JP2022014112A - Joined body of rubber and joining method - Google Patents

Abstract

To provide a joining technique capable of joining at least one kind selected from the group consisting of metal, glass, ceramics, a resin and a rubber with a rubber without using an adhesive, and capable of joining with stable joining strength.SOLUTION: A joined body in which a rubber surface A with a functional group having at least one or more kinds of functional groups selected from the group consisting of an amino group, an epoxy group, a mercapto group, a styryl group, a (meth)acryloyl group, an isocyanate group, and an alkenyl group on a surface of the rubber, and an adherent surface B with a functional group having at least one or more kinds of functional groups selected from the group consisting of an amino group, an epoxy group, a mercapto group, a styryl group, a (meth)acryloyl group, an isocyanate group, and an alkenyl group are directly joined on a surface of at least one kind of adherent selected from the group consisting of metal, glass, ceramics, a resin and a rubber, and at least one kind of the rubber surface A with the functional group and the adherent surface B with the functional group is formed with a two-dimensional structure and a three-dimensional structure mixed.SELECTED DRAWING: None

Description

The present invention is selected from the group consisting of at least one adherend and rubber conjugate selected from the group consisting of metal, glass, ceramic, resin and rubber, and the group consisting of metal, glass, ceramic, resin and rubber. It relates to a method of joining at least one type of adherend and rubber.

Silicone rubber and fluororubber have excellent heat resistance, water resistance, chemical resistance, weather resistance, ozone resistance, and cold resistance. It is widely used in parts and manufacturing sites. Specifically, electrical parts, electronic parts, food machinery parts, equipment parts, medical materials, medical equipment parts, packings, gaskets, O-rings, sealing parts, tubes, hoses, piping parts, rubber stoppers, caps, rubber Examples include strings, rubber rings, rubber sheets, sponge sheets, mats, research equipment parts, caster parts, wheels, ducts, and frame packings.

However, silicon rubber and fluororubber have a problem that they are difficult to adhere to each other and cannot be sufficiently bonded to an adherend in various applications.
To solve these problems, for example, in Patent Document 1, in a metal gasket in which a rubber layer is provided on a metal plate via an adhesive layer, hexavalent chromium is used for the surface treatment of the metal conventionally performed in the metal gasket. Instead of the chromate method, by using an adhesive containing a rust preventive pigment in consideration of environmental issues, the permeation of corrosive factors is suppressed, and the anion that gradually elutes from the rust preventive pigment reacts with the metal plate to adhere to each other. A method for producing a chemical conversion film having good properties is disclosed.
Further, Patent Document 2 describes acid phosphate having a polymerizable unsaturated group in the molecule and acid phosphate having a polymerizable unsaturated group in the molecule as a sulfide adhesive composition showing good adhesiveness with respect to a sulfide adhesive for adhering various rubbers and various metals. / Or a vulgarized adhesive composition comprising a salt thereof is disclosed.
Further, Patent Documents 3 and 4 describe between the fluororubber layer and the outer silicon rubber layer with respect to a rubber hose for connecting an intercooler from a turbocharger for an automobile using a fluororubber having high heat resistance and a silicone rubber having high flexibility. Disclosed is a method of improving the low durability and low adhesiveness of a fluororubber layer by vulcanizing by arranging a silicon rubber layer containing a specific adhesive component.

However, all of the conventional techniques use an adhesive, and there is a problem that it takes time to join. In addition, all of the prior arts have a problem that sufficient bonding strength cannot be obtained.

Japanese Unexamined Patent Publication No. 2008-164122 Japanese Unexamined Patent Publication No. 2003-221556 Japanese Unexamined Patent Publication No. 2003-214565 Japanese Unexamined Patent Publication No. 2003-214566

The present invention has been made in view of such technical background, in which at least one adherend selected from the group consisting of metal, glass, ceramic, resin and rubber and rubber are used with an adhesive. It is an object of the present invention to provide a joining technology capable of joining efficiently and with stable joining strength.

The present invention provides the following means for achieving the above object.
In the present specification, joining means connecting objects to each other, and crimping, thermocompression bonding, welding, and bonding are subordinate concepts thereof.
In the present specification, crimping means to bring the bonded state into a bonded state by pressurization, and includes bonding without entanglement due to molecular diffusion.
In the present specification, thermocompression bonding means that materials of the same type or different types are heated to a temperature below their respective melting points and pressurized to cause plastic deformation, and the surfaces of both surfaces are brought into a bonded state, or the materials are bonded to each other. It means that the solid state is made into a bonded state (solid phase bonding) by utilizing the diffusion of molecules existing on the bonding surface.
In the present specification, welding means that materials of the same type or different types are heated to exceed their respective melting points and pressure is applied, and contact pressure and cooling are used to entangle and crystallize the materials by molecular diffusion to form a bonded state. means.
In the present specification, bonding means a state in which two adherends (those to be bonded) are bonded via an organic material (thermosetting resin, thermoplastic resin, etc.) such as a tape or an adhesive. Means that.

(Joint body)
[1] With a functional group having one or more functional groups selected from the group consisting of an amino group, an epoxy group, a mercapto group, a styryl group, a (meth) acryloyl group, an isocyanato group, and an alkenyl group on the surface of the rubber. Amino group, epoxy group, mercapto group, styryl group, (meth) acryloyl group, on the surface of the rubber surface A and at least one of the adherends selected from the group consisting of metal, glass, ceramic, resin and rubber. A functional group-attached adherend surface B having one or more functional groups selected from the group consisting of an isocyanato group and an alkenyl group is directly bonded to the functional group-attached rubber surface A and the functional group-attached substrate. A bonded body in which a two-dimensional monomolecular structure and a three-dimensional multimolecular structure are mixed on at least one of the material surface B.
[2] The combination of the functional group of the rubber surface A with a functional group and the functional group of the adherend surface B with a functional group is at least one of the following (1) to (9), according to [1]. Of the joint.
(1) Combination of amino group and epoxy group (2) Combination of mercapto group and epoxy group (3) Combination of isocyanato group and amino group (4) Combination of mercapto group and (meth) acryloyl group (5) Combination of mercapto group and amino Group combination (6) Combination of mercapto group and alkenyl group (7) Combination of amino group and (meth) acryloyl group (8) Combination of (meth) acryloyl groups (9) Combination of amino groups [3] The above-mentioned functionality One or more functional groups selected from the group consisting of the amino group, epoxy group, mercapto group, styryl group, (meth) acryloyl group, isocyanato group, and alkenyl group having the based rubber surface A on the surface of the rubber. The above-mentioned compound imparted by reacting with one or more compounds selected from the group consisting of a compound having an isocyanato group, a compound having a mercapto group, a compound having an epoxy group, a compound having an amino group, and a radically polymerizable compound. The conjugate according to [1] or [2], which has a functional group of origin.
[4] The group consisting of the amino group, the epoxy group, the mercapto group, the styryl group, the (meth) acryloyl group, the isocyanato group, and the alkenyl group that the adherend surface B with the functional group has on the surface of the adherend. One or more selected from the group consisting of a compound having an isocyanato group, a compound having a mercapto group, a compound having an epoxy group, a compound having an amino group, and a radically polymerizable compound in one or more functional groups selected from the above. The conjugate according to any one of [1] to [3], which has a functional group derived from the compound given by reacting the compound.
[5] The bonded body according to any one of [1] to [4], wherein the rubber is at least one of silicon rubber and fluororubber.
[6] The bonded body according to any one of [1] to [5], wherein the shape of the rubber and the adherend is one or more selected from the group consisting of a lump, a plate, and a thin film. ..

(Joining method)
[7] With a functional group having one or more functional groups selected from the group consisting of an amino group, an epoxy group, a mercapto group, a styryl group, a (meth) acryloyl group, an isocyanato group, and an alkenyl group on the surface of the rubber. Amino group, epoxy group, mercapto group, styryl group, (meth) acryloyl group, on the surface of the rubber surface A and at least one of the adherends selected from the group consisting of metal, glass, ceramic, resin and rubber. A method for joining rubber and an adherend, wherein the adherend surface B with a functional group having one or more functional groups selected from the group consisting of an isocyanato group and an alkenyl group is pressure-bonded and bonded. A method for joining rubber and an adherend, wherein at least one of a functional group-attached rubber surface A and a functional group-attached adherend surface B has a mixture of a two-dimensional monomolecular structure and a three-dimensional multimolecular structure.
[8] The combination of the functional group of the rubber surface A with a functional group and the functional group of the adherend surface B with a functional group is at least one of the following (1) to (9), according to [7]. How to join rubber and adherend.
(1) Combination of amino group and epoxy group (2) Combination of mercapto group and epoxy group (3) Combination of isocyanato group and amino group (4) Combination of mercapto group and (meth) acryloyl group (5) Combination of mercapto group and amino Group combination (6) Mercapto group and alkenyl group combination (7) Amino group and (meth) acryloyl group combination (8) (Meta) acryloyl group combination (9) Amino group combination [9] With rubber , The rubber and the adherend according to [7] or [8], wherein the compound corresponding to at least one of the following (i) to (iii) is reacted to form the functional group-attached rubber surface A. Joining method.
(I) An alkoxysilane compound (ii) One compound selected from the group consisting of a compound having an amino group, a compound having an epoxy group, a compound having a mercapto group, and a compound having an isocyanato group (iii) a radically polymerizable group. [10] A compound corresponding to at least one of the following (i) to (iii) is reacted with at least one adherend selected from the group consisting of metal, glass, ceramic, resin and rubber. The method for joining rubber and an adherend according to [7] or [8], wherein the adherend surface B with a functional group is formed.
(I) An alkoxysilane compound (ii) One compound selected from the group consisting of a compound having an amino group, a compound having an epoxy group, a compound having a mercapto group, and a compound having an isocyanato group (iii) a radically polymerizable group. [11] A silane coupling in which the alkoxysilane compound has one or more functional groups selected from the group consisting of an amino group, an epoxy group, a mercapto group, a styryl group, a (meth) acryloyl group, and an isocyanato group. The method for joining a rubber and an adherend according to [9] or [10], which is an agent.
[12] The method for joining a rubber and an adherend according to [11], wherein the temperature at which the silane coupling agent is reacted is 5 to 30 ° C.
[13] The rubber according to [9] or [10], wherein the compound having an amino group is at least one of an amino compound having a (meth) acryloyl group and an amino compound having a bifunctional or higher functional group. And how to join the adherend.
[14] The compound having an epoxy group is at least one selected from the group consisting of an epoxy compound having a (meth) acryloyl group, an epoxy compound having an alkenyl group, and a bifunctional or higher functional epoxy compound. [9] Alternatively, the method for joining the rubber and the adherend according to [10].
[15] The method for joining a rubber to an adherend according to [9] or [10], wherein the compound having a mercapto group is a bifunctional or higher functional thiol compound.
[16] The rubber and adherend according to [9] or [10], wherein the compound having an isocyanato group is at least one of an isocyanato compound having a (meth) acryloyl group or a bifunctional or higher functional isocyanato compound. Joining method.
[17] The method for joining a rubber to an adherend according to [9] or [10], wherein the radically polymerizable compound is a compound having a (meth) acryloyl group.
[18] A rubber, amino group, and epoxy group having one or more functional groups on the surface selected from the group consisting of an amino group, an epoxy group, a mercapto group, a styryl group, a (meth) acryloyl group, an isocyanato group, and an alkenyl group. , Mercapto, a compound having an isocyanato group, at least one of an adherend having at least one functional group selected from the group consisting of a mercapto group, a styryl group, a (meth) acryloyl group, an isocyanato group, and an alkenyl group The rubber surface A with a functional group and the functional group are attached by reacting one or more compounds selected from the group consisting of a compound having a group, a compound having an epoxy group, a compound having an amino group, and a radically polymerizable compound. The method for joining a rubber and an adherend according to [7] or [8], which forms at least one of the adherend surfaces B.
[19] The rubber according to any one of [7] to [18], wherein at least one of the functional group-attached rubber surface A and the functional group-attached adherend surface B is washed before the crimping. How to join the adherend.
[20] The joining of rubber and adherend according to any one of [7] to [19], wherein the rubber surface A with a functional group and the adherend surface B with a functional group are bonded by thermocompression bonding. Method.
[21] The method for joining rubber and an adherend according to any one of [7] to [19], wherein the rubber surface A with a functional group and the adherend surface B with a functional group are joined by welding. ..
[22] The rubber according to [21], wherein the welding is by at least one selected from the group consisting of an ultrasonic welding method, a vibration welding method, an electromagnetic induction method, a high frequency method, a laser method, and a hot pressing method. How to join the adherend.
[23] The rubber surface A with a functional group and the adherend surface B with a functional group are formed by at least one of a spray coating method and a dipping method, according to any one of [7] to [22]. The method of joining the rubber and the adherend as described.

According to the present invention, at least one adherend selected from the group consisting of metal, glass, ceramic, resin and rubber and rubber can be efficiently applied without using an adhesive by a simple and short-time operation. Moreover, it is possible to join with stable joining strength.

Hereinafter, the joined body and the joining method according to the embodiment of the present invention will be described in detail.

《Joint body》
The conjugate of one embodiment has one or more functional groups selected from the group consisting of an amino group, an epoxy group, a mercapto group, a styryl group, a (meth) acryloyl group, an isocyanato group, and an alkenyl group on the surface of the rubber. An amino group, an epoxy group, a mercapto group, a styryl group, ( Meta) A functional group-attached adherend surface B having one or more functional groups selected from the group consisting of an acryloyl group, an isocyanato group, and an alkenyl group is directly bonded to the functional group-attached rubber surface A and the functional group. At least one of the functional group-attached adherend surfaces B has a mixture of a two-dimensional single molecule structure and a three-dimensional multimolecular structure.
Here, the "two-dimensional monomolecular structure" means that the functional groups constitute a monomolecular layer in which the functional groups are highly oriented and self-assembled at high density. It includes a so-called self-assembled monolayer (SAM). For example, a two-dimensional monomolecular structure can be formed by forming a silane coupling agent into a film by a chemical vapor deposition (CVD) method.
On the other hand, the "three-dimensional multimolecular structure" is a structure in which a molecular chain is branched and three-dimensionally extended or superposed, and a functional group addition process in two steps as described later. This means a structure in which a functional group is introduced and the functional group structure is three-dimensionally extended. For example, trifunctional alkoxysilanes form a network polymer called silsesquioxane (SQ: Silsesquioxane; (RSiO _1.5 ) _n ) by hydrolysis followed by condensation reaction, forming a cage-type, incomplete cage. It can form a three-dimensional polymolecular structure such as a mold or a double-decker type. Therefore, at least one of the functional group-attached rubber surface A and the functional group-attached adherend surface B in which the functional group is introduced into the surface of the rubber and at least one surface of the adherend using a trifunctional alkoxysilane having a functional group. Can be said to have more three-dimensional multimolecular structures.
On the bonding surface formed by directly bonding the rubber surface A with a functional group and the adherend surface B with a functional group, chemical bonds, hydrogen bonds, and van der Waals forces between the functional groups occur. Due to these bonding forces, the rubber and the adherend can be bonded with sufficient bonding strength without using an adhesive.
It should be noted that the properties of the bonded surface are diverse depending on the combination of functional groups and conditions such as the pressure at the time of bonding, and the specific mode thereof cannot be comprehensively expressed. Therefore, it can be said that it is impossible or impractical to directly specify the bonded body according to the present invention by its structure or characteristics.

<Rubber>
The type of rubber forming the rubber surface A with a functional group is not particularly limited, and general natural rubber or synthetic rubber can be used. Difficult-to-adhesive silicone rubber and fluororubber, which are excellent in heat resistance, cold resistance, chemical resistance, ozone resistance, and the like, can also be used. In addition, as the rubber, isoprene rubber, butadiene rubber, styrene / butadiene rubber, butyl rubber, nitrile rubber, ethylene / propylene rubber, chloroprene rubber, acrylic rubber, chlorosulfonated polyethylene rubber, urethane rubber, ethylene / vinyl acetate rubber, epichlorohydrin rubber, And known rubber such as polysulfide rubber can be exemplified.

(Preprocessing)
Before applying a treatment to the surface of the rubber to impart one or more functional groups selected from the group consisting of an amino group, an epoxy group, a mercapto group, a styryl group, a (meth) acryloyl group, an isocyanato group and an alkenyl group. It is preferable to apply the treatment.

The pretreatment is preferably a treatment in which one or more selected from the group consisting of a hydroxyl group, a formyl group, a carboxy group and a radical is generated on the surface of the rubber. All of these hydroxyl groups, formyl groups, carboxy groups, and radicals serve as starting points when imparting the functional group to the surface of rubber.

Examples of the pretreatment include plasma treatment, corona discharge treatment, UV ozone treatment and the like. These treatments may be performed with only one type or two or more types. As a specific method of these pretreatments, a known method can be used.
The plasma treatment is to create a plasma beam with a high-voltage power supply and a rod and hit it against the surface of the material to excite molecules to create a functional state. Be done.
The corona discharge treatment includes a method applied to surface modification of a polymer film, and a radical generated by cleaving a polymer main chain or a side chain of a polymer surface layer by electrons emitted from an electrode is used as a starting point. This is a method of generating a hydroxyl group or a polar group on the surface.
The UV ozone treatment is a method of cleaning or reforming the surface by the energy of short-wavelength ultraviolet rays emitted from a low-pressure mercury lamp and the power of ozone ₍ O3) generated by the energy. In the case of glass, it is one of the surface cleaning methods for removing organic impurities on the surface. Generally, a cleaning surface reforming device using a low-pressure mercury lamp is called a "UV ozone cleaner", a "UV cleaning device", an "ultraviolet surface modifying device" or the like.

The properties of the surface pretreated by the above method may be different from those immediately after the pretreatment due to the addition of the functional group described below on the surface treated surface. Therefore, it is considered impossible or impractical to specify and express the properties of the pretreated surface. Therefore, in the present invention, the pretreated surface is specified by the pretreatment method.

(Functional group imparting treatment)
By reacting the surface of the rubber with at least one of the following (a) and (b), the surface of the rubber is composed of an amino group, an epoxy group, a mercapto group, a styryl group, a (meth) acryloyl group, an isocyanato group and an alkenyl group. It is possible to impart one or more functional groups selected from the group.
(a) An alkoxysilane compound having at least one selected from the group consisting of an amino group, an epoxy group, a mercapto group, a styryl group, a (meth) acryloyl group, an isocyanato group and an alkenyl group.
(b) At least one compound selected from the group consisting of a compound having an amino group, a compound having an epoxy group, a compound having a mercapto group, a compound having an isocyanato group, and a compound having a radically polymerizable group.

After the pretreatment, a rubber having at least one selected from the group consisting of a hydroxyl group, a formyl group, a carboxy group and a radical is used on the surface thereof, and an amino group, an epoxy group, a mercapto group and a styryl group are used on the surface. Meta) It is more preferable to impart one or more functional groups selected from the group consisting of an acryloyl group, an isocyanato group and an alkenyl group.

The functional group-attached rubber surface A formed by the treatment for imparting a functional group by the above method (hereinafter referred to as a functional group imparting treatment) is a self-assembled monolayer (SAM) having a two-dimensional structure or a part of a molecule. It consists of a structure including a structure in which a chain is branched and three-dimensionally extended or superposed. In particular, it can be said that the rubber surface A with a functional group in which a functional group is introduced into the surface of the rubber by using a trifunctional alkoxysilane having a functional group has a larger three-dimensional multimolecular structure.

(Alkoxysilane compound)
A specific example of the alkoxysilane compound is a silane coupling agent, which has a functional group such as an amino group, an epoxy group, a mercapto group, a styryl group, a (meth) acryloyl group, an isocyanato group, and an alkenyl group.
Specific examples of the silane coupling agent include vinyltrimethoxysilane having a vinyl group, vinyltriethoxysilane, 2- (3,4-epyloxycyclohexyl) ethyltrimethoxysilane having an epoxy group, and 3-glyci having a glycidyl group. Sidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, P-styryltrimethoxysilane having a styryl group, 3-methacryloxypropylmethyldimethoxysilane having a methacrylo group, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxy Silane, 3-acryloxypropyltrimethoxysilane having an acryloxy group, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane having an amino group, N-2- (aminoethyl) -3-aminopropylmethyl Dimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl) -Buchilidene) Propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminopropyltrimethoxysilane hydrochloride, tris- (trimethoxysilylpropyl) isocia with isocyanurate group Nurate, 3-ureidopropyltrialkoxysilane with ureido group, 3-mercaptopropylmethyldimethoxysilane with mercapto group, 3-isocyanatopropyltriethoxysilane with isocyanato group, dithioltriazinepropyltriethoxysilane with triazine mercapto group, Examples thereof include 6- (triethoxysilylpropylamino) -1,3,5-triazine-2,4-dithiolmonosodium salt (TES) having an ethoxysilyl group and a mercapto group.

The method for imparting a functional group to the surface of the rubber with the silane coupling agent is not particularly limited, and examples thereof include a spray coating method and a dipping method.
In the dipping method, a low-concentration aqueous solution of the silane coupling agent or a low-concentration organic solvent solution of the silane coupling agent is brought into contact with the surface of the rubber, so that the hydroxyl group or the like existing on the surface of the rubber reacts with the silane coupling agent. Then, a silanol group is generated, and the oligomerized silanol group is bonded to the surface of the rubber. Specifically, for example, the material is immersed in a diluted solution obtained by diluting a silane coupling agent with an organic solvent to a concentration of about 0.5% by mass to 50% by mass at 1 to 100 ° C. for 1 minute to 5 days. By doing so, it is possible to introduce a functional group chemically bonded to the surface of the rubber.
In the spray coating method, the silane coupling agent itself or the silane coupling agent diluted in an organic solvent is sprayed on the surface of the rubber, and the rubber is dried at 1 to 100 ° C. for 1 minute to 5 days. After a drying treatment, a strong chemical bond is formed, and a functional group chemically bonded to the surface of the rubber can be introduced.
Suitable treatment conditions for imparting a functional group with the silane coupling agent are high temperature for a short time (40 to 100 ° C. for 1 minute to 60 minutes) or low temperature for a long time (5 to 30 ° C. for 1 hour to 3 days). ), And depending on the type of silane coupling agent, the treatment condition of "1 hour to 3 days at 5 to 30 ° C." is particularly suitable.

It is also effective to wash the surface into which the functional group is introduced by the silane coupling agent with an organic solvent, alcohol, water or the like. The strength of the bonded body can be increased by removing the silane coupling agent and the compound derived from the silane coupling agent remaining on the functional group introduced by the chemical bond with a weak adsorptive force.

(Compound with amino group)
Specific examples of the compound having an amino group include an amino compound having a (meth) acryloyl group and an amino compound having a bifunctional or higher functional group as the compound having an amino group. The compound having an amino group is not particularly limited, but for example, ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 1,4-diaminobutane, hexamethylenediamine, 2,5. -Dimethyl-2,5-hexanediamine, 2,2,4-trimethylhexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, 4-aminomethyloctamethylenediamine, 3,3'-iminobis (Propylamine), 3,3'-methylimiminobis (propylamine), bis (3-aminopropyl) ether, 1,2-bis (3-aminopropyloxy) ethane, mensendiamine, isophoronediamine, bisamino Methylnorbornan, bis (4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl) methane, 1,3-diaminocyclohexane, 3,9-bis (3-aminopropyl) -2,4,8, Examples thereof include 10-tetraoxaspiro [5,5] undecane, aminoethylpiperazine, (meth) acrylamide and the like.

The method for imparting a functional group with the compound having an amino group is not particularly limited, and examples thereof include a spray coating method and a dipping method. Specifically, for example, a diluted solution obtained by diluting a compound having an amino group with an organic solvent to a concentration of about 5% by mass to 50% by mass is heated to room temperature to 100 ° C. and rubber is added to the diluted solution. Examples thereof include a method in which the material is immersed for 1 minute to 5 days, then the material is taken out and dried at room temperature to 100 ° C. for 1 minute to 5 hours.

It is also effective to wash the surface into which the functional group is introduced by the compound having an amino group with an organic solvent or the like. The strength of the conjugate can be increased by removing the compound having an amino group or the compound derived from the compound having an amino group remaining on the functional group introduced by a strong bond with a weak adsorptive force.

(Compound with epoxy group)
Specific examples of the compound having an epoxy group include an epoxy compound having a (meth) acryloyl group, an epoxy compound having an alkenyl group, and a bifunctional or higher functional epoxy compound. Examples thereof include glycidyl (meth) acrylate, allyl glycidyl ether, 1,6-hexanediol diglycidyl ether, and epoxy resins having two or more epoxy groups in the molecule. It may also be an alicyclic epoxy compound, such as 3,4-epoxycyclohexylmethylmethacrylate (Cyclomer M100 manufactured by Daicel Co., Ltd.), 1,2-epoxy-4-vinylcyclohexane (Selokiside 2000 manufactured by Daicel Co., Ltd.), 3', Examples thereof include 4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (celloxide 2021P manufactured by Daicel Co., Ltd.).

The method for imparting a functional group to the rubber surface with the compound having an epoxy group is not particularly limited, and examples thereof include a spray coating method and a dipping method.
In the dipping method, a compound having an epoxy group and a low-concentration organic solvent solution of an amine-based or phosphorus-based catalyst are brought into contact with the surface of the rubber, so that the hydroxyl group or the like existing on the surface of the rubber reacts with the epoxy group to make it functional. A group can be added. Specifically, for example, a diluted solution obtained by diluting a compound having an epoxy group containing 0.5 to 5% by mass of a catalyst with an organic solvent to a concentration of about 0.5% by mass to 50% by mass is prepared at room temperature. By warming to 100 ° C. and immersing the material in this diluted solution for 1 minute to 5 days, a functional group chemically bonded to the surface of the rubber can be introduced.
In the spray coating method, a diluted solution obtained by diluting the compound having an epoxy group containing 0.5 to 5% by mass on the surface of the rubber with an organic solvent to a concentration of about 0.5% by mass to 50% by mass is used. Spray and dry at room temperature to 100 ° C for 1 minute to 5 hours. After a drying treatment, a strong chemical bond is formed, and a functional group chemically bonded to the surface of the rubber can be introduced.

Known amine-based and phosphorus-based catalysts can be used. The amine-based catalyst is not particularly limited, but for example, triethylenediamine, tetramethylguanidine, N, N, N', N'-tetramethylhexane-1,6-diamine, dimethyl etheramine, N, Examples thereof include N, N', N'', N''-pentamethyldipropylene-triamine, N-methylmorpholin, bis (2-dimethylaminoethyl) ether, dimethylaminoethoxyethanol, triethylamine and the like. The phosphorus-based catalyst is not particularly limited, and examples thereof include triphenylphosphine, benzyltriphenylphosphonium chloride, n-butyltriphenylphosphonium bromide, and the like.

It is also effective to wash the surface into which the functional group is introduced by the compound having an epoxy group with an organic solvent or the like. The strength of the bonded body can be increased by removing the compound having an epoxy group or the compound derived from the compound having an epoxy group remaining on the functional group introduced by the chemical bond with a weak adsorptive force.

(Compound having a mercapto group)
Specific examples of the compound having a mercapto group are a polyfunctional thiol compound and a compound having an alkenyl group other than the mercapto group. The compound having a mercapto group is not particularly limited, but for example, pentaerythritol tetrakis (3-mercaptopropionate) (for example, "QX40" manufactured by Mitsubishi Chemical Corporation and "QX40" manufactured by Toray Fine Chemicals Co., Ltd. QE-340M "), ether-based first-class thiol (for example," Cup Cure 3-800 "manufactured by Cognis), 1,4-bis (3-mercaptobutyryloxy) butane (for example," Karenz "manufactured by Showa Denko KK MT (registered trademark) BD1 "), pentaerythritol tetrakis (3-mercaptobutyrate) (for example," Karens MT (registered trademark) PE1 "manufactured by Showa Denko KK), 1,3,5-tris (3-mercaptobutyloxy) Ethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trion (for example, "Carens MT (registered trademark) NR1" manufactured by Showa Denko KK) and the like can be mentioned. Among them, pentaerythritol tetrakis (3-mercaptobutyrate) is excellent in stability in epoxy resin.

The method for imparting a functional group with the compound having a mercapto group is not particularly limited, and examples thereof include a spray coating method and a dipping method. Specifically, for example, a diluted solution obtained by diluting a compound having a mercapto group with an organic solvent to a concentration of about 5% by mass to 50% by mass is heated to room temperature to 100 ° C., and the material is contained in this diluted solution. For 1 minute to 5 days, the material is taken out and dried at room temperature to 100 ° C. for 1 minute to 5 hours. Amines may be contained as a catalyst in the diluted solution of the compound having a mercapto group.

It is also effective to wash the surface into which the functional group is introduced by the compound having a mercapto group with an organic solvent or the like. The strength of the conjugate can be increased by removing a compound having a mercapto group or a compound derived from a compound having a mercapto group remaining on the functional group introduced by a chemical bond with a weak adsorptive force.

(Compound having an isocyanato group)
Specific examples of the compound having an isocyanato group are an isocyanato compound having a (meth) acryloyl group, a bifunctional or higher functional isocyanate compound, and the like. For example, a known isocyanate compound or the like can be used. The compound having an isocyanato group is not particularly limited, but for example, it is a polyfunctional isocyanate such as diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), tolylene diisocyanate (TDI), and isophorone diisocyanate (IPDI). ) Etc., 2-isocyanatoethyl methacrylate (for example, "Carens MOI" (registered trademark) manufactured by Showa Denko Co., Ltd.) and 2-isocyanatoethyl acrylate (for example, Showa Denko Co., Ltd.), which are isocyanate compounds having a radically polymerizable group. "Karenzu AOI (registered trademark)" manufactured by "Karensu AOI (registered trademark)"), 1,1- (bisacryloyloxyethyl) ethyl isocyanate (for example, "Karenzu BEI (registered trademark)" manufactured by Showa Denko Co., Ltd.) and the like.

The method for treating the rubber surface with the compound having an isocyanato group is not particularly limited, and examples thereof include a spray coating method and a dipping method. Specifically, for example, a diluted solution obtained by diluting a compound having an isocyanato group with an organic solvent to a concentration of about 5% by mass to 50% by mass is heated to room temperature to 100 ° C., and the material is contained in this diluted solution. For 1 minute to 5 days, the material is taken out and dried at room temperature to 100 ° C. for 1 minute to 5 hours.

It is also effective to wash the surface into which the functional group is introduced by the isocyanate compound with an organic solvent or the like. The strength of the bonded body can be increased by removing the isocyanate compound remaining on the functional group introduced by the chemical bond with a weak adsorptive force or the compound derived from the isocyanate compound.

(Radical polymerizable compound)
As used herein, the term "radical polymerizable compound" means a compound having a radically polymerizable group such as an ethylenic carbon-carbon double bond. Specific examples of the radically polymerizable group include, but are not limited to, alkenyl groups such as a methacryloyloxy group, an acryloyloxy group, and a vinyl group.
Specific examples of the compound having a radically polymerizable group include a compound having a (meth) acryloyl group and a vinyl group. Glycidyl (meth) acrylate having a glycidyl group, (meth) acrylamide having an amino group, hydroxymethyl (meth) crylate having a hydroxyl group, (meth) acrylic acid having a carboxy group, 2-isocyanatoethyl methacrylate (for example, Showa Denko Co., Ltd.) Examples thereof include "Karenzu MOI" (registered trademark) manufactured by the company and 2-isocyanatoethyl acrylate (for example, "Karenzu AOI (registered trademark)" manufactured by Showa Denko Co., Ltd.). Further, a terminal styrene compound such as bifunctional or higher (meth) acrylate or divinylbenzene may be used.

The method for treating the rubber surface with the compound having a radically polymerizable group is not particularly limited, and examples thereof include a spray coating method and a dipping method. Specifically, for example, a diluted solution obtained by diluting a compound having a radically polymerizable group with an organic solvent to a concentration of about 5% by mass to 50% by mass is heated to room temperature to 100 ° C. and contained in this diluted solution. After immersing the material in the solvent for 1 minute to 5 days, the material is taken out and dried at room temperature to 100 ° C. for 1 minute to 5 hours.

It is also effective to wash the surface into which the functional group is introduced by the compound having a radically polymerizable group with an organic solvent or the like. The strength of the conjugate can be increased by removing a compound having a radically polymerizable group or a compound derived from a compound having a radically polymerizable group remaining on the functional group introduced by a chemical bond with a weak adsorptive force. ..

(Functional group extension treatment)
As described above, on the surface of the rubber after the functional group imparting treatment, a SAM having a two-dimensional structure or a structure in which the molecular chain is branched and three-dimensionally stretched or superposed is formed. However, the SAM of the two-dimensional structure can be further extended in the three-dimensional direction by the following functional group extension treatment.
Here, the functional group extension treatment is one or more selected from the group consisting of an amino group, an epoxy group, a mercapto group, a styryl group, a (meth) acryloyl group, an isocyanato group and an alkenyl group through the functional group addition treatment. One or more selected from the group consisting of a rubber having a functional group on the surface, a compound having an isocyanato group, a compound having a mercapto group, a compound having an epoxy group, a compound having an amino group, and a radically polymerizable compound. It means a process of reacting a compound.

When an amino group is imparted to the rubber surface by the functional group imparting treatment, a compound having an isocyanato group, a compound having an epoxy group, or the like is reacted with the amino group to extend the functional group structure of the rubber surface in a three-dimensional direction. Can be made to.
For example, when 2-isocyanatoethyl methacrylate (for example, "Carens MOI (registered trademark)" manufactured by Showa Denko Co., Ltd.) or glycidyl methacrylate, which is an isocyanate compound having a radically polymerizable group, is reacted with the amino group, the amino group is reacted in a three-dimensional direction. The extended extreme end becomes a radically polymerizable (meth) acryloyl group.

When a (meth) acryloyl group is imparted to the rubber surface by the functional group imparting treatment, a compound having a mercapto group or the like is reacted with the (meth) acryloyl group to extend the functional group structure of the rubber surface in a three-dimensional direction. Can be made to.
For example, 1,4-bis (3-mercaptobutylyloxy) butane (for example, "Karens MT (registered trademark) BD1" manufactured by Showa Denko KK), which is a bifunctional thiol compound, and pentaerythritol tetrakis, which is a trifunctional thiol compound (for example, 3-Mercaptobutyrate) (for example, "Karensu MT (registered trademark) PE1" manufactured by Showa Denko KK) is reacted with a (meth) acryloyl group, and the terminal end extended in the three-dimensional direction is an epoxy group or (meth). It becomes a mercapto group capable of an addition reaction with an acryloyl group.

When an epoxy group is added to the rubber surface by the functional group imparting treatment, an amino group, an amino compound having another amino group or another functional group, a mercapto group, and a thiol having another mercapto group or another functional group are used. A compound, a carboxy group, a compound having another carboxy group or another functional group, or the like can be reacted with the epoxy group to extend the functional group structure on the rubber surface in a three-dimensional direction.
For example, when (meth) acrylic acid is reacted with an epoxy group of a silane coupling agent, the terminal end extending in the three-dimensional direction becomes a (meth) acryloyl group which is also radically polymerizable.

When a mercapto group is imparted to the rubber surface by the functional group imparting treatment, the (meth) acryloyl group can be reacted with the mercapto group to extend the functional group structure of the rubber surface in the three-dimensional direction.
For example, by reacting a methacryloyl group of Karens MOI® with a mercapto group on the rubber surface, the most terminally extended in the three-dimensional direction can be an isocyanato group, and the (meth) acrylamide (meth) acryloyl group can be used. Can be reacted with a mercapto group to make the terminal end extending in the three-dimensional direction an amino group. Further, if the (meth) acryloyl group of glycidyl (meth) acrylate is reacted with the mercapto group, the terminal end extending in the three-dimensional direction can be used as an epoxy group.

The terminal end extending in the three-dimensional direction in this way can be used as various functional groups. In addition to the above compounds, for example, it can be expected that if a diisocyanate compound is reacted, only one isocyanato group will react and the terminal end will be an isocyanato group, and if a diamine is reacted, only one amino group will react. It can also be expected that the terminal will be an amino group.

Examples of the method for functional group extension treatment include a dipping method and a spray coating method.
In the dipping method, a low-concentration organic solvent solution of a compound having an isocyanato group, a compound having a mercapto group, a compound having an epoxy group, a compound having an amino group, and a radically polymerizable compound in which a catalyst such as a tertiary amine coexists is used. The functional group structure of the rubber surface can be extended in the three-dimensional direction by contacting the rubber surface after the functional group imparting treatment at 5 ° C to 120 ° C.
In the spray coating method, a compound having an isocyanato group, a compound having a mercapto group, a compound having an epoxy group, a compound having an amino group, and a radical in which a catalyst such as a tertiary amine coexists on the rubber surface after the functional group addition treatment. The organic solvent solution of the polymerizable compound is sprayed and dried at room temperature to 100 ° C. for 1 minute to 5 hours. By performing such a treatment, the functional group structure of the rubber surface can be extended in the three-dimensional direction.

The compounds having an isocyanato group, the compounds having a mercapto group, the compounds having an epoxy group, the compounds having an amino group, and the radically polymerizable compounds used for the functional group extension treatment are the same as those used for the functional group imparting treatment. Can be used.

<Applied material>
The adherend forming the surface B of the adherend with a functional group comprises at least one selected from the group consisting of metal, glass, ceramic, resin and rubber.
The form of the adherend is not particularly limited, and may be, for example, one or more shapes selected from the group consisting of a lump, a plate, and a thin film.

"metal"
The metal is not particularly limited. For example, iron, aluminum, copper, magnesium, titanium and the like can be mentioned. Of these, aluminum and copper are particularly preferably used from the viewpoint of light weight and ease of processing. In the present invention, the term "aluminum" is used to include aluminum and its alloys. Similarly, iron, copper, aluminum, magnesium, and titanium are also used in the sense that they include these simple substances and their alloys (stainless steel, duralumin, etc.).

《Glass》
Examples of the glass include soda-lime glass, lead glass, borosilicate glass, quartz glass and the like.

"ceramic"
Examples of the ceramic include oxide-based ceramics such as alumina, zirconia and barium titanate, hydroxide-based ceramics such as hydroxyapatite, carbide-based ceramics such as silicon carbide, and nitride-based ceramics such as silicon nitride.
When the adherend is made of ceramic, the thickness is preferably 1.0 mm or more, more preferably 2.0 mm or more, respectively, from the viewpoint of strength. The upper limit of the thickness of the ceramic is not particularly limited, but is preferably 20 mm or less, more preferably 15 mm or less.

"resin"
The resin is preferably a thermoplastic resin or a thermosetting resin (cured product). The resin may be a known resin alone, or may be reinforced with glass fiber or carbon fiber such as FRP. The resin to be joined is a preformed member.

The type of resin is not particularly limited, and a general synthetic resin may be used. Polypropylene (PP) resin, polyamide 6 (PA6) resin, polyamide 66 (PA66) resin, modified polyphenylene ether (m-PPE) resin, polyphenylene terfide (PPS) resin, polyetherimide (PEI) resin, polycarbonate (PC) Examples thereof include resins, polybutylene terephthalate (PBT) resins, and acrylic resins. In addition, PTFE (polytetrafluoroethylene), LCP (liquid crystal polymer), PPE (polyphenylene ether), Low, which are used in combination with low-roughness copper foil in high-frequency printed substrates that require low dielectric constant and low dielectric adjacency. -K materials (low dielectric constant epoxy resin, etc.) are mentioned, and in the automobile field, general-purpose resins such as polypropylene, polycarbonate resin, polyester resin, nylon, polybutylene terephthalate resin, polyetherimide resin, engineering plastic, super engineering plastic, etc. Can also be mentioned. Alternatively, FRP or a thermosetting resin may be used. FRP means a composite material in which fibers such as glass fiber and carbon fiber are put in plastic to improve the strength.
FRP may be hand lay-up molded or filament winding molded a woven fabric or non-woven fabric using resin and glass fiber, carbon fiber, aramid fiber or the like. Further, a sheet molding compound (C-SMC) or a bulk molding compound (BMC) may be used.
The sheet molding compound (C-SMC) is a mixture of at least one of an unsaturated polyester resin and a vinyl ester resin, a polymerizable unsaturated monomer, a curing agent, a low shrinkage agent, a filler, and the like, and then further reinforced with fibers. It is a sheet-shaped molding material obtained by containing the material. The bulk molding compound (BMC) is a bulk molding material. These molding materials are molded into a target molded product by a molding method such as compression molding, transfer molding, or injection molding.

The resin is preferably one or more selected from the group consisting of lumps, films, sheets, FRPs, and prepregs.
The resin may be in the form of a film, and may be, for example, a coating film made of a paint.
Here, the coating film means a film formed by applying a coating material containing a pigment, a resin, an additive, and a solvent. The coating film can be formed by applying the paint and then drying it.

《Rubber》
The type of rubber is not particularly limited as in the rubber forming the rubber surface A with a functional group, and general natural rubber or synthetic rubber may be used. Difficult-to-adhesive silicone rubber and fluororubber, which are excellent in heat resistance, cold resistance, chemical resistance, ozone resistance, etc., can also be used. In addition, isoprene rubber, butadiene rubber, styrene / butadiene rubber, butyl rubber, nitrile rubber, ethylene / propylene rubber, chloroprene rubber, acrylic rubber, chlorosulfonated polyethylene rubber, urethane rubber, ethylene / vinyl acetate rubber, epichlorohydrin rubber, polysulfide rubber, etc. Known rubber is mentioned.
The rubber as an adherend may be of the same type as or different from the rubber forming the rubber surface A with a functional group.

(Preprocessing)
Before applying a treatment to the surface of the adherend to apply one or more functional groups selected from the group consisting of an amino group, an epoxy group, a mercapto group, a styryl group, a (meth) acryloyl group, an isocyanato group and an alkenyl group. , It is preferable to perform pretreatment.
The pretreatment is preferably a treatment in which one or more selected from the group consisting of a hydroxyl group, a formyl group, a carboxy group and a radical is generated on the surface of the adherend. All of these hydroxyl groups, formyl groups, carboxy groups, and radicals serve as base points when the functional group is applied to the surface of the adherend.

(Metal pretreatment)
Examples of the metal pretreatment include cleaning with a solvent, degreasing treatment, blasting treatment, polishing treatment, etching treatment, caustic treatment, plasma treatment, corona discharge treatment, UV ozone treatment and the like. Among them, for a copper foil whose surface is not roughened or a copper foil plated with chromate, nickel or the like, a pretreatment for generating a hydroxyl group on the surface of a metal material is preferable. These treatments may be performed with only one type or two or more types. As a specific method of these pretreatments, a known method can be used.
The cleaning and degreasing treatment is a method of removing stains such as oils and fats on the surface of the material layer by dissolving them with an organic solvent such as acetone and toluene.
Examples of the blasting treatment include wet blasting treatment, shot blasting treatment, sandblasting treatment and the like. Above all, the wet blast treatment is preferable because a finer surface can be obtained as compared with the drive last treatment.
Examples of the polishing treatment include buffing using a polishing cloth, roll polishing using polishing paper (sandpaper), electrolytic polishing and the like.
The etching treatment includes, for example, a chemical etching treatment such as an alkali method, a phosphoric acid-sulfuric acid method, a fluoride method, a chromic acid-sulfuric acid method, and a salt iron method, and an electrochemical etching treatment such as an electrolytic etching method. Can be mentioned.
The caustic treatment is a method in which a treatment agent is allowed to act on the surface of an adherend to cause a chemical reaction.
The plasma treatment, the corona discharge treatment, and the UV ozone treatment are the same as those described in the rubber pretreatment, and thus the description thereof will be omitted.
The properties of the surface pretreated by the above method may be different from those immediately after the pretreatment due to the addition of the functional group described later on the surface treated surface. Therefore, it is considered impossible or impractical to specify and express the properties of the pretreated surface. Therefore, in the present embodiment, the pretreated surface is specified by the pretreatment method.

Pretreatments limited to aluminum include boehmite treatment, zirconium treatment, alumite treatment, and zinc phosphate treatment, but laser treatment, plasma treatment, corona discharge treatment, UV ozone treatment, blast treatment, and wet blast treatment for all metals. , At least one of sanding treatment is preferable, and from the viewpoint of generating a hydroxyl group, any one of plasma treatment, corona discharge treatment, and UV ozone treatment is preferable.
As the etching treatment of aluminum, for example, known etching treatments such as chemical etching treatment and electrochemical etching treatment can be applied. The chemical etching treatment is not particularly limited, and examples thereof include a caustic soda method, a phosphoric acid-sulfuric acid method, a fluoride method, a chromic acid-sulfuric acid method, and a salt iron method. The electrochemical etching treatment is not particularly limited, and examples thereof include an electrolytic etching method. Among these, it is preferable to perform the etching treatment by the caustic soda method, and it is more preferable to perform the etching treatment by the caustic soda method using an aqueous solution of sodium hydroxide or an aqueous solution of potassium hydroxide. Specifically, for example, at least a part of the aluminum material is placed in a 3% by mass to 20% by mass sodium hydroxide aqueous solution or a 3% by mass to 20% by mass potassium hydroxide aqueous solution at a temperature of 20 ° C to 70 ° C for 1 minute. After soaking for about 15 minutes, it is preferable to soak in a 5% by mass to 20% by mass aqueous nitrate solution for neutralization, and then wash and dry. In the caustic soda method, a chelating agent, an oxidizing agent, a phosphate or the like can also be used as an additive.
As the boehmite treatment for aluminum, a known boehmite treatment or the like can be used. Specifically, for example, it is a treatment of subjecting an aluminum material to hot water treatment to form a boehmite film on the surface. The boehmite is a needle-like crystal, and as the treatment time becomes longer, the crystal grows and the shape becomes complicated.
Distilled water is used for the boehmite treatment, but ammonia, triethanolamine, or the like may be added as a reaction accelerator. For example, distilled water to which 0.1% by mass to 5.0% by mass of triethanolamine is added is made into hot water at 90 ° C. to 100 ° C. and immersed in the hot water for 3 seconds to 5 minutes for boehmite treatment. Is good.
The aluminum material after the boehmite treatment may be directly subjected to the treatment with the next silane coupling agent, but after degreasing or etching treatment by the caustic soda method, the silane coupling agent is used. It may be subjected to processing.
As the zirconium treatment for aluminum, a known zirconium treatment or the like can be used. In the zirconium treatment, for example, a zirconium salt film is formed on the surface of an aluminum material using a zirconium compound such as zirconium phosphate or a zirconium salt. Since fine irregularities are formed on the surface of this film, it can contribute to the improvement of the adhesive force with the article to be joined. Specifically, for the zirconium treatment, for example, the chemical agents "Palcoat 3762" and "Palcoat 3796" manufactured by Nihon Parkerizing Co., Ltd. are heated to 45 ° C to 70 ° C and immersed in this liquid for 0.5 minutes to 3 minutes. Examples thereof include a method of immersing for a minute to perform zirconium treatment. When performing this zirconium treatment, it is desirable to first perform the etching treatment by the caustic soda method and then perform the zirconium treatment.

(Pretreatment of glass, ceramic, resin and rubber)
Examples of the pretreatment of glass, ceramic, resin and rubber include plasma treatment, corona discharge treatment, UV ozone treatment and the like.
The plasma treatment, the corona discharge treatment, and the UV ozone treatment are the same as those described in the rubber pretreatment, and thus the description thereof will be omitted.

(Functional group imparting treatment)
The method for imparting one or more functional groups selected from the group consisting of an amino group, an epoxy group, a mercapto group, a styryl group, a (meth) acryloyl group, an isocyanato group and an alkenyl group to the surface of the adherend is described above. A method of reacting at least one of the following (a) and (b) with an adherend having at least one selected from the group consisting of a hydroxyl group, a carboxy group and a radical on the surface after pretreatment is preferable.
(a) An alkoxysilane compound having at least one selected from the group consisting of an amino group, an epoxy group, a mercapto group, a styryl group, a (meth) acryloyl group, an isocyanato group and an alkenyl group.
(b) At least one compound selected from the group consisting of a compound having an amino group, a compound having an epoxy group, a compound having a mercapto group, a compound having an isocyanato group, and a compound having a radically polymerizable group by a functional group addition treatment. The formed adherend surface B with a functional group is a self-assembled monomolecular film (SAM) having a two-dimensional structure, or a part of the molecular chain is branched and three-dimensionally extended or superposed. It consists of a structure including the existing structure. In particular, it can be said that the functional group-attached adherend surface B in which a functional group is introduced into the surface of the adherend using a trifunctional alkoxysilane having a functional group has a larger three-dimensional multimolecular structure.
The details of the functional group imparting treatment are the same as those of the rubber functional group imparting treatment, and thus the description thereof will be omitted.

(Functional group extension treatment)
As described above, on the surface of the adherend after the functional group imparting treatment, a SAM having a two-dimensional structure or a structure in which the molecular chain is branched and three-dimensionally extended or superposed is formed. However, the SAM of the two-dimensional structure can be further extended in the three-dimensional direction by the following functional group extension treatment.
The details of the functional group extension treatment are the same as those of the rubber functional group imparting treatment, and thus the description thereof will be omitted.

《Joining method》
In the bonding method of one embodiment, one or more functional groups selected from the group consisting of an amino group, an epoxy group, a mercapto group, a styryl group, a (meth) acryloyl group, an isocyanato group, and an alkenyl group are attached to the surface of the rubber. An amino group, an epoxy group, a mercapto group, a styryl group, ( Meta) A method for joining rubber and an adherend, in which an adherend surface B with a functional group having one or more functional groups selected from the group consisting of an acryloyl group, an isocyanato group, and an alkenyl group is pressure-bonded and bonded. The bonding method, wherein at least one of the functional group-attached rubber surface A and the functional group-attached adherend surface B is a resin surface in which a two-dimensional monomolecular structure and a three-dimensional multimolecular structure are mixed. Is.

The crimping method may be any method as long as the functional group on the surface of rubber and at least one surface functional group selected from the group consisting of metal, glass, ceramic, resin and rubber can be brought close to each other within about 3 Å. It may be any method. By bringing them closer to each other within about 3 Å, chemical bonds between functional groups, hydrogen bonds, and van der Waals force bonds are formed. As a result, the rubber and the adherend can be bonded with sufficient bonding strength without using an adhesive.
Examples of the crimping method include pressing, but it is preferable to raise the temperature, and thermocompression bonding defined in JIS Z 3001 4.6.416402 (pressing a plurality of base materials at an appropriate temperature below the melting point is applied). A method of bringing them into close contact with each other to cause plastic deformation and joining them by contacting both surfaces) is more preferable.
The pressure at the time of crimping shall be a pressure within the range where the rubber and the adherend are not destroyed.

The combination of the functional group of the rubber surface A with the functional group and the functional group of the adherend surface B with the functional group is preferably a combination in which hydrogen bonds or chemical bonds can be expected, and at least any of the following (1) to (9). It is more preferable that it is. A stronger bond can be expected by any combination of at least one of the following (1) to (9). The following "combination of X and Y" includes "X is the functional group of the rubber surface A with the functional group, Y is the functional group of the adherend surface B with the functional group", and "the functional group of the rubber surface A with the functional group". Is Y, and the functional group of the adherend surface B with a functional group is X ”.
(1) Combination of amino group and epoxy group (2) Combination of mercapto group and epoxy group (3) Combination of isocyanato group and amino group (4) Combination of mercapto group and (meth) acryloyl group (5) Combination of mercapto group and amino Group combination (6) Combination of mercapto group and alkenyl group (7) Combination of amino group and (meth) acryloyl group (8) Combination of (meth) acryloyl group (9) Combination of amino group

By cleaning at least one of the functional group-attached rubber surface A and the functional group-attached adherend surface B before crimping, the compound remaining on the functional group with a weak adsorptive force is removed, and the bonding is performed. You can increase the strength of your body.

At least one of the functional group-attached rubber surface A and the functional group-attached adherend surface B is subjected to a functional group extension treatment after the functional group imparting treatment, and the functional groups on the surface are extended in a three-dimensional direction. By using, it may be possible to join under more lenient conditions. Depending on the combination of functional groups, it may be possible to lower the temperature when crimping with a press, for example.

Next, specific examples of the present invention will be described, but the present invention is not particularly limited to those of these examples.

[Preparation of rubber for test piece]
As the rubber for the test piece, the rubber shown in Table 1 below was prepared.

[Adhesive material for test piece_Preparation of metal, glass, ceramic]
As the adherend for the test piece, the metal, glass, and ceramic shown in Table 2 below were prepared.

[Preparation of adherend material for test piece_thermoplastic resin material]
As an adherend for a test piece, an injection molding machine (SE100V manufactured by Sumitomo Heavy Industries, Ltd.) is used under the conditions shown in Table 3 below, and the thermoplastic is an adherend for a test piece for a tensile test. Resin material: (10 mm × 45 mm × 3 mm) was prepared.

表３において、ＧＦ３０Ｗｔ％とは、ガラス繊維が３０質量％配合されたガラス繊維強化タイプ、を意味する。

In Table 3, GF30 Wt% means a glass fiber reinforced type containing 30% by mass of glass fiber.

[Preparation of adherend for test piece_thermosetting resin material, thermosetting resin film]
As the adherend for the test piece, a thermosetting resin material and a thermosetting resin film shown in Table 4 below were prepared.

[Rubber functional group imparting treatment]
(Epoxy group added)
Each of the ultratransparent silicone rubber, silicone rubber, and fluororubber shown in Table 1 was subjected to corona discharge treatment, and immediately, 0.5 g of 3-glycidoxytrimethoxysilane (KBM-403 manufactured by Shinetsu Silicone Co., Ltd .; silane coupling agent) was added. After immersing it in a silane coupling agent solution at 70 ° C. dissolved in 100 g of industrial ethanol for 10 minutes, it is taken out, washed with ethanol, and the surface is imparted with an epoxy group. Ultratransparent silicone rubber, silicone rubber, and fluorine. Rubbers (hereinafter referred to as ultratransparent silicone rubber-403, silicone rubber-403, and fluororubber-403, respectively) were produced.

(Addition of methacryloyl group)
Each of the ultratransparent silicone rubber, silicone rubber, and fluororubber shown in Table 1 was subjected to corona discharge treatment, and immediately 3-methacryloxypropyltrimethoxysilane (KBM-503 manufactured by Shinetsu Silicone Co., Ltd .; silane coupling agent) 0.5 g. Is immersed in 100 g of industrial ethanol in a silane coupling agent solution at 70 ° C. for 10 minutes, then taken out, washed with ethanol, and ultra-transparent silicone rubber, silicone rubber, and fluorine having a methacryloyl group on the surface. Rubber (hereinafter referred to as ultratransparent silicon rubber-503, silicon rubber-503, and fluororubber-503) was produced.

(Amino group addition)
Each of the ultratransparent silicone rubber, silicone rubber, and fluororubber shown in Table 1 was subjected to corona discharge treatment, and immediately, 0.5 g of 3-aminopropyltrimethoxysilane (KBM-903 manufactured by Shinetsu Silicone Co., Ltd .; silane coupling agent) was added. After immersing it in a silane coupling agent solution at 70 ° C. dissolved in 100 g of industrial ethanol for 10 minutes, it is taken out, washed with ethanol, and the surface is imparted with an amino group. Ultratransparent silicone rubber, silicone rubber, and fluorine. Rubbers (hereinafter referred to as ultratransparent silicone rubber-903, silicone rubber-903, and fluororubber-903, respectively) were produced.

[Rubber functional group extension treatment]
(Treatment with a compound having a mercapto group)
Ultra-transparent silicone rubber-903, silicone rubber-903, fluorine rubber-903, 1,4 bis (3-mercaptobutylyloxy) butane, which is a bifunctional thiol compound (Showa Denko Corporation, Karenz MT (registered trademark) BD1 ): 0.6 g, 2,4,6-tris (dimethylaminomethyl) phenol (DMP-30): 0.05 g is immersed in a solution dissolved in 150 g of toluene at 70 ° C. for 10 minutes, then withdrawn, and further toluene. Washed with and dried. In this way, ultratransparent silicon rubber-903BD1, silicon rubber-903BD1, and fluororubber-903BD1 in which the functional group structures of ultratransparent silicon rubber-903, silicon rubber-903, and fluororubber-903 are extended in a three-dimensional direction are produced. did.

(Treatment with 2-isocyanate ethyl methacrylate)
Ultra-transparent silicone rubber-503, silicone rubber-503, fluorine rubber-503, 2-isosianet ethyl methacrylate (Showa Denko KK Karens MOI (registered trademark)): 1.2 g, 2,4,6-tris ( Dimethylaminomethyl) phenol (DMP-30): 0.05 g was immersed in a solution dissolved in 150 g of toluene at 70 ° C. for 5 minutes, then withdrawn, washed with toluene and dried. In this way, ultratransparent silicon rubber-903MOI, silicon rubber-903MOI, and fluororubber-903MOI, in which the functional group structures of ultratransparent silicon rubber-503, silicon rubber-503, and fluororubber-503 are extended in a three-dimensional direction, are produced. did.

[Metal, glass, ceramic functional group addition treatment]
(Epoxy group added)
Each of the iron, stainless steel, aluminum, chemically strengthened glass, ultra-thin glass, and ceramic shown in Table 2 was plasma-treated and immediately treated with 3-glycidoxytrimethoxysilane (KBM-403 manufactured by Shin-Etsu Silicone Co., Ltd .; silane coupling agent). ) 0.5 g is dissolved in 100 g of industrial ethanol and immersed in a silane coupling agent solution at 70 ° C. for 10 minutes, then taken out, washed with ethanol, and iron, stainless steel, and aluminum having an epoxy group on the surface. , Chemically strengthened glass, ultra-thin glass, and ceramic (hereinafter referred to as iron-403, stainless steel-403, aluminum-403, chemically strengthened glass-403, ultra-thin glass-403, and ceramic-403, respectively). did.

(Addition of methacryloyl group)
Each of the iron, stainless steel, aluminum, chemically strengthened glass, ultra-thin glass, and ceramic shown in Table 2 was plasma-treated and immediately treated with 3-methacryloxypropyltrimethoxysilane (KBM-503 manufactured by Shinetsu Silicone Co., Ltd .; silane coupling). Agent) 0.5 g is dissolved in 100 g of industrial ethanol and immersed in a silane coupling agent solution at 70 ° C. for 10 minutes, the PC plate is taken out, and the iron is further washed with ethanol to impart a methacryloyl group. Stainless steel, aluminum, chemically strengthened glass, ultra-thin glass, and ceramic (hereinafter referred to as iron-503, stainless-503, aluminum-503, chemically strengthened glass-503, ultra-thin glass-503, and ceramic-503, respectively. ) Was produced.

(Amino group addition)
Each of the iron, stainless steel, aluminum, chemically strengthened glass, ultra-thin glass, and ceramic shown in Table 2 was plasma-treated and immediately treated with 3-aminopropyltrimethoxysilane (KBM-903 manufactured by Shinetsu Silicone Co., Ltd .; silane coupling agent). ) After immersing 0.5 g in 100 g of industrial ethanol and immersing it in a silane coupling agent solution at 70 ° C. for 10 minutes, the PC plate is taken out, further washed with ethanol, and iron and stainless steel to which an amino group is added. , Aluminum, chemically strengthened glass, ultra-thin glass, and ceramic (hereinafter referred to as iron-903, stainless-903, aluminum-903, chemically strengthened glass-903, ultra-thin glass-903, and ceramic-903, respectively). Was produced.

[Functional group extension treatment for metal, glass and ceramic]
(Treatment with a compound having a mercapto group)
Iron-903, stainless steel-903, aluminum-903, chemically strengthened glass-903, ultra-thin glass-903, ceramic-903, and 1,4 bis (3-mercaptobutylyloxy) butane, which is a bifunctional thiol compound (3-mercaptobutylyloxy) butane ( Showa Denko Corporation Karenz MT (registered trademark) BD1): 0.6 g, 2,4,6-tris (dimethylaminomethyl) phenol (DMP-30): 0.05 g in a solution of 0.05 g in toluene 70 After soaking at ° C. for 10 minutes, the mixture was withdrawn, washed with toluene and dried. In this way, iron-503BD1, stainless steel-503BD1, aluminum-503BD1, chemically strengthened glass-503BD1, ultra-thin film glass-503BD1, and ceramic-903BD1 having the functional group structure of the functional group-imparted surface extended in the three-dimensional direction are formed. Made.

(Treatment with 2-isocyanate ethyl methacrylate)
Iron-503, Stainless Steel-503, Aluminum-503, Chemically Reinforced Glass-503, Ultra Thin Glass-503, Ceramic-503, 2-Isocyanetethyl Methacrylate (Showa Denko Corporation Karenz MOI (registered trademark)): 1.2 g, 2,4,6-tris (dimethylaminomethyl) phenol (DMP-30): 0.05 g is immersed in a solution dissolved in 150 g of toluene at 70 ° C. for 5 minutes, then withdrawn, washed with toluene and dried. did. In this way, iron-503MOI, stainless steel-503MOI, aluminum-503MOI, chemically strengthened glass-503MOI, ultra-thin film glass-503MOI, and ceramic-503MOI, in which the functional group structure of the functional group-imparted surface is extended in the three-dimensional direction, are formed. Made.

[Resin functional group imparting treatment]
(Epoxy group added)
Each of the PP, PA6, PA66, m-PPE, PPS, PEI, PC, PBT, C-SMC, and acrylic resin films shown in Tables 3 and 4 was treated with UV ozone and immediately treated with 3-glycidoxytrimethoxysilane (3-glycidoxytrimethoxysilane). KBM-403 manufactured by Shin-Etsu Silicone Co., Ltd .; silane coupling agent) 0.5 g is dissolved in 100 g of industrial ethanol, soaked in a silane coupling agent solution at 70 ° C for 10 minutes, taken out, and further washed with ethanol. , PP, PA6, PA66, m-PPE, PPS, PEI, PC, PBT, C-SMC and acrylic resin film with epoxy group (hereinafter, PP-403, PA6-403, PA66-403, m-, respectively). PPE-403, PPS-403, PEI-403, PC-403, PBT-403, C-SMC-403 and acrylic resin film-403) were produced.

(Addition of methacryloyl group)
Each of the PP, PA6, PA66, m-PPE, PPS, PEI, PC, PBT, C-SMC, and acrylic resin film shown in Tables 3 and 4 was treated with UV ozone and immediately treated with 3-methacryloxypropyltrimethoxysilane. (KBM-503 manufactured by Shin-Etsu Silicone Co., Ltd .; silane coupling agent) 0.5 g is dissolved in 100 g of industrial ethanol, soaked in a silane coupling agent solution at 70 ° C. for 10 minutes, taken out, and further washed with ethanol. PP, PA6, PA66, m-PPE, PPS, PEI, PC, PBT, C-SMC and acrylic resin film (hereinafter, PP-503, PA6-503, PA66-503, m, respectively) to which a methacryloyl group is added. -PPE-503, PPS-503, PEI-503, PC-503, PBT-503, C-SMC-503 and acrylic resin film-503) were produced.

(Amino group addition)
Each of the PP, PA6, PA66, m-PPE, PPS, PEI, PC, PBT, C-SMC, and acrylic resin film shown in Tables 3 and 4 was treated with UV ozone and immediately treated with 3-aminopropyltrimethoxysilane (3-aminopropyltrimethoxysilane). KBM-903 manufactured by Shin-Etsu Silicone Co., Ltd .; silane coupling agent) 0.5 g is dissolved in 100 g of industrial ethanol, soaked in a silane coupling agent solution at 70 ° C. for 10 minutes, taken out, and further washed with ethanol. , PP, PA6, PA66, m-PPE, PPS, PEI, PC, PBT, C-SMC and acrylic resin film with amino groups (hereinafter, PP-903, PA6-903, PA66-903, m-, respectively). PPE-903, PPS-903, PEI-903, PC-903, PBT-903, C-SMC-903, and acrylic resin film-903) were produced.

[Resin functional group extension treatment]
(Treatment with a compound having a mercapto group)
PP-903, PA6-903, PA66-903, m-PPE-903, PPS-903, PEI-903, PC-903, PBT-903, C-SMC-903, acrylic resin film-903, bifunctional thiol. Compound 1,4 bis (3-mercaptobutylyloxy) butane (Showa Denko KK Karens MT (registered trademark) BD1): 0.6 g, 2,4,6-tris (dimethylaminomethyl) phenol (DMP) -30): After immersing 0.05 g in a solution of 0.05 g in 150 g of toluene at 70 ° C. for 10 minutes, the mixture was withdrawn, washed with toluene and dried. In this way, PP-903BD1, PA6-903BD1, PA66-903BD1, m-PPE-903BD1, PPS-903BD1, PEI-903BD1, PC-903BD1 in which the functional group structure of the functional group-imparting surface is extended in the three-dimensional direction. , PBT-903BD1, C-SMC-903BD1, and acrylic resin film-903BD1 were prepared.

(Treatment with 2-isocyanate ethyl methacrylate)
PP-503, PA6-503, PA66-503, m-PPE-503, PPS-503, PEI-503, PC-503, PBT-503, C-SMC-503, and acrylic resin film-503, 2- Isosianet ethyl methacrylate (Showa Denko KK Karens MOI (registered trademark)): 1.2 g, 2,4,6-tris (dimethylaminomethyl) phenol (DMP-30): 0.05 g dissolved in 150 g of toluene After soaking in the above solution at 70 ° C. for 5 minutes, it was withdrawn, washed with toluene and dried. In this way, PP-503MOI, PA6-503MOI, PA66-503MOI, m-PPE-503MOI, PPS-503MOI, PEI-503MOI, PC-503MOI, in which the functional group structure of the functional group-imparting surface is extended in the three-dimensional direction. , PBT-503MOI, C-SMC-503MOI, and acrylic resin film-503MOI were prepared.

[Rubber-rubber joint]
<Example 1-1 to Example 1-5>
The ultra-transparent silicone rubbers shown in Table 5 are overlapped with each other so that the overlapping part is 1 cm x 1 cm, sandwiched between double clips, left in a 150 ° C drying oven for 5 minutes, removed from the drying oven, cooled to room temperature, and the double clip is removed. A joint between ultratransparent silicone rubbers was obtained. Next, a tensile test of the joint was performed at a tensile speed of 5 mm / min and a measurement temperature of 23 ° C., and the results are shown in Table 5 (Combination 1).
Further, after the functional group treatment, those not washed with the solvent used for the treatment were joined by the same method and the tensile strength was measured, and the results are shown in Table 5 (Combination 2).
<Comparative Example 1-1>
Attempts were made to join the ultratransparent silicone rubbers that had not been subjected to the functional group imparting treatment in the same manner as in Examples 1-1 to 1-5, but they could not be joined.
<Comparative Example 1-2>
The combination of the ultratransparent silicone rubber-503BD1 (washed) used in Example 1-5 and the ultratransparent silicone rubber not treated with the functional group, and the ultratransparent silicone rubber-503BD1 (unwashed) not treated with the functional group. I tried to join two types of ultra-transparent silicone rubber combinations in the same way, but neither of them could be joined.

<Examples 2-1 to 2-5>
Silicone rubbers shown in Table 6 are overlapped with each other so that the overlapping part is 1 cm x 1 cm, sandwiched between double clips, left in a 150 ° C drying oven for 5 minutes, removed from the drying oven, cooled to room temperature, and the double clips are removed. I got a joint between them. Next, a tensile test of the joint was performed at a tensile speed of 5 mm / min, and the results are shown in Table 6.
<Comparative Example 2>
Silicone rubbers that had not been subjected to the functional group imparting treatment were attempted to be bonded in the same manner as in Examples 2-1 to 2-5, but could not be bonded.

<Examples 3-1 to 3-5>
Fluororubber shown in Table 7 is overlapped with each other so that the overlapping part is 1 cm x 1 cm, sandwiched between double clips, left in a drying oven at 150 ° C for 5 minutes, removed from the drying oven, cooled to room temperature, and the double clip is removed to remove the fluororubber. We obtained a joint between them. Next, a tensile test of the joint was performed at a tensile speed of 5 mm / min, and the results are shown in Table 7.
<Comparative Example 3>
Fluororubbers that had not been subjected to the functional group imparting treatment were joined to each other in the same manner as in Example 3, a tensile test was performed, and the results are shown in Table 7.

<Examples 4-1 to 4-5>
The silicon rubber and fluorine rubber shown in Table 8 are overlapped so that the overlapping part is 1 cm x 1 cm, sandwiched between double clips, left in a 150 ° C drying furnace for 5 minutes, removed from the drying furnace, cooled to room temperature, and the double clip is removed. A composite of silicon rubber and fluorine rubber was obtained. Next, a tensile test of the joint was performed at a tensile speed of 5 mm / min, and the results are shown in Table 8 (Condition 1).
Further, a tensile test was performed by obtaining a bonded product under the same conditions except that the functional group imparting treatment condition using the silane coupling agent was 20 ° C. for 24 hours, and the results are shown in Table 8 (Condition 2).
<Comparative Example 4>
Attempts were made to join the silicone rubber and the fluororubber that had not been subjected to the functional group imparting treatment in the same manner as in Examples 4-1 to 4-5, but they could not be joined.

[Rubber-metal joint]
<Examples 5-1 to 5-5>
Put the rubber and metal shown in Table 9 on top of each other so that the overlapping part is 1 cm x 1 cm, sandwich them with double clips, leave them in a drying oven at 150 ° C for 5 minutes, remove them from the drying oven, cool them to room temperature, remove the double clips, and remove the rubber. A metal joint was obtained. Next, a tensile test of the joint was performed at a tensile speed of 5 mm / min, and the results are shown in Table 9.
<Comparative Example 5>
Attempts were made to join the rubber and metal that had not been subjected to the functional group imparting treatment in the same manner as in Examples 5-1 to 5-5, but they could not be joined.

[Rubber-glass joint, rubber-ceramic joint]
<Examples 6-1 to 6-5>
Put the rubber and glass or ceramic shown in Table 10 on top of each other so that the overlapping part is 1 cm x 1 cm, sandwich them with double clips, leave them in a drying oven at 150 ° C for 5 minutes, remove them from the drying oven, cool them to room temperature, and remove the double clips. Bonds of rubber and glass and rubber and ceramic were obtained. Next, a tensile test of the joint was performed at a tensile speed of 5 mm / min, and the results are shown in Table 10.
<Comparative Example 6>
Attempts were made to join rubber and glass, and rubber and ceramic, which had not been subjected to the functional group imparting treatment, in the same manner as in Examples 6-1 to 6-5, but they could not be joined.

[Rubber-resin joint]
<Examples 7-1 to 7-5>
The rubber and resin shown in Table 11 are overlapped so that the overlapping part is 1 cm x 1 cm, sandwiched between double clips, left in a drying oven at 150 ° C for 5 minutes, removed from the drying oven, cooled to room temperature, and the double clip is removed to remove the rubber. A resin joint was obtained. Next, a tensile test of the joint was performed at a tensile speed of 5 mm / min, and the results are shown in Table 11.
<Comparative Example 7>
Attempts were made to join the rubber and the resin that had not been subjected to the functional group imparting treatment in the same manner as in Examples 7-1 to 7-5, but they could not be joined.

<Example 8-1 to Example 8-2>
Silicone rubber-903 and fluorine rubber-403 were put together and sandwiched between glass plates and kept at 150 ° C. for 10 minutes and returned to room temperature to prepare a silicon rubber-fluorine rubber bonded rubber.
Next, the silicon rubber surface of the silicon rubber-fluorine rubber bonded rubber and C-SMC-403 are overlapped so that the overlapping part is 1 cm x 1 cm, sandwiched between double clips, left in a 150 ° C. drying furnace for 5 minutes, and then removed from the drying furnace. It was taken out and cooled to room temperature, and the double clip was removed to obtain rubber and C-SMC junction-1.
In addition, the fluororubber surface of the silicone rubber-fluororubber bonded rubber and C-SMC-903 are overlapped so that the overlapping portion is 1 cm x 1 cm, sandwiched between double clips, left in a 150 ° C. drying furnace for 5 minutes, and then removed from the drying furnace. After cooling to room temperature, the double clip was removed to obtain a rubber-C-SMC junction-2.
Next, a tensile test of the joint was performed at a tensile speed of 5 mm / min, and the results are shown in Table 12.
<Comparative Example 8-1 to Comparative Example 8-2>
Silicon rubber-fluorine rubber bonding The silicon rubber surface of the rubber, the fluorine rubber surface and the C-SMC were overlapped so that the overlapping portion was 1 cm × 1 cm, and an attempt was made to join in the same manner as in Examples 8-1 to 8-2. Could not be joined.

[Rubber-acrylic resin film bonding, rubber-ultra-thin glass bonding]
<Example 9>
When the fluororubber-903 and the acrylic resin film-403 were overlapped and passed through a 150 ° C. hot roll press machine, the acrylic resin film could be bonded to the fluororubber.
When silicon rubber-903 and ultra-thin film glass-403 were stacked and passed through a 150 ° C. hot roll press machine, the ultra-thin film glass could be bonded to the silicon rubber.
<Comparative Example 9>
The fluororubber-903 and the acrylic resin film were overlapped and passed through a 150 ° C. hot roll press machine, but the acrylic resin film could not be bonded to the fluororubber.
Silicone rubber and ultra-thin glass-403 were stacked and passed through a 150 ° C hot roll press machine, and the ultra-thin glass could be bonded to the silicon rubber.

The joint according to the present invention includes, for example, electrical parts, electronic parts, food machinery parts, equipment parts, medical / biological parts, medical equipment parts, packings, gaskets, O-rings, sealing parts, tubes, hoses, and other piping parts and rubber. It is used for stoppers, caps, rubber cords, rubber rings, rubber sheets, sponge sheets, mats, research equipment parts, caster parts, wheels, ducts, frame packings, etc., but is not particularly limited to these exemplary applications.

Claims (23)

A rubber surface with a functional group having one or more functional groups selected from the group consisting of an amino group, an epoxy group, a mercapto group, a styryl group, a (meth) acryloyl group, an isocyanato group, and an alkenyl group on the surface of the rubber. When,
On the surface of at least one adherend selected from the group consisting of metal, glass, ceramic, resin and rubber, an amino group, an epoxy group, a mercapto group, a styryl group, a (meth) acryloyl group, an isocyanato group, and an alkenyl. The adherend surface B with a functional group having one or more functional groups selected from the group consisting of groups is directly bonded.
A bonded body in which a two-dimensional monomolecular structure and a three-dimensional multimolecular structure are mixed on at least one of the functional group-attached rubber surface A and the functional group-attached adherend surface B. The bonding according to claim 1, wherein the combination of the functional group of the rubber surface A with the functional group and the functional group of the adherend surface B with the functional group is at least one of the following (1) to (9). body.
(1) Combination of amino group and epoxy group (2) Combination of mercapto group and epoxy group (3) Combination of isocyanato group and amino group (4) Combination of mercapto group and (meth) acryloyl group (5) Combination of mercapto group and amino Group combination (6) Combination of mercapto group and alkenyl group (7) Combination of amino group and (meth) acryloyl group (8) Combination of (meth) acryloyl group (9) Combination of amino group One or more selected from the group consisting of the amino group, epoxy group, mercapto group, styryl group, (meth) acryloyl group, isocyanato group, and alkenyl group having the functional group-attached rubber surface A on the surface of the rubber. The functional group was imparted by reacting one or more compounds selected from the group consisting of a compound having an isocyanato group, a compound having a mercapto group, a compound having an epoxy group, a compound having an amino group, and a radically polymerizable compound. The conjugate according to claim 1 or 2, which has a functional group derived from the compound. The adherend surface B with a functional group is selected from the group consisting of the amino group, the epoxy group, the mercapto group, the styryl group, the (meth) acryloyl group, the isocyanato group and the alkenyl group having on the surface of the adherend. One or more functional groups are reacted with one or more compounds selected from the group consisting of a compound having an isocyanato group, a compound having a mercapto group, a compound having an epoxy group, a compound having an amino group, and a radically polymerizable compound. The conjugate according to any one of claims 1 to 3, which has a functional group derived from the compound. The bonded body according to any one of claims 1 to 4, wherein the rubber is at least one of silicon rubber and fluororubber. The bonded body according to any one of claims 1 to 5, wherein the shape of the rubber and the adherend is one or more selected from the group consisting of a lump, a plate, and a thin film. A rubber surface with a functional group having one or more functional groups selected from the group consisting of an amino group, an epoxy group, a mercapto group, a styryl group, a (meth) acryloyl group, an isocyanato group, and an alkenyl group on the surface of the rubber. When,
On the surface of at least one adherend selected from the group consisting of metal, glass, ceramic, resin and rubber, an amino group, an epoxy group, a mercapto group, a styryl group, a (meth) acryloyl group, an isocyanato group, and an alkenyl. A method for joining rubber and an adherend, wherein the adherend surface B with a functional group having one or more functional groups selected from the group consisting of groups is pressure-bonded, and the rubber surface with a functional group is bonded. A method for joining rubber and an adherend, wherein at least one of A and an adherend surface B with a functional group has a mixture of a two-dimensional monomolecular structure and a three-dimensional multimolecular structure. The rubber according to claim 7, wherein the combination of the functional group of the rubber surface A with the functional group and the functional group of the adherend surface B with the functional group is at least one of the following (1) to (9). And how to join the adherend.
(1) Combination of amino group and epoxy group (2) Combination of mercapto group and epoxy group (3) Combination of isocyanato group and amino group (4) Combination of mercapto group and (meth) acryloyl group (5) Combination of mercapto group and amino Group combination (6) Combination of mercapto group and alkenyl group (7) Combination of amino group and (meth) acryloyl group (8) Combination of (meth) acryloyl group (9) Combination of amino group The rubber and the adherend according to claim 7 or 8, wherein the rubber is reacted with a compound corresponding to at least one of the following (i) to (iii) to form the rubber surface A with a functional group. Joining method.
(I) An alkoxysilane compound (ii) One compound selected from the group consisting of a compound having an amino group, a compound having an epoxy group, a compound having a mercapto group, and a compound having an isocyanato group (iii) a radically polymerizable group. Compounds with The functional group is obtained by reacting at least one adherend selected from the group consisting of metal, glass, ceramic, resin and rubber with a compound corresponding to at least one of the following (i) to (iii). The method for joining rubber and an adherend according to claim 7 or 8, wherein the adherend surface B is formed.
(I) An alkoxysilane compound (ii) One compound selected from the group consisting of a compound having an amino group, a compound having an epoxy group, a compound having a mercapto group, and a compound having an isocyanato group (iii) a radically polymerizable group. Compounds with The alkoxysilane compound is a silane coupling agent having one or more functional groups selected from the group consisting of an amino group, an epoxy group, a mercapto group, a styryl group, a (meth) acryloyl group, and an isocyanato group. 9. The method for joining a rubber and an adherend according to 9 or 10. The method for joining a rubber and an adherend according to claim 11, wherein the temperature at which the silane coupling agent is reacted is 5 to 30 ° C. The rubber and adherend according to claim 9 or 10, wherein the compound having an amino group is at least one of an amino compound having a (meth) acryloyl group or an amino compound having a bifunctional or higher functional group. Joining method. 9. The method of joining the rubber and the adherend as described. The method for joining a rubber to an adherend according to claim 9, wherein the compound having a mercapto group is a bifunctional or higher functional thiol compound. The method for joining a rubber to an adherend according to claim 9 or 10, wherein the compound having an isocyanato group is at least one of an isocyanato compound having a (meth) acryloyl group or a bifunctional or higher functional isocyanato compound. The method for joining a rubber to an adherend according to claim 9, wherein the radically polymerizable compound is a compound having a (meth) acryloyl group. A rubber and amino group, an epoxy group, a mercapto group having one or more functional groups on the surface selected from the group consisting of an amino group, an epoxy group, a mercapto group, a styryl group, a (meth) acryloyl group, an isocyanato group, and an alkenyl group. It has at least one of the adherend having one or more functional groups on the surface selected from the group consisting of a styryl group, a (meth) acryloyl group, an isocyanato group, and an alkenyl group, and a compound having an isocyanato group, a mercapto group. The rubber surface A with a functional group and the adherend with a functional group are reacted by reacting one or more compounds selected from the group consisting of a compound, a compound having an epoxy group, a compound having an amino group, and a radically polymerizable compound. The method for joining a rubber and an adherend according to claim 7 or 8, wherein at least one of the surfaces B is formed. The rubber and the adherend according to any one of claims 7 to 18, wherein at least one of the functional group-attached rubber surface A and the functional group-attached adherend surface B is washed before the crimping. How to join. The method for joining rubber and an adherend according to any one of claims 7 to 19, wherein the rubber surface A with a functional group and the adherend surface B with a functional group are bonded by thermocompression bonding. The method for joining a rubber and an adherend according to any one of claims 7 to 19, wherein the rubber surface A with a functional group and the adherend surface B with a functional group are joined by welding. The rubber and an adherend according to claim 21, wherein the welding is at least one selected from the group consisting of an ultrasonic welding method, a vibration welding method, an electromagnetic induction method, a high frequency method, a laser method, and a hot pressing method. Joining method. The one according to any one of claims 7 to 22, wherein at least one of the functional group-attached rubber surface A and the functional group-attached adherend surface B is formed by at least one of a spray coating method and a dipping method. How to join rubber and adherend.