and the newly formed hydroxyl group, the carboxyl group or the carbonyl group are exposed and scattered. It becomes.

Thereto, the reactive functional group-containing alkoxy silane and immersing a plurality vinyl group-containing alkoxy silane coating, the process of spraying or the like performed. Then, first, a reactive functional group-containing alkoxy containing a functional group selected from an unsaturated group, an epoxy group, a ureido group, a mercapto group, a sulfide group, an isocyanate group, a plurality of alkoxysilyl groups, an amino group, a nitrile group and an azido group. Silane is bonded to a surface-exposed reactive group such as a hydroxyl group, a carboxyl group or a carbonyl group via a covalent bond such as an ether bond, an ester bond, an amide bond, an imino bond or a urethane bond, and the surface is exposed with low reactivity. reactive group, are surface modified with highly reactive these reactive functional group-containing alkoxy silane, the reactive functional group-containing exposed alkoxysilyl group derived from the alkoxy silane, for example, is formed monomolecular film, the surface It is reformed.

Then, the alkoxysilyl group at the modified sites, alkoxysilyl group of the plurality vinyl group-containing alkoxy silane is bound to via the new siloxy bond by reaction with an alcohol reaction. Then, originally from one of the groups of low reactivity surface exposed reactive group, is amplified by the highly reactive plurality of vinyl groups derived from plural vinyl group-containing alkoxy silanes, for example, is formed monomolecular film. Surface of the joining side of the bonded substrate likewise, surface modified with a reactive functional group-containing alkoxy silanes, are amplified by a plurality vinyl group-containing alkoxy silanes.

Then, an amplification site in which a plurality of vinyl groups are exposed is formed from both substrates. If necessary, when the surface where the amplification site is exposed is subjected to corona discharge treatment, plasma treatment, ultraviolet treatment, and / or excimer treatment, at least a part or all of the vinyl groups are oxidatively cleaved and exposed silanol. It is an amplification site that produces a group or a silyl group.

When the two substrates are simply brought into contact with each other or further overlapped under pressure or reduced pressure, the bonding surface side of one substrate is covalently bonded to the bonding surface side of the other substrate via an amplification site. And are joined. At this time, the vinyl groups, silanol groups, silyl groups, and combinations thereof at the amplification sites of both substrates react with each other.

Thus, the surface-exposed reactive groups of each substrate, a reactive functional group-containing alkoxy silane one molecule is a molecule adhesive is reacted with speak monomolecular film form, is another molecule adhesive thereto one further forming a monomolecular film-like plurality vinyl group-containing alkoxy silane molecules react, contributes to bonding of both substrates. A monomolecular film of the reactive functional group-containing alkoxy silanes by covalent binding via a monolayer of a plurality vinyl group-containing alkoxy silane is another molecule adhesive, each of the addition reaction and / or alkoxy between vinyl groups Both substrates are chemically bonded by a condensation reaction between siloxy groups.

Although an example of processing a bonding side face of the bonding substrate and the surface of the bonding side of the bonded substrate with a reactive functional group-containing alkoxy silane and a plurality vinyl group-containing alkoxy silane, either one of the base And the other substrate is untreated or surface activated such as corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, or excima treatment, and then contacted to add and / or condense both groups. The materials may be chemically bonded.

More vinyl group-containing alkoxy silane, as long as it can amplify the reforming portion by reactive functional group-containing alkoxy silane, but are not limited to, Formula
R ² (OR ^1- ) ₂ -Si-O-[(CH ₂ = CH-) (OR ^1- ) Si-O] _n -Si (-OR ¹ ) ₂ R ³
(In the equation, n is a number from ¹ to 20, R 1 is C _a H _{2a + 1} , and a is a number from 1 to 3, and R ² and R ³ are CH ₃ or CH ₂ = CH). More specifically, in the equation, n is a number from 1 to 5, a is a number from 1 to 3, R ₂ = CH ₃ , and R ₃ = CH ₂ = CH. Agents can be mentioned.

The reactive functional group-containing alkoxysilane is an unsaturated group, an epoxy group, a ureido group, a mercapto group, a sulfide group, an isocyanate group, a plurality of alkoxysilyl groups, an amino group, a nitrile group and an azide group, which are bonded to a surface exposure reactive group. As long as it contains a functional group selected from the above, it is not particularly limited. For example as the reactive functional group-containing alkoxy silane,
Vinyl and alkoxy group-containing silane compounds such as vinyltrimethoxysilane (KBM-1003) and vinyltriethoxysilane (KBE-1003);
2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (KBM-303), 3-glycidoxypropylmethyldimethoxysilane (KBM-402), 3-glycidoxypropyltrimethoxysilane (KBM-403), Epoxide and alkoxy group-containing silane compounds such as 3-glycidoxypropylmethyldiethoxysilane (KBE-402), 3-glycidoxypropyltriethoxysilane (KBE-403);
Styryl group- and alkoxy group-containing silane compounds such as p-styryltrimethoxysilane (KBM-1403);
3-methacryloxymethyldiethoxysilane, 3-methacryloxymethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane (KBM-502), 3-methacryloxypropyltrimethoxysilane (KBM-503), 3-methacryloxy Contains (meth) acrylic and alkoxy groups such as propylmethyldiethoxysilane (KBE-502), 3-methacryloxypropylmethyldiethoxysilane (KBE-503), 3-acryloxypropyltrimethoxysilane (KBM-5103) Silane compound;
Ureido group and alkoxy-containing silane compounds such as 3-ureidopropyltriethoxysilane (KBE-585);
Mercapto group and alkoxy-containing silane compounds such as 3-mercaptopropylmethyldimethoxysilane (KBM-802), 3-mercaptopropyltrimethoxysilane (KBM-803);
Sulfide groups such as bis (triethoxysilylpropyl) tetrasulfide (KBE-846) and alkoxy-containing silane compounds;
3-Isocyanate group such as propyltriethoxysilane (KBE-9007) and alkoxy-containing silane compound (all manufactured by Shin-Etsu Silicone Co., Ltd .; trade name);
Can be mentioned.

Further, vinyl group and acetoxy-containing silane compounds such as vinyl triacetoxysilane (Z-6075); allyl group and alkoxy-containing silane compounds exemplified by allyltrimethoxysilane (Z-6825); methyltrimethoxysilane (Z-). 6366), dimethyldimethoxysilane (Z-6329), trimethylmethoxysilane (Z-6013), methyltriethoxysilane (Z-6383), methyltriphenoxysilane (Z-6721), ethyltrimethoxysilane (Z-6321) , N-propyltrimethoxysilane (Z-6265), diisopropyldimethoxysilane (Z-6258), isobutyltrimethoxysilane (Z-2306), diisobutyldimethoxysilane (Z-6275), isobutyltriethoxysilane (Z-6403) , N-hexitrimethoxysilane (Z-6583), n-hexitriethoxysilane (Z-6586), cyclohexylmethyldimethoxysilane (Z-6187), n-octyltriethoxysilane (Z-6341), n-decyl Alkyl group and alkoxy group-containing silane compounds such as trimethoxysilane (Z-6210); aryl group and alkoxy group-containing silane compounds such as phenyltrimethoxysilane (Z-6124); n-octyldimethylchlorosilane (ACS-8) ) And chlorosilane group-containing silane compounds; silane compounds which are alkoxysilanes such as tetraethoxysilane (Z-6697) (all manufactured by Toray Dow Corning Co., Ltd .; trade name) can be mentioned.

Reactive functional group-containing alkoxy silanes, among others, if it is an aminoalkyl trialkoxysilane, or amino group and alkoxy group-containing silane compounds such as aminoalkyl aminoalkyl trialkoxysilane, from the alkoxy group of the plurality vinyl group-containing alkoxy silane Since the amino group easily reacts with the surface-exposed reactive group of the bonding base material or the base material to be bonded, surface modification is given priority in competition.

The amino group- and alkoxy group-containing silane compound is not particularly limited as long as it reacts with the surface-exposed reactive group of the bonding substrate or the substrate to be bonded to modify the surface, but specifically, aminoalkylamino. alkyltrialkoxysilane, more _{specifically, H 2 N- (C p H} 2p) -NH- (C q H 2q) -Si (-OC r H 2r + 1) 3 (p, q, r are each It is independently indicated by a number (1 to 6), and preferably aminoethylaminopropyltrimethoxysilane (p = 2, q = 3, r = 1).

The material of the bonding base material or the base material to be bonded in the bonded body is not particularly limited as long as it is a metal, a polymer resin, crosslinked rubber, glass or ceramics.

Polycarbonate, cycloolefin polymer, polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, polyether (meth) acrylate, and silicone (meth) (Meta) acrylates and (meth) acrylic resins such as pentaerythritol tetra (meth) acrylate; additional crosslinked silicones similar to those described above; vinyl methyl silicones (VMQ), methylphenyl silicones (PVMQ), fluoromethyl silicones (FVMQ) , And silicone resins such as dimethyl silicone (MQ), peroxide-crosslinked silicone resins, condensation-crosslinked silicone resins, UV-crosslinked silicone resins, rigid silicone resins exemplified by radiation-crosslinked silicone resins, and these silicone resins. Examples include co-blends with olefins.

As the metal of the base material to be joined, which is the material of the base material to be joined or the material to be joined, it is composed of ordinary metals, functional metals, amorofus metals, fiber-reinforced metal blocks, shape memory alloys, superelastic alloys, etc. in terms of metal classification. In terms of metal shape classification, it includes plates, sheets, films, square bars, round bars, spheres, hemispheres, fibers, nets, mesh wires, films, sheets and their complex circuit shapes, punched and machined alloys. On the 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, neodym, iron alloy (steel (steel), carbon steel, cast iron), Copper alloys (phosphorus bronze, brass, dipronickel, beryllium copper, titanium copper), aluminum alloys (copper, manganese, silicon, magnesium, zinc, nickel alloys, etc.), magnesium alloys (Mg / Zn alloys, Mg / Ca alloys, etc.) ), Zinc alloy, bell and bell alloy, nickel alloy, gold alloy, silver alloy, platinum alloy, palladium alloy, lead alloy, titanium alloy (α type, β type and α + β type alloy), cadmium, zirconium alloy, cobalt alloy, Chromium alloy, molybdenum alloy, tungsten alloy, manganese alloy, ferrite-based stainless steel, martensite-based stainless steel, austinite-based stainless steel, precipitation-reinforced stainless steel, nickel-titanium alloy, iron-manganese-titanium alloy, superelastic alloy (nickel-titanium alloy) ) And other materials.

As the crosslinked rubber of the material of the bonded base material and the base material to be bonded, additional crosslinked silicone rubber; silicone rubber such as VMQ, PVMQ, FVMQ, and MQ, peroxide crosslinked silicone rubber, condensation crosslinked silicone rubber, ultraviolet rays. Cross-linked silicone rubber, radiation-cross-linked silicone rubber, ethylene / propylene / diene rubber (EPDM), vinylidene fluoride (FKM), tetrafluoroethylene-propylene (FEPM), tetrafluoroethylene-purple orovinyl ether (FFKM) Fluorine rubber, butadiene rubber (BR), isoprene rubber (IR), isobutylene-isoprene rubber (IIR), natural rubber (NR), urethane rubber (U), acrylic rubber (ACM), these crosslinked rubbers and olefins. Co-blend product of.

Examples of the glass as the material of the bonded base material and the base material to be bonded include quartz, borosilicate glass, and non-alkali glass.

As the ceramics used as the material of the bonded base material and the base material to be bonded, ceramics, glass, cement, gypsum, wax, etc. are hardened at a high temperature, and the composition is element-based (diamond, C), oxide-based (alumina, Al ₂ O ₃ ), zirconia type, hydroxide type (hydroxyapatite), carbide type (silicon carbide, SiC), carbonate type, nitride type (silicon nitride type), (7 halide type (firestone), phosphorus Including acid salt (apatite), specifically 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, HTS ceramics, zinc oxide, aluminum nitride (AlN), silicon carbide (SiC), nitride silicon _{(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 ) _, 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 ) and the like, and include shapes such as blocks, plates, sheets, films, square bars, round bars, spheres, hemispheres, fibers and nets, and composite materials such as fiber-reinforced ceramics and carbon fiber-reinforced carbon.

Among the combinations of the materials of the bonding base material and the base material to be bonded in the bonded body, it is preferable that one is a silicone resin or a silicone rubber and the other is a resin other than silicone.

At least one of the exposed surface of the bonded substrate, the surface of the modified portion thereof, and the surface of the amplified portion thereof, and / or the exposed surface of the substrate to be bonded, the surface of the modified portion thereof, and the amplification thereof. It is more preferable that at least one of the surface of the portion is activated by corona discharge treatment, plasma treatment, ultraviolet treatment, or excimer treatment because it is easy to react.

The bonded base material and the base material to be bonded are modified and amplified on the bonded side surface of one base material, and the silanepropyltriethoxysilane compound, titanate compound, and aluminum are modified on the bonded side surface of the other base material. The surface is modified by immersion, coating, or spraying in a solution of a nate compound, a thiol compound, or an azide compound, or a surface modification treatment by corona discharge, plasma treatment, ultraviolet irradiation treatment, or excima treatment. May be good.

The reactive functional group-containing alkoxy silane and a plurality vinyl group-containing alkoxy silane, as a molecular glue, separately may be used in two-liquid, it may be used by mixing the first liquid. The usage ratio or mixing ratio is preferably a composition of 1 to 0.1: 1 by weight. Especially the mixture
R ² (OR ^1- ) ₂ -Si-O-[(CH ₂ = CH-) (OR ^1- ) Si-O] _n -Si (-OR ¹ ) ₂ R ³
(In the formula, n is a number from ^{1 to} 5, R 1 is C _a H _{2a + 1} , and a is a number from 1 to 3, R ₂ = CH ₃ , R ₃ = CH ₂ = CH) It is even more preferable to use a mixture of a plurality of vinyl-containing silane coupling agents such as N- (3- (trimethoxysilyl) propyl) ethylenediamine.

When joining the bonded base material and the base material to be bonded, the bonded surfaces are subjected to surface activation treatments such as corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, and excimer treatment, and then laminated at normal pressure. It may be covalently bonded under normal pressure, or it may be covalently bonded under reduced pressure or pressure. Proximity of the reactive groups of the surface-exposed reactive groups with the reactive functional group-containing alkoxy silane or more vinyl group-containing alkoxy silane such as a hydroxyl group, the vacuum or vacuum conditions, for example 50torr or less, and more specifically 50~10torr The gas medium at the contact interface is removed under the reduced pressure conditions of less than 10 ^{torr, or more specifically, less than 10 torr to 1 × 10 -3} torr, preferably less than 10 ^{torr to 1 × 10 -2 torr.} This is accelerated by this, or by applying a stress (load), eg, 10-200 kgf, to its contact interface and further heating the contact interface.

As the corona discharge treatment applied to the surface on the bonding side between the bonding substrate and the substrate to be bonded, for example, an atmospheric pressure corona surface modifier (manufactured by Shinko Electric Measurement Co., Ltd., product name: Corona Master) is used, for example. Power supply: AC100V, output voltage: 0 to 20kV, oscillation frequency: 0 to 40kHz for 0.1 to 60 seconds, temperature 0 to 60 ° C. Such a corona discharge treatment may be carried out in a state of being wet with water, alcohols, acetones, esters and the like.

Atmospheric pressure plasma treatment and / or ultraviolet irradiation treatment (general UV treatment or excimer UV treatment that generates ozone by UV irradiation) applied to activate the surface on the bonding side between the bonding substrate and the substrate to be bonded. ) May be.

As the atmospheric pressure plasma treatment, for example, an atmospheric pressure plasma generator (manufactured by Panasonic Corporation, product name: Aiplasuma) is used, for example, a plasma processing speed of 10 to 100 mm / s, a power source: 200 or 220 V AC (30 A), and the like. Compressed air: 0.5 MPa (1 NL / min), 10 kHz / 300 W to 5 GHz, power: 100 W to 400 W, irradiation time: 0.1 to 60 seconds.

The ultraviolet irradiation treatment is carried out using an excimer lamp light source (manufactured by Hamamatsu Photonics Co., Ltd., product name: L11751-01), for example, at an integrated light intensity of 50 to 1500 mJ / cm ² .

When one of the surface on the bonding side of the bonding substrate and the surface on the bonding side of the substrate to be bonded is amplified by these multiple vinyl group-containing alkoxysilanes , the surface on the bonding side of the bonding substrate and the surface to be bonded are used. the other of the junction side surface of, may be amplified by the plurality vinyl group-containing alkoxy silanes, organic aluminate, inorganic aluminate, an organic titanate, inorganic titanates, triazine ring-containing compound, CH ₂ = CH-Si (-OCH _{3) 3 (vinylmethoxysilane: VMS), CH 2 = CH} -Si (-OC 2 H 5) 3, CH 2 = CH-Si (-OC 3 H 7) a silane coupling agent such as ₃ The reactivity may be enhanced by.

As an organic aluminate and / or an organic titanate
-{O-Si (-A ¹ ) (-B ¹ )}-Repeat unit is p unit,
-{O-Ti (-A ² ) (-B ² )}-Repeat unit is q unit,
-{O-Al (-A ³ )}-repetition unit r unit (however, in each repetition unit, p and q are numbers of 0 or 2 to 200 and r is a number of 0 or 2 to 100. p + q + r> 2, and -A ¹ , -A ² and -A ³ are -CH ₃ , -C ₂ H ₅ , -CH = CH ₂ , -CH (CH ₃ ) _2, -CH ₂ CH (CH _3). ) ₂ , -C (CH ₃ ) ₃ , -C ₆ H ₅ or -C ₆ H ₁₂ , and -OCH ₃ , -OC ₂ H ₅ , -OCH = CH ₂ , -OCH (CH ₃ ) ₂ , -OCH ₂ CH (CH ₃ ) ₂ , -OC (CH ₃ ) ₃ , -OC ₆ H ₅ and -OC ₆ H ₁₂ , which are any of the reactive groups forming the covalent bond, -B ¹ and -B ² is -N (CH ₃ ) COCH ₃ or -N (C ₂ H ₅ ) COCH ₃ and -OCH ₃ , -OC ₂ H ₅ , -OCH = CH ₂ , -OCH (CH ₃ ) ₂ , -OCH ₂ CH (CH ₃ ) ₂ , -OC (CH ₃ ) ₃ , -OC ₆ H ₅ , -OC ₆ H ₁₂ , -OCOCH ₃ , -OCOCH (C ₂ H ₅ ) C ₄ H ₉ , -OCOC ₆ Any of the reactive groups selected from H ₅ , -ON = C (CH ₃ ) ₂ and -OC (CH ₃ ) = CH ₂ to form the covalent bond, p, q and r are positive numbers. Examples thereof include compounds schematically represented by (the reactive group is at least any one of -A ¹ , -A ² , -A ³ , -B ¹ and -B ^{2" in the repeating unit.} This compound may have a repeat unit of block copolymerization or random copolymerization. It may be an aluminate coupling agent such as organic aluminate or inorganic aluminate, or a titanate coupling agent such as organic titanate or inorganic 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（Ｐ−ＴＥＳ）；
アルコキシシリル基を有するチオール化合物、具体的にはトリアルコキシシリルアルキル基を有するチオール化合物；
アルコキシシリル基を有するエポキシ化合物、具体的にはトリアルキルオキシシリルアルキル基を有するエポキシ化合物；
アルコキシシリル基とメルカプト基とアジド基との少なくとも何れかを有するトリアジン化合物；
アルコキシシリル基を有するアミン化合物、具体的にはＮ−（３−（トリメトキシシリル）プロピル）エチレンジアミン；
が挙げられる。 More specifically, as a triazine ring-containing compound,
Amino group-containing compounds such as triethoxysilylpropylamino-1,3,5-triazine-2,4-dithiol (TES), aminoethylaminopropyltrimethoxysilane; trialkoxysilyls such as triethoxysilylpropylamino group A triazine compound having an alkylamino group and a mercapto group or an azide group, the following chemical formula (I)

(In the formula (I), W may be a spacer group, for example, an alkylene group which may have a substituent, an aminoalkylene group, or a direct bond. Y is a hydroxyl group or hydrolysis. A reactive functional group that produces a hydroxyl group by desorption or desorption, such as a trialkoxyalkyl group. -Z is -N ₃ or -NR ¹ R ² (provided that R ¹ , R ² are the same or different H or Alkyl group, -R ³ Si (R ⁴ ) _m (OR ⁵ ) _3-m [R ³ , R ⁴ is an alkyl group, R ⁵ is an H or alkyl group, m is 0 to 2]. An alkylene group and an 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-. Diazid-4- {3- (triethoxysilyl) propylamino} -1,3,5-triazine (P-TES);
A thiol compound having an alkoxysilyl group, specifically a thiol compound having a trialkoxysilylalkyl group;
Epoxy compounds having an alkoxysilyl group, specifically epoxy compounds having a trialkyloxysilylalkyl group;
A triazine compound having at least one of an alkoxysilyl group, a mercapto group and an azide group;
Amine compounds having an alkoxysilyl group, specifically N- (3- (trimethoxysilyl) propyl) ethylenediamine;
Can be mentioned.

The joint is manufactured, for example, as follows. A bonded base material and a bonded base material are prepared from metal, polymer resin, crosslinked rubber, glass or ceramics, respectively. When corona discharge treatment, plasma treatment, ultraviolet treatment, and / or excimer treatment are performed in advance, the originally existing surface exposure reactive groups or the surface exposure reactive groups newly generated by these treatments are exposed from the surface. .. The surface of the bonding side of at least one of the substrate between the bonding substrate and the bonded substrate is treated by dipping, coating, spraying at reactive functional group-containing alkoxy silane and a plurality vinyl group-containing alkoxy silanes. Then, the treated bonded substrate and the bonded substrates, reactive functional group-containing alkoxy silane is surface modified to react competitively to the surface exposed reactive groups of the surface of the cemented side, forming the modified region do. A siloxy group derived from the reactive functional group-containing alkoxy silane in the reforming portion and siloxy groups from more vinyl group-containing alkoxy silane and condensation reaction, amplified by a vinyl group derived from a plurality vinyl group-containing alkoxy silane To form an amplification site. Finally, if necessary, corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, or excimer treatment is performed to expose the vinyl group at the amplification site, the silanol group formed by cleavage thereof, and the silyl group to the surface. A bonded body is obtained when the surfaces on the bonding side of both of the base materials are brought into contact with each other and heated at room temperature or under pressure under reduced pressure, under pressure, and under pressing conditions.

Since this bonded body has high peel strength, applications that require mechanical strength such as peel resistance, applications that require chemical resistance / water resistance, for example, alcohol resistance, water resistance, and high-pressure steam resistance, It can be used for all applications that require heat resistance.

In this bonded body, the bonding base material and the base material to be bonded are molecularly bonded with only one of the reactive functional group-containing alkoxysilane and the plurality of vinyl group-containing alkoxysilanes, and the vinyl group-containing alkoxy is obtained in advance. It is superior in boiling resistance (water resistance / heat resistance) and alcohol resistance as compared with the case where it is treated with silane and then treated with a reactive functional group-containing alkoxysilane. This is because when only a reactive functional group-containing alkoxysilane, for example, an alkoxy group-containing silane compound is reacted with a bonding base material and a base material to be bonded, the alkoxy group is easily deactivated and deactivated after the reaction, or a plurality of vinyl groups are used. reactive-containing alkoxy silane is presumed to be due to low or. As in this conjugate, using a reactive functional group-containing alkoxy silane and a plurality vinyl group-containing alkoxy silanes, it is important to bonding.

A bonded sample of the bonded body of the example to which the present invention was applied and an adhesive sample of the bonded body of the comparative example to which the present invention was not applied were prepared as follows, and their physical characteristics were evaluated.

(Example 1)
Peroxide cross-linked silicone rubber: SH-851U (manufactured by Toray Dow Corning Co., Ltd.) is used as the bonding base material A, and 2,5-dimethyl-2,5 is used as an organic peroxide cross-linking agent in 100 parts of the silicone rubber. 0.5 part of −dihexane was mixed, mixed with an open roll, placed in a mold, and pressed under pressure at 170 ° C. for 10 minutes to prepare a silicone rubber (Q) molded product. The prepared adhesive substrate was washed with ethanol and air-dried. On the surface of these silicone rubber molded bodies, an atmospheric pressure corona discharge processor (manufactured by Shinko Denki Keiso Co., Ltd.) has a gap length of 1.0 mm, an output voltage of 10 kV (surface voltage), and a moving speed of 4.2 m / sec. , Number of movements: Corona discharge treatment was performed under the condition of 3 times.

On the other hand, polyethylene terephthalate (PET): Lumirror S10 (manufactured by Toray Industries, Inc.) was used as the non-bonded base material B. The substrate to be bonded was washed with ethanol and air-dried. On the surface of these non-adhesive substrates, an atmospheric pressure corona discharge processor (manufactured by Shinko Denki Keiso Co., Ltd.) has a gap length of 1.0 mm, an output voltage of 10 kV (surface voltage), and a moving speed of 4.2 m / sec. , Number of movements: Corona discharge treatment was performed under the condition of 3 times. Then, a solution prepared by diluting 0.1 wt% of reactive functional group-containing alkoxysilane : SZ6020 (manufactured by Toray Dow Corning Co., Ltd.) in ethanol was applied, and the mixture was heated in a heating oven at 80 ° C. for 10 minutes to form one layer. The eyes were subjected to molecular adhesion treatment. Then, the corona discharge treatment was performed in the same manner as described above, a solution of a plurality of vinyl group-containing alkoxysilane VMM-010 (manufactured by Azumax Co., Ltd.) diluted with 0.1 wt% in ethanol was applied, and the mixture was heated in an oven at 80 ° C. for 10 minutes. It was heated and subjected to a second layer of molecular adhesion treatment.

The treated base material to be bonded is subjected to corona discharge treatment in the same manner as described above, bonded to the bonded base material, the residual air on the bonded surface is pushed away by a plastic roller to remove air, and then a heating press is performed at 80 ° C. for 5 minutes. Crimping was performed to obtain a bonded sample in which both members were bonded.

(Example 2)
A peroxide crosslinked silicone rubber was used as the joining member, and PET was used for the joining member, and the corona discharge treatment was performed in the same manner as in Example 1. Then heated for 10 minutes at coating a mixed solution of reactive functional group-containing alkoxy silane and a plurality vinyl group-containing alkoxy silane bonded members were diluted each 0.1 wt% in the same ethanol, 80 ° C. in a heating oven , Molecular adhesion treatment was applied. After the treatment, a bonding treatment was performed in the same manner as in Example 1 to obtain a bonded sample in which both members were bonded.

(Comparative Examples 1 to 3)
A peroxide crosslinked silicone rubber was used as the joining member, and PET was used for the joining member, and the corona discharge treatment was performed in the same manner as in Example 1. Thereafter, the bonded reactive functional group-containing alkoxy silane member (Comparative Example 1), a single vinyl group-containing alkoxy silane SZ6300 (manufactured by Dow Corning Toray Co., Ltd.) (Comparative Example 2), a plurality vinyl group-containing alkoxy silane (compare Example 3) was coated with a solution obtained by diluting each of 0.1 wt% with ethanol and heated at 80 ° C. for 10 minutes in a heating oven to carry out molecular adhesion treatment. After the treatment, a laminating treatment was carried out in the same manner as in Example 1 to obtain a comparative sample.

(Peeling strength test)
Various immersion tests were performed on the bonded samples of the optical members of Examples 1 and 2 and the bonded samples of Comparative Examples 1 to 3, and then the speed was 100 mm / sec with a force gauge: ZP-200P (manufactured by Imada Co., Ltd.). A T-type peeling test was carried out in the above, the pulling strength was measured for each, and the state on the peeling surface was observed. In the immersion test, the bonded sample was immersed in warm water and ethanol for 1 hour. The results are shown in Table 1.

As is clear from Table 1, no joining was performed in Comparative Examples 2 and 3. In Comparative Example 1, the initial adhesion was performed, but peeling was observed in warm water and ethanol immersion. On the other hand, in both Examples 1 and 2, it was found that the silicone, which is the adhesive base material, was destroyed, so that they were firmly bonded. Furthermore, since it was not peeled off by immersion in warm water or ethanol, it was found that the adhesive base material and the base material to be adhered were firmly bonded by a covalent bond with a molecular adhesive.

(Examples 3 to 5)
Peroxide cross-linked silicone rubber (Q) as the bonding base material A, plate-shaped transparent base material made of cycloolefin polymer (COP) as the resin-made base material B to be bonded: Zeonoa 1420R (manufactured by Nippon Zeon Co., Ltd.), polycarbonate (manufactured by Nippon Zeon Co., Ltd.) PC) Plate-made transparent base material: PC610 (manufactured by Takiron Co., Ltd.), Polymethylmethacrylate (PMMA) plate-shaped transparent base material which is an acrylic resin: Comoglass DK3 (manufactured by Kuraray Co., Ltd.) Similarly, corona discharge treatment was performed. Then heated for 10 minutes at coating a mixed solution of reactive functional group-containing alkoxy silane and a plurality vinyl group-containing alkoxy silane bonded members were diluted each 0.1 wt% in the same ethanol, 80 ° C. in a heating oven , Molecular adhesion treatment was applied. After the treatment, a bonding treatment was performed in the same manner as in Example 1 to obtain a bonded sample in which both members were bonded.

(Examples 6 to 8)
Corona discharge treatment was performed in the same manner as in Example 1 using peroxide crosslinked silicone rubber (Q) as the bonding base material A and SUS304, aluminum, and titanium (manufactured by Nirako Co., Ltd.) as the metal bonding base material B. rice field. Then heated for 10 minutes at coating a mixed solution of reactive functional group-containing alkoxy silane and a plurality vinyl group-containing alkoxy silane were diluted each 0.2 wt% in the same ethanol workpieces, 120 ° C. in a heating oven , Molecular adhesion treatment was applied. After the treatment, a bonding treatment was performed in the same manner as in Example 1 to obtain a bonded sample in which both members were bonded.

(Peeling strength test)
The bonded samples of Examples 3 to 8 were subjected to a 90 ° peeling test at a speed of 50 mm / sec with a force gauge: ZP-200P (manufactured by Imada Co., Ltd.), and the pulling strength was measured and peeled. The condition on the surface was observed. The results are shown in Table 2.

As is clear from Table 2, since the silicone as the adhesive base material was destroyed in all of Examples 3 to 8, it was found that they were firmly bonded.

(Example 9)
Corona discharge treatment was performed in the same manner as in Example 1 using a peroxide crosslinked silicone rubber as the joining member and the member to be joined. Then heated for 10 minutes at coating a mixed solution of reactive functional group-containing alkoxy silane and a plurality vinyl group-containing alkoxy silane bonded members were diluted each 0.1 wt% in the same ethanol, 80 ° C. in a heating oven , Molecular adhesion treatment was applied. After the treatment, a bonding treatment was performed in the same manner as in Example 1 to obtain a bonded sample in which both members were bonded.

(Peeling strength test)
The bonded sample of Example 9 was subsequently subjected to a T-type peeling test at a speed of 100 mm / sec with a force gauge: ZP-200P (manufactured by Imada Co., Ltd.), and the pulling strength was measured for each, and the peeling surface was measured. The condition was observed. The results are shown in Table 3.

As is clear from Table 3, since the silicone of Example 9 was broken, it was found that the silicone was firmly bonded.

(Examples 10 to 12)
Corona discharge treatment was performed in the same manner as in Example 1 using PC, COP, and PMMA as the bonding base material A and the bonding base material B, respectively. Then heated for 10 minutes at coating a mixed solution of reactive functional group-containing alkoxy silane and a plurality vinyl group-containing alkoxy silane bonded members were diluted each 0.1 wt% in the same ethanol, 80 ° C. in a heating oven , Molecular adhesion treatment was applied. After the treatment, a joint sample was obtained in which both members were joined.

After the treated joint member and the member to be joined are subjected to corona discharge treatment in the same manner as described above, they are bonded together to remove air, and then a crimp press: 20 kN heater press N4020-20 (manufactured by NPa System Co., Ltd.) is used at 140 ° C. and 10 The pressure was applied for a minute to obtain a bonded sample in which both members were bonded.

(Shear strength test)
For the bonded samples of Examples 10 to 12, a shear strength test was performed at a test speed of 50 mm / min using a tensile tester: Autograph AGS-X (manufactured by Shimadzu Corporation), and the shear strength was measured for each. The state on the sheared surface was observed. The results are shown in Table 4.

As is clear from Table 4, since one layer of the substrate surface of Examples 10 to 12 was peeled off and coagulated and fractured, it was found that the base material was firmly bonded by a covalent bond with a molecular adhesive.

The bonded body of the present invention is made of the same or different metal, polymer resin, crosslinked rubber, glass or ceramics as the metal, polymer resin, crosslinked rubber, glass or ceramics bonded base material. reactive functional group-containing alkoxy silane and a plurality vinyl group-containing appliances housings joined via the alkoxy silane, its electrical and electronic components, various cases, containers, equipment, used in stationery and the like.

Claims (11)

The surface of at least one of the bonding base material and the base material to be bonded formed of metal, polymer resin, crosslinked rubber, glass or ceramics is
Unsaturated groups attached to the surface exposed reactive groups of its epoxy group, a ureido group, a mercapto group, a sulfide group, an isocyanate group, a plurality of alkoxysilyl group, an amino group, and at least one functional either nitrile groups found selected amplifying said surface exposed reactive group by a reactive functional group-containing alkoxy silanes containing groups and the modification site of the first layer surface-modified by a plurality vinyl group-containing alkoxy silane bonded to the modified site Gasoko by having an amplifier portion of the second layer which is,
It is bonded to the surface of the other base material via the amplification site .
A bonded body characterized by being a heat-pressed bonded body. And the bonding substrate and the object to be bonded substrate, by the amplification and the reactive functional group-containing alkoxy silane and a plurality vinyl group-containing alkoxy silane by surface modification, to claim 1, characterized in that it is joined The described conjugate. And the bonding substrate and the object to be bonded substrate, the surface-exposed reactive group on the surface of each other's side joined, via a covalent bond of the reactive functional group-containing alkoxy silane and the plurality vinyl group-containing alkoxy silane The joined body according to claim 1, wherein the joined body is joined. The plural vinyl group-containing alkoxysilane has the following chemical formula.
R ² (OR ^1- ) ₂ -Si-O-[(CH ₂ = CH-) (OR ^1- ) Si-O] _n -Si (-OR ¹ ) ₂ R ³
(In the equation, n is a number from ¹ to 20, R 1 is C _a H _{2a + 1} , and a is a number from 1 to 3, and R ² and R ³ are CH ₃ or CH ₂ = CH). The joined body according to claim 1, wherein the joint is made of one. The conjugate according to claim 1, wherein the reactive functional group-containing alkoxysilane is a silane coupling agent. The reactive functional group-containing alkoxysilane is an amino group- and alkoxy group-containing silane compound; a vinyl group and an alkoxy group-containing silane compound; an epoxy group and an alkoxy group-containing silane compound, a styryl group and an alkoxy group-containing silane compound; (meth) acrylic. Group and alkoxy group-containing silane compound; ureido group and alkoxy-containing silane compound; mercapto group and alkoxy-containing silane compound; sulfide group and alkoxy-containing silane compound; isocyanate group and alkoxy-containing silane compound, allyl group and alkoxy-containing silane compound; alkyl group The conjugate according to claim 1, further comprising an alkoxy group-containing silane compound; an aryl group and an alkoxy group-containing silane compound; an alkyl group and a chlorosilane group-containing silane compound; or a tetraalkoxysilane compound. The reactive functional group-containing alkoxy silane is bonded body according to claim 6, characterized in that the aminoalkyl trialkoxysilanes, or the amino group and aminoalkyl aminoalkyl trialkoxysilane and alkoxy group-containing silane compound .. The aminoalkyl aminoalkyl _{trialkoxysilanes, H 2 N- (C p H} 2p) -NH- (C q H 2q) -Si (-OC r H 2r + 1) 3 (p, q, r are independently The joined body according to claim 7, wherein the number is 1 to 6). At least one of the exposed surface of the bonded substrate, the surface of the modified portion thereof, and the surface of the amplified portion thereof, and / or the exposed surface of the substrate to be bonded and the surface of the modified portion thereof. The junction according to claim 1, wherein at least one of the surface and the surface of the amplification portion thereof is a corona discharge-treated surface, a plasma-treated surface, an ultraviolet-treated surface, and / or an excimer-treated surface. The surface on the bonding side between the bonding substrate and the substrate to be bonded has the modification site and the amplification site on the one hand, and the silanepropyltriethoxysilane compound-treated surface and the titanate compound-treated surface on the other hand. The junction according to claim 1, wherein the bonding surface is an aluminate compound-treated surface, a thiol compound-treated surface, an azide compound-treated surface, a corona discharge-treated surface, a plasma-treated surface, an ultraviolet-treated surface, and / or an excimer-treated surface. body. Surface of at least one base material of a bonding base material formed of metal, polymer resin, crosslinked rubber, glass or ceramics and a base material to be bonded made of metal, polymer resin, crosslinked rubber, glass or ceramics. the unsaturated group, an epoxy group, a ureido group, a mercapto group, a sulfide group, an isocyanate group, a plurality of alkoxysilyl group, the reactive functional group containing at least one functional group which amino group, and are chosen nitrile group or al by sequentially processed by containing alkoxy silane and a plurality vinyl group-containing alkoxy silane, the reactive surface-exposed reactive groups of the surface of the cemented side of at least one of the substrate and the bonding base material and the object to be bonded substrate after forming the modified region as a first layer by the reactive functional group-containing alkoxysilane with surface modification by the surface-exposed reactive groups by reacting a functional group-containing alkoxy silane, the plurality in its modified portion forming an amplification portion as a second layer by said plurality vinyl group-containing alkoxy silane is amplified by the modified site by a vinyl group-containing alkoxy silane,
The step of joining the surfaces on the joining side of both of these base materials and heat-pressing to obtain a heat-pressed joint body.
A method for producing a bonded body, which comprises having.