JP2016023197A - Laminate for rubber adhesion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate for rubber adhesion, capable of firmly bonding a vulcanized rubber and an unvulcanized rubber.SOLUTION: The laminate for rubber adhesion according to the present invention includes a vulcanized rubber adhesive layer and an unvulcanized rubber adhesive layer arranged in this order. The vulcanized rubber adhesive layer has a vulcanized rubber adhesive composition obtained by blending a polythiol compound (A) containing a plurality of thiol groups, a thiol-reactive compound (B) having a thiol-reactive group having reactivity with the thiol groups, and a radical generator (C).SELECTED DRAWING: None

Description

  The present invention relates to a rubber bonding laminate for bonding vulcanized rubber and unvulcanized rubber.

Conventionally, as a method of bonding a rubber member to another member, a method has been disclosed in which a vulcanized rubber member is surface-treated and the other member is bonded to the surface-treated surface via an adhesive (see Patent Document 1). .
In the case of bonding rubbers together, vulcanization bonding is known. In particular, when the unvulcanized rubber is bonded to each other, the unvulcanized rubber members can be bonded by being vulcanized in a state where the unvulcanized rubber members are pressed and brought into close contact with each other. As a method of bonding vulcanized rubbers, a technique of vulcanizing and bonding using unvulcanized adhesive rubber or gasoline cement has been proposed.
In recent years, reuse technology is required in a wide range of fields from the viewpoint of global environmental conservation. In the field of application of rubber products, for example, replacement of worn tread members and rehabilitation tires that recycle so-called base tires, heavy duty tires used in mines and construction sites, crawlers, conveyor belts, etc. Examples include rejoining.

JP-A-10-139901

The above-mentioned conventional rubber-to-rubber bonding technology may be applicable to the above-mentioned repair and rejoining of rubber products. However, depending on the bonding method, the process is complicated or a large amount of solvent is used. In some cases, it was difficult to apply. In addition, depending on the conventional bonding method, there are cases where the bonding force required for the recycled product cannot be satisfied.
The present invention relates to a rubber bonding laminate capable of firmly bonding vulcanized rubber and unvulcanized rubber.

  The inventor mixes a polythiol compound (A) containing a plurality of thiol groups, a thiol-reactive compound (B) having a thiol-reactive group having reactivity with the thiol group, and a radical generator (C). It has been found that the problems of the present invention can be solved by using the composition obtained as a vulcanized rubber adhesive, and the present invention has been completed.

That is, the present invention relates to the following [1] to [14].
[1] A laminated body for rubber bonding in which a vulcanized rubber adhesive layer and an unvulcanized rubber adhesive layer are arranged in this order, and the vulcanized rubber adhesive layer contains a plurality of thiol groups It has a vulcanized rubber adhesive composition comprising a compound (A), a thiol-reactive compound (B) containing a group having reactivity with the thiol group, and a radical generator (C). A laminate for bonding rubber.
[2] The thiol-reactive compound (B) is an isocyanate group-containing compound, a monoacrylate having one acryloyl group, a polyacrylate having two or more acryloyl groups, a polymethacrylate having two or more methacryloyl groups, two or more epoxies Selected from an epoxy compound having a group, a vinyl compound having two or more vinyl groups, a vinyl ether compound having two or more vinyloxy groups, an allyl compound having two or more allyl groups, and an allyl ether compound having two or more allyloxy groups. The rubber-bonded laminate according to claim 1, which is at least one compound.
[3] The rubber according to [2], wherein the thiol-reactive compound (B) is at least one compound selected from the isocyanate group-containing compound, the monoacrylate, the polyacrylate, the polymethacrylate, and the epoxy compound. Adhesive laminate.
[4] The rubber bonded laminate according to any one of [1] to [3], wherein the vulcanized rubber adhesive layer is processed into a sheet shape.
[5] The rubber bonded laminate according to any one of [1] to [4], wherein the vulcanized rubber adhesive composition is formulated with a catalyst (D).
[6] The catalyst (D) is an amine catalyst, and the thiol-reactive compound (B) is at least one selected from the isocyanate group-containing compound, the monoacrylate, the polyacrylate, and the epoxy compound. The laminated body for rubber bonding according to [5], which is a compound.
[7] The rubber bonding laminate according to any one of [1] to [6], wherein the radical generator (C) is a thermal radical generator.
[8] The rubber adhesive laminate according to [7], wherein the thermal radical generator is a peroxide.
[9] The rubber bonding laminate according to [8], wherein the peroxide is an organic oxide.
[10] The rubber adhesive laminate according to any one of [1] to [6], wherein the radical generator (C) is a photoradical generator.
[11] The radical generator (C) is a photo radical generator, and the thiol-reactive compound (B) is selected from acrylate compounds, methacrylate compounds, allyl compounds, vinyl compounds, allyl ether compounds, and vinyl ether compounds. The laminate for rubber bonding according to [10], which is at least one compound.
[12] Ratio of the total number of moles of the thiol-reactive group contained in the thiol-reactive compound (B) to the total number of moles of the thiol group contained in the polythiol compound (A) (thiol-reactive group / thiol group ) Is 0.20 or more and 0.78 or less, the laminated body for rubber bonding according to any one of [1] to [11].
[13] Ratio of the total number of moles of the thiol-reactive group contained in the thiol-reactive compound (B) to the total number of moles of the thiol group contained in the polythiol compound (A) (thiol-reactive group / thiol group ) Is 0.30 or more and 0.60 or less, the laminated body for rubber bonding according to any one of [1] to [11].
[14] The rubber adhesion according to any one of [1] to [13], wherein a main component of the unvulcanized rubber adhesive composition forming the unvulcanized rubber adhesive layer is chlorinated rubber or chlorosulfonated polyethylene. Laminated body.

  ADVANTAGE OF THE INVENTION According to this invention, the laminated body for rubber adhesion which can adhere | attach a vulcanized rubber and an unvulcanized rubber firmly can be provided.

[Laminate for rubber bonding]
The laminated body for rubber bonding according to an embodiment of the present invention is a laminated body for rubber bonding in which a vulcanized rubber adhesive layer and an unvulcanized rubber adhesive layer are arranged in this order, and the vulcanized rubber adhesive The layer comprises a polythiol compound (A) containing a plurality of thiol groups, a thiol-reactive compound (B) having a thiol-reactive group having reactivity with the thiol group, and a radical generator (C). It is characterized by having a vulcanized rubber adhesive composition.

According to the laminated body for rubber bonding according to the embodiment of the present invention, the vulcanized rubber and the unvulcanized rubber can be firmly bonded. The reason is estimated as follows.
It is considered that the laminate for rubber bonding is hardened by bonding a part of the polythiol compound (A) and the thiol-reactive compound (B). Further, it is considered that another part of the polythiol compound (A) reacts with the radical generator (C) to generate a thiyl radical, and this thiyl radical reacts with a carbon-carbon double bond present in the rubber. Such a thiol-ene reaction is considered to cause the rubber adhesive laminate to be chemically bonded to the vulcanized rubber and the unvulcanized rubber. Since carbon-carbon double bonds exist not only in unvulcanized rubber but also in vulcanized rubber, according to the laminated body for rubber bonding according to this embodiment, rubber, in particular, vulcanized rubber is strongly bonded. It is thought that you can.
It is also considered that the sulfur atom of the thiol group of the polythiol compound (A) and the carbon atom of the carbon-carbon bond are chemically bonded by a hydrogen abstraction reaction from the carbon-carbon bond main chain present in the rubber. Therefore, the carbon-carbon double bond does not necessarily exist in the rubber.
In the present specification, the polythiol compound (A), the thiol-reactive compound (B), and the radical generator (C) may be referred to as component (A), component (B), and component (C), respectively.

[Vulcanized rubber adhesive layer]
The vulcanized rubber adhesive layer constituting the laminated body for rubber bonding according to this embodiment will be described. The vulcanized rubber adhesive layer is formed of a vulcanized rubber adhesive composition. The vulcanized rubber adhesive composition includes a polythiol compound (A) containing a plurality of thiol groups, a thiol-reactive compound (B) having a thiol-reactive group having reactivity with the thiol group, and a radical generator ( C).
<Polythiol compound (A)>
In the present embodiment, the polythiol compound (A) refers to a compound having two or more thiol groups in one molecule. Here, as long as it has two or more thiol groups in one molecule, even if it has other functional groups together, it corresponds to the component (A). From the viewpoint of adhesion to vulcanized rubber and durability after adhesion, the polythiol compound (A) preferably does not contain a carbon-carbon double bond.
From the viewpoint of improving adhesiveness, the polythiol compound (A) preferably has 2 to 6 thiol groups in one molecule.
In addition, the polythiol compound (A) includes primary, secondary and tertiary compounds, but the primary is more preferable from the viewpoint of improving adhesiveness.
From the viewpoint of improving adhesiveness, the molecular weight of the polythiol compound (A) is preferably 3000 or less, more preferably 2000 or less, still more preferably 1000 or less, still more preferably 900 or less, more More preferably, it is 800 or less. In addition, when a polythiol compound (A) is a polymer, molecular weight means the number average molecular weight of styrene conversion.

Examples of the polythiol compound (A) include aliphatic polythiols that may contain heteroatoms and aromatic polythiols that may contain heteroatoms. From the viewpoint of improving adhesiveness, polythiol compounds (A) may contain heteroatoms. Good aliphatic polythiols are preferred.
Here, the aliphatic polythiol which may contain a hetero atom refers to an aliphatic compound which may contain a hetero atom having two or more thiol groups in one molecule. Moreover, the aromatic polythiol which may contain the hetero atom means the aromatic compound which may contain the hetero atom which has two or more thiol groups in 1 molecule.
The heteroatom is preferably at least one selected from oxygen, nitrogen, sulfur, phosphorus, halogen atoms, and silicon, more preferably oxygen, nitrogen, sulfur, phosphorus, and halogen atoms, from the viewpoint of improving adhesive strength. It is at least one selected, and more preferably at least one selected from oxygen, nitrogen and sulfur.

Examples of the aliphatic polythiol that may contain a hetero atom include, for example, a polythiol other than a thiol group, such as an alkanedithiol having 2 to 20 carbon atoms, and a halogen atom of a halohydrin adduct of alcohol. Thioglycolic acid ester obtained by esterification of polythiol substituted with thiol group, polythiol composed of hydrogen sulfide reaction product of polyepoxide compound, polyhydric alcohol having 2-6 hydroxyl groups in the molecule and thioglycolic acid Contains a mercapto fatty acid esterified product obtained by esterification of a polyhydric alcohol having 2 to 6 hydroxyl groups in the molecule and a mercapto fatty acid, a thiol isocyanurate compound obtained by reacting an isocyanurate compound and a thiol, and a polysulfide group Thiol Silicones modified with thiol groups, silsesquioxane or the like which is modified with a thiol group.
Examples of the polyhydric alcohol having 2 to 6 hydroxyl groups in the molecule include alkanediol having 2 to 20 carbon atoms, poly (oxyalkylene) glycol, glycerol, diglycerol, trimethylolpropane, ditrimethylolpropane, and pentane. Examples include erythritol and dipentaerythritol.

  Among these, from the viewpoint of improving adhesiveness, polythiols other than thiol groups are aliphatic hydrocarbons, polythiols obtained by substituting halogen atoms of alcohol halohydrin adducts with thiol groups, hydrogen sulfides of polyepoxide compounds A polythiol, a thioglycolic acid ester, a mercapto fatty acid ester, and a thiol isocyanurate compound are more preferable, a mercapto fatty acid ester and a thiol isocyanurate compound are more preferable, and a mercapto fatty acid ester is more preferable. From the same viewpoint, a thiol containing no polysulfide group or siloxane bond is more preferable.

(Polythiol whose part other than thiol group is aliphatic hydrocarbon)
Examples of the polythiol in which the portion other than the thiol group is an aliphatic hydrocarbon include alkanedithiol having 2 to 20 carbon atoms.
Examples of the alkanedithiol having 2 to 20 carbon atoms include 1,2-ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 1,4 -Butanedithiol, 2,3-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol, 1,10-decanedithiol, 1,1-cyclohexanedithiol, 1,2- And cyclohexanedithiol.

(Thioglycolic acid ester)
Examples of the thioglycolic acid ester include 1,4-butanediol bisthioglycolate, 1,6-hexanediol bisthioglycolate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthioglycolate, and the like.

(Mercapto fatty acid esterified product)
As the mercapto fatty acid ester product, a mercapto fatty acid ester product having a primary thiol group is preferable from the viewpoint of improving adhesiveness, and a β-mercaptopropionic acid ester product of a polyhydric alcohol having 2 to 6 hydroxyl groups in the molecule. Is more preferable. In addition, the mercapto fatty acid ester having a primary thiol group preferably has 4 to 6 thiol groups in one molecule from the viewpoint of improving adhesiveness, and preferably 4 or 5. Preferably, it is four.

  The β-mercaptopropionate esterified product having a primary thiol group is preferably tetraethylene glycol bis (3-mercaptopropionate) (EGMP-4), trimethylolpropane tris (3-mercaptopropionate). (TMMP), pentaerythritol tetrakis (3-mercaptopropionate) (PEMP), pentaerythritol tetraglycidyl ether (PETG) and dipentaerythritol hexakis (3-mercaptopropionate) (DPMP). Among these, PEMP, PETG, and DPMP are preferable, and PEMP and PETG represented by the following structural formula are more preferable.

  Examples of the β-mercaptopropionic acid esterified product having a secondary thiol group include esterified products of polyhydric alcohols having 2 to 6 hydroxyl groups in the molecule and β-mercaptobutanoic acid. 1,4-bis (3-mercaptobutyryloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate) and the like.

(Thiol isocyanurate compound)
As a thiol isocyanurate compound obtained by reacting an isocyanurate compound with a thiol, a thiol isocyanurate compound having a primary thiol group is preferable from the viewpoint of improving adhesive strength. Moreover, as a thiol isocyanurate compound which has a primary thiol group, it is preferable that the number of thiol groups in 1 molecule is 2-4, and it is more preferable that it is three from a viewpoint of an adhesive improvement. .
As the thiol isocyanurate compound having a primary thiol group, tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate (TEMPIC) is preferable.

(Silicone modified with thiol group)
Examples of silicone modified with a thiol group include trade names KF-2001, KF-2004, X-22-167B (Shin-Etsu Chemical), SMS042, SMS022 (Gelest), PS849, PS850 (UCT), and the like. .

(Aromatic polythiol)
Aromatic polythiols include 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis (mercaptomethyl) benzene, 1,3-bis (mercaptomethyl) Benzene, 1,4-bis (mercaptomethyl) benzene, 1,2-bis (mercaptoethyl) benzene, 1,3-bis (mercaptoethyl) benzene, 1,4-bis (mercaptoethyl) benzene, 1,2, 3-trimercaptobenzene, 1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene, 1,2,3-tris (mercaptomethyl) benzene, 1,2,4-tris (mercaptomethyl) Benzene, 1,3,5-tris (mercaptomethyl) benzene, 1,2,3-tris (mercaptoethyl) benze 1,2,4-tris (mercaptoethyl) benzene, 1,3,5-tris (mercaptoethyl) benzene, 2,5-toluenedithiol, 3,4-toluenedithiol, 1,3-di (p-methoxy) Phenyl) propane-2,2-dithiol, 1,3-diphenylpropane-2,2-dithiol, phenylmethane-1,1-dithiol, 2,4-di (p-mercaptophenyl) pentane and the like.

<Thiol-reactive compound (B)>
The thiol-reactive compound (B) is a compound containing a group having reactivity with the thiol group of the polythiol compound.
Examples of groups having reactivity with thiol groups include isocyanate groups, acryloyl groups, acryloyl groups, methacryloyl groups, epoxy groups, vinyl groups, vinyloxy groups, allyl groups, allyloxy groups, norbornenyl groups, and the like.
However, in this embodiment, the vinyl group does not include a vinyloxy group and an allyl group, the allyl group does not include an allyloxy group, and the vinyloxy group does not include an allyloxy group.
Examples of the compound containing a group having reactivity with a thiol group include an isocyanate group-containing compound, an acryloyl group-containing compound, a methacryloyl group-containing compound, an epoxy group-containing compound, a vinyl group-containing compound, a vinyloxy group-containing compound, and an allyl group-containing compound. , Allyloxy group-containing compounds, norbornenyl group-containing compounds, and the like.
Among the above compounds, the acryloyl group-containing compound is preferably a monoacrylate having one acryloyl group or a polyacrylate having two or more acryloyl groups. The methacryloyl group-containing compound is preferably a polymethacrylate having two or more methacryloyl groups.
The epoxy group-containing compound is preferably an epoxy compound having two or more epoxy groups.
As the vinyl group-containing compound, a vinyl compound having two or more vinyl groups is preferable. As the vinyloxy group-containing compound, a vinyl ether compound or a vinyl ester compound having two or more vinyloxy groups is preferable. The allyl group-containing compound is preferably an allyl compound having two or more allyl groups. Furthermore, the allyloxy group-containing compound is preferably an allyl ether compound or an allyl ester compound having two or more allyloxy groups. As the norbornenyl group-containing compound, a norbornene compound having two or more norbornenyl groups is preferable.
In addition, a component (B) may use only 1 type from the compound mentioned above, and may use 2 or more types together.

  As the thiol-reactive compound (B), among the above-mentioned compounds, an isocyanate group-containing compound, a monoacrylate having one acryloyl group, a polyacrylate having two or more acryloyl groups, and a polymethacrylate having two or more methacryloyl groups An epoxy compound having two or more epoxy groups, a vinyl compound having two or more vinyl groups, a vinyl ether compound having two or more vinyloxy groups, an allyl compound having two or more allyl groups, and an allyl having two or more allyloxy groups It is preferably at least one compound selected from ether compounds.

  Among the above-described thiol-reactive compounds (B), from the viewpoint of further increasing the bonding strength with the vulcanized rubber, the thiol-reactive compounds (B) include isocyanate group-containing compounds and acryloyl groups among the above-described compounds. It is preferable that it is at least one compound selected from a monoacrylate having one, a polyacrylate having two or more acryloyl groups, a polymethacrylate having two or more methacryloyl groups, and a compound having two or more epoxy groups.

(Isocyanate group-containing compound)
Examples of the isocyanate group-containing compound include aromatic, aliphatic, and alicyclic diisocyanates, and modified products thereof.
Examples of aromatic, aliphatic and alicyclic diisocyanates include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI), naphthylene diisocyanate (NDI), phenylene diisocyanate (PPDI), m. -Tetramethylxylylene diisocyanate (TMXDI), methylcyclohexane diisocyanate (hydrogenated TDI), dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclohexane diisocyanate (hydrogenated PPDI), bis (isocyanatomethyl) cyclohexane (Hydrogenated XDI), norbornene diisocyanate (NBDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), butanediiso Aneto, hexamethylene diisocyanate 2,2,4-trimethyl hexamethylene diisocyanate to 2,4,4-trimethyl like.

  When the blended polythiol compound (A) is a mercapto fatty acid esterified product and a thiol isocyanurate compound, the blended isocyanate group-containing compound is hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), tolylene diisocyanate ( One or more of TDI), xylylene diisocyanate (XDI), and diphenylmethane diisocyanate (MDI) are preferred. Among these, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), xylylene diisocyanate (XDI), bis (isocyanatomethyl) cyclohexane (hydrogenated XDI) and tolylene diisocyanate (TDI). 1 type or 2 types or more are more preferable.

  In addition, as modified products of aromatic, aliphatic and alicyclic diisocyanates, TMP (trimethylolpropane) adduct modified products obtained by reaction of trimethylolpropane and isocyanate, isocyanurate obtained by trimerization of isocyanate Type modified products, burette modified products obtained by reaction of urea and isocyanate, allophanate modified products obtained by reaction of urethane and isocyanate, prepolymers obtained by reaction with polyol, etc. Can be used.

In addition, as a TMP adduct type modified body, an isocyanurate type modified body, a burette type modified body, and an allophanate type modified body, the following modified body is preferable from a viewpoint of an adhesive improvement.
That is, as the TMP adduct type modified product, a TMP adduct type modified product obtained by the reaction of TMP and TDI, a TMP adduct type modified product obtained by the reaction of TMP and XDI, and a reaction of TMP and hydrogenated XDI are obtained. TMP adduct-type modified product, TMP adduct-type modified product obtained by reaction of TMP and IPDI, TMP adduct-type modified product obtained by reaction of TMP and HDI, and TMP adduct type obtained by reaction of TMP and MDI Modified products are preferred.
Further, the isocyanurate-type modified product is an isocyanurate-type modified product obtained by trimming HDI, an isocyanurate-type modified product obtained by trimming IPDI, an isocyanurate-type modified product obtained by trimming TDI, and An isocyanurate type modified product obtained by trimerization of hydrogenated XDI is preferred.
Moreover, as a burette type modified body, the burette type modified body obtained by reaction of urea and HDI is preferable.
Moreover, as an allophanate type modified body, the allophanate type modified body obtained by reaction of urethane and IPDI is preferable.
Of the above-mentioned aromatic, aliphatic, and alicyclic diisocyanates, or modified products thereof, it is preferable to use IPDI isocyanurate-modified isocyanate as the isocyanate group-containing compound.

The polythiol compound (A) used in combination with at least one of the above-mentioned TMP adduct type modified product, isocyanurate type modified product, burette type modified product and allophanate modified product is preferably β having a primary thiol group -One or two mercaptopropionic acid ester compounds and a thiol isocyanurate compound having a primary thiol group.
Here, as the β-mercaptopropionate esterified product having a primary thiol group, preferably pentaerythritol tetrakis (3-mercaptopropionate) (PEMP) and dipentaerythritol hexakis (3-mercaptopropionate) DPMP At least one of the following. The thiol isocyanurate compound having a primary thiol group is preferably a thiol isocyanurate compound having a primary thiol group having 3 thiol groups in 11 molecules, more preferably tris- [ (3-mercaptopropionyloxy) -ethyl] -isocyanurate (TEMPIC).

(Acryloyl group-containing compound)
The acryloyl group-containing compound is preferably a monoacrylate having one acryloyl group or a polyacrylate having two or more acryloyl groups.
Monoacrylates include, for example, linear alkanol acrylates such as hexyl acrylate and stearyl acrylate, alkanol acrylates having a branched structure such as 2-ethylhexyl acrylate, and aliphatic alkanols having a ring structure such as cyclohexyl acrylate and isobornyl acrylate. Acrylates, aromatic alcohol acrylates such as benzyl acrylate, and the like, as well as halogenated alcohol acrylates such as 2-chloroethyl acrylate, alkoxy alcohol acrylates such as 3-methoxybutyl acrylate, and the like. .
Specific examples of the polyacrylate having two or more acryloyl groups include compounds in which the methacryloyl group of the dimethacrylate and polyfunctional methacrylate is replaced with an acryloyl group.
More preferable polyacrylates include compounds represented by the following structural formulas (1) to (3), and a compound represented by the structural formula (1) is more preferable.

(Methacryloyl group-containing compound)
As the methacryloyl group-containing compound, polymethacrylate having two or more methacryloyl groups is preferable. Among polymethacrylates having two or more methacryloyl groups, as specific examples of dimethacrylate, for example, a straight-chain alkanediol dimethacrylate such as 1,6-hexanediol dimethacrylate, a branched structure such as neopentylglycol dimethacrylate, etc. Examples include alkanediol dimethacrylate, dicyclopentanediol dimethacrylate and other alkanediol dimethacrylates having a ring structure, polyether diol dimethacrylates such as polyethylene glycol dimethacrylate, and alkylene oxide adducts thereof. .
In addition, as carbon number of alkanediol in the dimethacrylate of the said linear alkanediol, the dimethacrylate of the alkanediol which has the said branched structure, and the dimethacrylate of the alkanediol which has a ring structure, 2 or more and 50 or less are mentioned, for example.
Moreover, as a repeating unit number of the polyether in the diol dimethacrylate of the said polyether, 2-15 is mentioned, for example.

Specific examples of the trifunctional or higher polyfunctional methacrylate include, for example, methacrylic acid-modified products of polyhydric alcohols such as trimethylolpropane, pentaerythritol, and glycerin, or alkylene oxide-modified products thereof. In addition, as carbon number of a polyhydric alcohol, 6 or more and 100 or less are mentioned, for example.
More specifically, examples of the trifunctional or higher polyfunctional methacrylate include trimethylolpropane trimethacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexamethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, and the like.

As a compound having a methacryloyl group, epoxy polymethacrylate, polyester polymethacrylate, a methacryloyl group-containing methacrylic acid ester copolymer, and the like can also be used.
Specific examples of the epoxy polymethacrylate include bisphenol type epoxy dimethacrylate obtained by reacting bisphenol type epoxy resin obtained by condensation reaction of bisphenol A and epichlorohydrin and methacrylic acid.
Specific examples of the polyester polymethacrylate include compounds obtained by reacting a polybasic acid such as phthalic acid, a polyhydric alcohol such as ethylene glycol, and methacrylic acid.

  More preferable polymethacrylates include compounds represented by the following structural formulas (4) to (6), and a compound represented by the structural formula (6) is more preferable.

(Epoxy group-containing compound)
As the epoxy group-containing compound, an epoxy compound having two or more epoxy groups is preferable. Examples of the epoxy compound having two or more epoxy groups include aromatic epoxides, aliphatic epoxides, alicyclic epoxides, and modified products thereof.
Examples of aromatic epoxides include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type epoxy compounds, phenol novolac type epoxy compounds, cresol novolak type epoxy compounds, polyphenol type epoxy compounds, biphenyl type epoxy compounds, and naphthalene rings. Examples thereof include a containing epoxy compound and a fluorene type epoxy compound.

Examples of the aliphatic epoxide include polyalkylene glycol diglycidyl ether such as trimethylolpropane triglycidyl ether, glycerol polyglycidyl ether, and the like.
Examples of the alicyclic epoxide include cyclohexane dimethanol diglycidyl ether.
Examples of modified aromatic epoxides, aliphatic epoxides, and alicyclic epoxides include hydrogenated bisphenol A type epoxy compounds, hydrogenated bisphenol F type epoxy compounds, hydrogenated biphenyl type epoxy compounds, brominated bisphenol type epoxy compounds, and the like. Is mentioned.

  Among these, a cresol novolac type epoxy compound (for example, product name “Jer152” manufactured by Mitsubishi Chemical Corporation), a bisphenol A type epoxy compound (for example, product name “Jer1001B80” manufactured by Mitsubishi Chemical Corporation, manufactured by ADEKA Corporation) , Trade name "EP-4100"), aromatic epoxide of epoxy compound having urethane skeleton, alicyclic epoxide of epoxy compound having urethane skeleton, hydrogenated bisphenol A type epoxy compound (for example, manufactured by Kyoeisha Chemical Co., Ltd. The name “Epolite 4000”) is preferred.

(Vinyl group-containing compound, vinyloxy group-containing compound, and allyl group-containing compound)
As the vinyl group-containing compound, a vinyl compound having two or more vinyl groups is preferable. The vinyloxy group-containing compound is preferably a vinyl ether compound or a vinyl ester compound having two or more vinyloxy groups. The allyl group-containing compound is preferably an allyl compound having two or more allyl groups.
Specific examples of a vinyl compound having two or more vinyl groups, a vinyl ether compound having two or more vinyloxy groups, and an allyl compound having two or more allyl groups include an allyloxy group of the allyl ether compound, a vinyl group, The compound replaced with the vinyloxy group and the allyl group is mentioned. Moreover, as a vinyl ester compound which has a 2 or more vinyloxy group, the compound which replaced the allyloxy group of the said allyl ester compound with the vinyloxy group is mentioned.

(Allyloxy group-containing compound)
The allyloxy group-containing compound is preferably an allyl ether compound or an allyl ester compound having two or more allyloxy groups.
Examples of allyl ether compounds having two or more allyloxy groups include trimethylolpropane diallyl ether, trimethylolpropane triallyl ether, pentaerythritol triallyl ether, glycerin 1,3-diallyl ether, bisphenol A diallyl ether, urethane allyl ether Examples thereof include compounds in which two or more alcoholic hydroxyl groups in dialcohol or polyhydric alcohol are substituted with allyloxy groups, such as oligomers. Examples of the allyl ester compound having two or more allyloxy groups include diallyl phthalate.

  More preferable allyl ether compounds include compounds represented by the following structural formulas (7) to (9), and a compound represented by the structural formula (8) is more preferable.

<Radical generator (C)>
As the radical generator (C), at least one of a thermal radical generator and a photo radical generator can be used. Among these, from the viewpoint of improving the adhesive force and from the viewpoint of being able to adhere rubber that is not transparent (not transmitting light), a thermal radical generator is preferable, a thermal radical generator composed of peroxide is more preferable, and organic A thermal radical generator made of peroxide is more preferred.
A radical generator (C) can also be used individually by 1 type or in combination of 2 or more types.

  Examples of the thermal radical generator composed of an organic peroxide include t-butyl-2-ethylperoxyhexanoate, dilauroyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexa. Noate, 1,1-di (t-hexylperoxy) cyclohexanone, di-t-butyl peroxide, t-butylcumyl peroxide, 1,1-di (t-hexylperoxy) -3,3,5 -Trimethylcyclohexane, t-amylperoxy-2-ethylhexanoate, di (2-t-butylperoxyisopropyl) benzene, di (t-butyl) peroxide, benzoyl peroxide 1,1'-di (2 -T-butylperoxyisopropyl) benzene, benzoyl peroxide, 1,1'-di (t-butylperoxy) cyclohexane Sun, di (3,5,5-trimethyl hexanoyl) peroxide, t- butyl peroxyneodecanoate, t-hexyl peroxyneodecanoate, dicumyl peroxide and the like. Among these, preferably t-butyl-2-ethylperoxyhexanoate, dilauroyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 1,1-di It is at least one of (t-hexylperoxy) cyclohexanone, di-t-butyl peroxide, and t-butylcumyl peroxide. The thermal radical generator composed of an organic peroxide can be used alone or in combination of two or more.

  Redox generation consisting of a combination of oxidizing agent and reducing agent such as a combination of hydrogen peroxide and iron (II) salt, a combination of persulfate and sodium bisulfite, etc. Agents. The thermal radical generator composed of an inorganic oxide can be used alone or in combination of two or more.

When it is a photo radical generator, the thiol-reactive compound (B) is preferably at least one compound selected from acrylate compounds, methacrylate compounds, allyl compounds, vinyl compounds, allyl ether compounds, and vinyl ether compounds. .
Examples of the photo radical generator include intramolecular cleavage type photo radical generators, and benzoin alkyl ether photo radical generators such as benzoin ethyl ether, benzoin isobutyl ether and benzoin isopropyl ether; 2,2-diethoxy Acetophenone photo radical generators such as acetophenone, 4′-phenoxy-2,2-dichloroacetophenone; 2-hydroxy-2-methylpropiophenone, 4′-isopropyl-2-hydroxy-2-methylpropiophenone, 4 Propiophenone photoradical generators such as'-dodecyl-2-hydroxy-2-methylpropiophenone; anthra such as benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone and 2-ethylanthraquinone, 2-chloroanthraquinone Non-based photoradical generating agents; acylphosphine oxide-based photoradical generating agents and the like.

Other hydrogen abstraction type photo radical generators include benzophenone / amine photo radical generator, Michler ketone / benzophenone photo radical generator, thioxanthone / amine photo radical generator, and the like. In order to avoid migration of the unreacted photoradical generator, a non-extractable photoradical generator can be used. For example, there are those obtained by polymerizing an acetophenone radical generator and those obtained by adding a double bond of an acrylic group to benzophenone.
These photo radical generators can be used alone or in combination of two or more.
In addition to the component (C), the composition used in the present invention may contain other radical generators such as a radical generator for promoting the formation of a sheet of the composition. When using together the radical generator used as a component (C), and another radical generator, the same kind of energy required for activation may mutually be used together, and a different thing may be used together.

Specifically, for example, when the reactive functional group of the component (B) is a group having a carbon-carbon double bond, for example, light as a radical generator for promoting sheet formation of the adhesive composition. A radical generator can be used, and a thermal radical generator can be used as component (C). Then, the polythiol compound (A) and the component (B) are polymerized by light irradiation to form an adhesive composition, and an overlapped body may be formed using the obtained adhesive composition sheet. .
Here, examples of the reactive functional group having a carbon-carbon double bond include an acryloyl group, a methacryloyl group, a vinyl group, a vinyloxy group, an allyl group, an allyloxy group, and a norbornenyl group.

The adhesive composition may further contain a polymerization catalyst for polymerizing the component (A) and the component (B) at room temperature in addition to the radical generator for promoting sheet formation. However, the adhesive composition can be formed into a sheet even if the polymerization catalyst is not included.
The adhesive composition contains a radical generator for promoting sheet formation, and does not contain the polymerization catalyst, so that the storage stability of the adhesive composition and energy are imparted to the laminated body. Both the film strength of the adhesive layer in the obtained laminate can be obtained.

  In the case where the component (C) and other radical generator are used in combination, for example, a photoradical generator is used as the component (C), and a thermal radical is generated as a radical generator for promoting sheet formation of the adhesive composition. The form using an agent may be sufficient. In addition, using two types of photo radical generators activated by light of different wavelengths, the adhesive composition is formed into a sheet by light irradiation, and then light having a wavelength different from the wavelength used for forming the adhesive composition into a sheet is used. May be irradiated to the laminated body to obtain a laminated body.

<Optional component>
In the laminated body for rubber bonding according to the embodiment of the present invention, an optional component may be further blended in the vulcanized rubber adhesive composition forming the vulcanized rubber adhesive layer. As optional components, a catalyst used for forming a vulcanized rubber adhesive composition into a sheet, a surface conditioner, a solvent, a binder, a filler, a pigment dispersant, a conductivity imparting agent, an ultraviolet absorber, an antioxidant , Anti-drying agents, penetrants, pH adjusters, metal sequestering agents, antibacterial and fungicides, surfactants, plasticizers, waxes, leveling agents and the like.

(Catalyst (D))
You may use the catalyst (D) which accelerates | stimulates reaction with a component (A) and a component (B). For example, when the component (B) contains an isocyanate group as a reactive functional group, any thiourethanization catalyst can be used as the catalyst (D). Examples of the thiourethanization catalyst include dibutyltin dilaurate, dibutyltin diacetate, dibutyltin thiocarboxylate, dibutyltin dimaleate, dioctyltin thiocarboxylate, tin octenoate, monobutyltin oxide, and the like; Inorganic tin compounds; organic lead compounds such as lead octenoate; bis (2-dimethylaminoethyl) ether, N, N, N ′, N′-tetramethylhexamethylenediamine, triethylenediamine (TEDA), benzyldimethylamine, 2 Amine catalysts such as 2,2'-dimorpholinoethyl ether and N-methylmorpholine; organic sulfonic acids such as p-toluenesulfonic acid, methanesulfonic acid and fluorosulfuric acid; inorganic acids such as sulfuric acid, phosphoric acid and perchloric acid Sodium alcoholate, hydroxylated Lithium, aluminum alcoholate, bases such as sodium hydroxide; tetrabutyl titanate, tetraethyl titanate, titanium compounds such as tetraisopropyl titanate; bismuth compounds; quaternary ammonium salts, and the like.
Among these, an amine catalyst is preferable, and triethylenediamine (TEDA) is more preferable. These catalysts may be used alone or in combination of two or more.

When component (B) contains at least one of an acryloyl group and a methacryloyl group as a reactive functional group, any Michael addition catalyst can be used as the catalyst (D).
Examples of the Michael addition catalyst include amine-based catalysts, base catalysts, and organometallic catalysts.
Examples of amine-based catalysts include proline, triazabicyclodecene (TBD), diazabicycloundecene (DBU), hexahydromethylpyrimidopyridine (MTBD), diazabicyclononane (DBN), tetramethylguanidine (TMG). ), Triethylenediamine (TEDA), and the like.
Examples of the base catalyst include sodium methoxide, sodium ethoxide, potassium tertiary butoxide, potassium hydroxide, sodium hydroxide, sodium metal, lithium diisopropylamide (LDA), butyl lithium and the like.
Examples of organometallic catalysts include ruthenium-based catalysts such as ruthenium cyclooctadiene cyclooctatriene and hydridoruthenium, iron-based catalysts such as iron trichloride and iron acetylacetonate, nickel acetylacetonate, nickel acetate, and nickel salicylaldehyde. Nickel catalyst, copper catalyst, palladium catalyst, scandium catalyst, lanthanum catalyst, ytterbium catalyst, tin catalyst and the like.
These catalysts may be used alone or in combination of two or more.
Among these, as the Michael addition catalyst, an amine catalyst is preferable, an amine catalyst having two or more amino groups in one molecule is more preferable, an amine catalyst having a ring structure is particularly preferable, and triethylenediamine is particularly preferable. Most preferred.

Moreover, when a component (B) contains an epoxy group as a reactive functional group, arbitrary anion polymerization catalysts can be used as a catalyst (D). Examples of the anionic polymerization catalyst include amine-based catalysts.
Examples of amine-based catalysts include diamines, and specific examples include bis (2-dimethylaminoethyl) ether, N, N, N ′, N′-tetramethylhexamethylenediamine, and triethylenediamine (TEDA). , Benzyldimethylamine, 2,2′-dimorpholinoethyl ether, N-methylmorpholine, and the like. Among these, triethylenediamine (TEDA) is preferable. These catalysts may be used alone or in combination of two or more.

(Surface conditioner (E))
Any surface conditioning agent can be used as the surface conditioning agent (E). Examples of the surface conditioner include acrylic, vinyl, silicone, and fluorine. Among these, a silicone type is preferable from the viewpoint of compatibility and surface tension reducing ability.

(solvent)
As a solvent, what is necessary is just a thing which does not react with another compounding component, and an aromatic solvent and an aliphatic solvent are mentioned. Specific examples of the aromatic solvent include toluene, xylene and the like. Hexane etc. are mentioned as an aliphatic solvent.

<Amount of each component in the vulcanized rubber adhesive composition>
Ratio of the total number of moles of thiol-reactive groups contained in the thiol-reactive compound (B) blended to the total number of thiol groups contained in the polythiol compound (A) blended in the vulcanized rubber adhesive composition (Thiol reactive group / thiol group) is preferably 0.20 or more and 0.78 or less.
If the ratio (thiol-reactive group / thiol group) is 0.20 or more, the laminate for rubber bonding is cured firmly and sufficient adhesive strength is obtained.
If the ratio (thiol-reactive group / thiol group) is 0.78 or less, sufficient thiol-ene reaction occurs between the thiol group and the carbon-carbon double bond of the rubber member, and for rubber adhesion. The laminate can be firmly adhered to the vulcanized rubber, and the adhesive strength is increased.
Therefore, the ratio (thiol reactive group / thiol group) is more preferably 0.30 or more and 0.60 or less.
Here, the total number of moles of thiol groups contained in the blended polythiol compound (A) is obtained by multiplying the number of moles of the blended polythiol compound (A) by the number of thiol groups possessed by one molecule of the polythiol compound (A). Can be calculated.
Moreover, the total number of moles of the thiol-reactive group contained in the thiol-reactive compound (B) can be measured by JIS K1603-1 B method.
Furthermore, the ratio of the number of moles (thiol-reactive group / thiol group) is the total number of moles of the thiol-reactive group obtained as described above by the total number of moles of thiol groups contained in the polythiol compound (A). It can be obtained by dividing.

  Ratio of the total number of moles of radical generator (C) blended in the vulcanized rubber adhesive composition to the total number of moles of thiol groups contained in the polythiol compound (A) blended in the vulcanized rubber adhesive composition (Radical generator (C) / thiol group) is preferably 0.025 or more. Thereby, adhesiveness improves. From this viewpoint, the ratio (radical generator (C) / thiol group) is preferably 0.03 or more, more preferably 0.035 or more, and further preferably 0.04 or more. From the viewpoint of improving adhesiveness, the ratio (radical generator (C) / thiol group) is preferably 0.5 or less, more preferably 0.45 or less, and still more preferably 0.4. It is as follows.

The vulcanized rubber adhesive composition may contain a compound containing a carbon-carbon double bond as an optional component. However, when the compounding quantity of this compound containing a carbon-carbon double bond increases, a polythiol compound (A) will react with the compound containing this carbon-carbon double bond. Thereby, the thiol-ene reaction between the polythiol compound (A) and the carbon-carbon double bond in the rubber becomes difficult to occur, and the adhesive force of the composition to the rubber may be reduced. Alternatively, the hydrogen abstraction reaction from the carbon-carbon bond main chain of the rubber hardly causes a reaction in which the sulfur atom of the thiol group of the polythiol compound (A) and the carbon atom of the carbon-carbon bond are chemically bonded. Therefore, the adhesive strength of the composition to rubber may be reduced. Therefore, the ratio of the total number of moles of carbon-carbon double bonds contained in the compound containing carbon-carbon double bonds to be blended to the total number of moles of thiol groups contained in the blended polythiol compound (A) (carbon -Carbon double bond / thiol group) is preferably less than 0.4, preferably less than 0.1, more preferably 0.08 or less, and 0.05 or less. More preferably, it is still more preferably 0.01 or less.
Here, the total number of moles of carbon-carbon double bonds contained in the compound containing a carbon-carbon double bond to be blended is the carbon-carbon of one molecule of the compound in the number of moles of the compound to be blended. It can be determined by multiplying the number of double bonds.
Moreover, the ratio of the number of moles (carbon-carbon double bond / thiol group) is the total number of moles of the radical generator (C) to be blended obtained as described above, and the polythiol compound (A ) By dividing by the total number of moles of thiol groups contained in.

As described above, the vulcanized rubber adhesive composition may contain an optional component in addition to the essential components (A) to (C). However, the total content of components (A) to (C) in the vulcanized rubber adhesive composition is preferably 80% by mass or more, more preferably from the viewpoint of firmly bonding to rubber, particularly vulcanized rubber. Is 90% by mass or more, more preferably 95% by mass or more, and still more preferably 98% by mass or more.
From the same viewpoint, the total content of the components (A) to (E) is preferably 90% by mass or more, more preferably 95% by mass or more, further preferably 99% by mass or more, and further preferably 100% by mass. .

[Unvulcanized rubber adhesive layer]
The unvulcanized rubber adhesive layer constituting the laminated body for rubber bonding according to this embodiment will be described. The unvulcanized rubber adhesive layer is formed of an unvulcanized rubber adhesive composition.
The main component of the unvulcanized rubber adhesive composition is preferably chlorinated rubber or chlorosulfonated polyethylene. The main component includes 50% by mass or more of chlorinated rubber alone, 50% by mass or more of chlorosulfonated polyethylene alone, based on the total amount of the unvulcanized rubber adhesive composition, or chlorinated rubber and chlorosulfonated polyethylene. It means that 50 mass% or more is included in total.
Chlorinated rubber is chlorinated natural rubber or synthetic rubber. Chlorosulfonated polyethylene is an elastomer obtained by chlorosulfonated polyethylene.
The adhesive composition mainly composed of chlorinated rubber and chlorosulfonated polyethylene is manufactured by Toyo Chemical Laboratory Co., Ltd., trade name “Metaloc F-112”, manufactured by LORD Co., Ltd., trade names “Chemok 6108” and “Chemok 6125”. Is commercially available.

[Form of vulcanized rubber adhesive layer]
The vulcanized rubber adhesive layer is preferably processed into a sheet shape. A vulcanized rubber adhesive composition (hereinafter referred to as an adhesive sheet) processed into a sheet is formed by applying the vulcanized rubber adhesive composition on a release sheet such as a release paper or a release film, and maintaining the sheet shape. Can be manufactured. By maintaining the sheet shape, it is considered that at least a part of the thiol group and the thiol reactive group in the vulcanized rubber adhesive composition reacts to form a sheet shape.
In addition, an adhesive sheet can be suitably manufactured by leaving it at normal temperature after apply | coating to a peeling sheet. Moreover, you may manufacture an adhesive sheet by heating so that the radical reaction by a radical generator may not start after application | coating.
The holding time can be adjusted by the amount of the catalyst. From the viewpoint of workability in forming a sheet and maintaining the shape to such an extent that the sheet shape can be maintained during the bonding operation, it is preferably 1 minute or longer, more preferably 3 minutes or longer. The holding temperature can usually be made into a sheet at room temperature, but it can also be heated to such an extent that the radical generator in the material is not cleaved. From the above viewpoint, it is preferably 0 to 60 ° C, more preferably 15 to 40 ° C.
In the production of the adhesive sheet (hereinafter referred to as sheeting process), the adhesive sheet can also be produced by using a photoinitiator instead of a catalyst and performing light irradiation at room temperature.

Examples of release sheet materials include polyester resins such as polyethylene terephthalate, polycyclohexylene terephthalate, and polyethylene naphthalate; polyamide resins such as nylon 46, modified nylon 6T, nylon MXD6, and polyphthalamide, polyphenylene sulfide, and polythioether sulfone. In addition to sulfone resins such as polysulfone and polyethersulfone, polyether nitrile, polyarylate, polyetherimide, polyamideimide, polycarbonate, polymethyl methacrylate, triacetyl cellulose, polystyrene, polyvinyl chloride, etc. A transparent resin substrate mainly composed of an organic resin can be suitably used.
The vulcanized rubber adhesive composition processed into a sheet shape, that is, the thickness of the adhesive sheet can be appropriately selected according to the object to be bonded, the required adhesive strength, etc., for example, 20 to 1000 μm Yes, preferably 30 to 300 μm, more preferably 30 to 200 μm.

[Complex]
According to the rubber bonding laminate according to the present embodiment, a composite of vulcanized rubber and unvulcanized rubber can be formed by bonding vulcanized rubber and unvulcanized rubber.
The composite is obtained by arranging and bonding vulcanized rubber, a rubber bonding laminate, and unvulcanized rubber in this order. In the composite, first, the vulcanized rubber adhesive layer and the vulcanized rubber of the laminate for rubber bonding are brought into close contact with each other, and the unvulcanized rubber adhesive layer and the unvulcanized rubber are brought into close contact with each other, followed by vulcanization adhesion Can be formed.
In a state where the vulcanized rubber, the rubber bonding laminate and the unvulcanized rubber are in close contact, pressing may be performed in the thickness direction as necessary. In the case of pressing, from the viewpoint of improving the adhesive force, the pressing pressure is preferably 0.1 to 5.0 MPa, more preferably 0.4 to 4.0 MPa, and still more preferably 0.5 to 3. 0 MPa.
The composite may be formed by alternately arranging a plurality of vulcanized rubbers and unvulcanized rubbers as described above.

<Vulcanized rubber and unvulcanized rubber>
According to the laminated body for rubber bonding according to the present embodiment, it is estimated that the sulfur atom of the thiol group of the polythiol compound (A) included in the vulcanized rubber adhesive layer in close contact with the vulcanized rubber forms a carbon-sulfur bond. Therefore, the vulcanized rubber and unvulcanized rubber forming the composite are preferably those having a carbon-carbon double bond.
However, it is presumed that the composite can be formed even if the vulcanized rubber and the unvulcanized rubber do not have a carbon-carbon double bond. In this case, a reaction occurs in which the polythiol compound (A) extracts hydrogen from the carbon-carbon bond main chain present in the vulcanized rubber or the unvulcanized rubber, and the sulfur atom of the thiol group of the polythiol compound (A) and the carbon-carbon bond. It is presumed that the carbon atom is chemically bonded.
From the viewpoint of improving adhesive strength, the vulcanized rubber or unvulcanized rubber preferably has a carbon-carbon double bond.

  Examples of vulcanized rubber and unvulcanized rubber include natural rubber; polyisoprene synthetic rubber (IR), polybutadiene rubber (BR), styrene-butadiene copolymer rubber (SBR), acrylonitrile butadiene rubber (NBR), and chloroprene rubber. (CR), conjugated diene-based synthetic rubber such as butyl rubber (IIR); ethylene-propylene copolymer rubber (EPM), ethylene-propylene-diene copolymer rubber (EPDM), polysiloxane rubber, etc. Of these, natural rubber and conjugated diene synthetic rubber are preferred. Moreover, you may use a rubber component in combination of 2 or more types.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.
[Measuring method]
<Total moles of thiol groups contained in polythiol compound (A) (SH)>
The total number of moles (SH) of thiol groups contained in the polythiol compound (A) was calculated by dividing the blending amount by the theoretical molecular weight and multiplying by the number of thiol groups possessed by one molecule of the polythiol compound (A).

<Total moles of reactive functional groups (FG) contained in thiol-reactive compound (B)>
The total number of moles of reactive functional groups (FG) contained in the thiol-reactive compound (B) is the number of reactive functional groups possessed by one molecule of the thiol-reactive compound (B) by dividing the blending amount by the theoretical molecular weight. It can be obtained by multiplying.
When all the reactive functional groups of the thiol-reactive compound (B) are isocyanate groups, the total number of moles of isocyanate groups contained in the isocyanate group-containing compound to be blended was measured by JIS K1603-1 B method. When the thiol-reactive compound (B) is an epoxy resin, the epoxy equivalent of the epoxy resin (the mass of the resin containing 1 equivalent of an epoxy group) is measured by a method based on JIS K7236: 2001, and the epoxy resin The total number of moles of epoxy groups contained in the thiol-reactive compound (B) may be calculated by dividing the number average molecular weight by the obtained epoxy equivalent.
In addition, after preparing a vulcanized rubber adhesive composition by a method to be described later or after being formed into a sheet through a sheet forming process, the total number of thiol groups (SH) and the total number of reactive functional groups When obtaining the number (FG), for example, using a known measurement technique such as NMR measurement or IR measurement, the polythiol compound (A) contained in the vulcanized rubber adhesive composition before becoming an adhesive layer or an adhesive sheet is used. ) And the thiol-reactive compound (B), and the (SH) value and (FG) value may be determined by the above method.

<Measurement of total number of moles of carbon-carbon double bond (Ene)>
The total number of moles of carbon-carbon double bonds (Ene) contained at the end of the thiol-reactive compound (B) is obtained by dividing the blending amount by the theoretical molecular weight, and one molecule of the thiol-reactive compound (B) It was obtained by multiplying by the number of carbon-carbon double bonds.

<Measurement of the total number of moles of epoxy groups (Ep)>
The epoxy equivalent of the epoxy resin (the mass of the resin containing 1 equivalent of an epoxy group) was measured by a method based on JIS K7236: 2001. The number average molecular weight of the epoxy resin is divided by the obtained epoxy equivalent to calculate the number of epoxy groups that one molecule of the thiol-reactive compound (B) has. Here, the number average molecular weight means the number average molecular weight in terms of styrene. Moreover, the number average molecular weight of an epoxy resin can be calculated | required by the chromatography method.

<Method of measuring peel force>
(T-type peel strength test and 180 ° peel strength test)
Measured based on JIS K 6854 (1999) peel adhesion strength test.
It applied to two rubber members so that thickness might be set to 30 micrometers, the application surface was bonded together and it was hardened. Curing was performed by holding at a temperature of 150 ° C. for 30 minutes while applying a press pressure of 0.05 MPa. The rubber member was pulled in the direction of 180 degrees under the condition of a pulling speed of 50 mm / min, and the peel strength (N / 25 mm) was measured as an adhesive index.

[Vulcanized rubber adhesives A to G]
Vulcanized rubber adhesives A to G were prepared according to the formulation shown in Table 1. Each vulcanized rubber adhesive was processed into a sheet through a sheeting process. The sheeting process is as follows. That is, for the one using an amine catalyst, it was set at room temperature (25 ° C.) while being kept at a thickness of 100 μm and kept for a predetermined time.
On the other hand, those using optical radical generator, while maintaining the thickness of 100μm, 100~2000mW / cm ^2, was irradiated with ultraviolet rays under conditions of 150~1800mJ / cm ^2.

The details of each component in Table 1 are as follows.
* 1 Polythiol compound: Pentaerythritol tetrakis (3-mercaptopropionate) (PEMP), manufactured by SC Organic Chemical Co., Ltd. * 2 Polythiol compound: Pentaerythritol tetrakis (thioglycolate) (PETG): manufactured by Sakai Chemical Co., Ltd. (1 Grade thiol)
* 3 Isocyanate group-containing compound: IPDI isocyanurate-modified isocyanate: manufactured by Sumika Bayer Urethane Co., Ltd., trade name “Desmodur Z4470BA”, NCO content 11.9%
* 4 Methacrylate compound: Compound described in the above structural formula (6) * 5 Epoxy compound: Bisphenol A type epoxy compound: Product name “Jer1001B80” manufactured by Mitsubishi Chemical Corporation
* 6 Allyl ether compound: Compound described in the above structural formula (8) * 7 Acrylate compound: Compound described in the above structural formula (1) * 8 Thermal radical generator: t-butyl-2-ethylperoxyhexanoate, Product name "Perbutyl O", manufactured by Nippon Oil & Fat Co., Ltd.
* 9 Photoradical generator: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, manufactured by BASF Corporation, trade name “LUCIRIN TPO”
* 10 Triethylenediamine (TEDA): Product name “DABCO 33LV catalyst” manufactured by Air Products
* 11 Silicone acrylate surface conditioner: Toyo Chemicals, trade name “Miramer SIU2400”

[Examples 1-7 and Comparative Examples 1-4]
In Examples 1 to 7 and Comparative Examples 1 to 3, unvulcanized rubber adhesives 1 and 2 were sprayed on the vulcanized rubber adhesives A to G processed into a sheet shape so as to have a thickness of 10 μm. This was applied to prepare a laminated body for rubber bonding. Comparative Examples 1 to 3 were produced by using a rubber bonded laminate without using a vulcanized rubber adhesive. In Comparative Example 4, a rubber bonded laminate without using an unvulcanized rubber adhesive. Is produced.
Vulcanization so that the vulcanized rubber adhesive and vulcanized rubber of the obtained rubber bonding laminate face each other, and the unvulcanized rubber adhesive and the unvulcanized rubber of the rubber bonding laminate face each other. A rubber, unvulcanized rubber, and a rubber bonding laminate were laminated and bonded to obtain a specimen. The adhesive strength of each obtained specimen was evaluated by the evaluation method described above. The results are shown in Tables 2 and 3.

The details of each component in Tables 2 and 3 are as follows.
* 12: NR: Natural rubber (RSS # 3), SBR: Styrene-butadiene copolymer rubber (manufactured by JSR, trade name “JSR 1500”) The parentheses indicate the mixing ratio. That is, NR (20) / SBR (80) indicates that the mixture is 20% by mass of natural rubber and 80% by mass of SBR.
* 13: Unvulcanized rubber adhesive 1 Product name “Chemok CH6125” manufactured by LORD Corporation
* 14: Unvulcanized rubber adhesive 2 Product name “Chemok CH6108” manufactured by LORD Corporation

[result]
As shown in Tables 2 and 3, sufficient adhesive strength is not obtained when vulcanized rubber adhesive is not used, and sufficient adhesive strength is not obtained when only vulcanized rubber adhesive is used. It was. That is, it can be seen that the laminate for rubber bonding according to the present invention can firmly bond the vulcanized rubber and the unvulcanized rubber.

  Since the laminated body for rubber bonding according to the present invention can firmly bond a vulcanized rubber article and an unvulcanized rubber article, for example, a rubber hose, an anti-vibration rubber, a rubber belt, a rubber dam, a belt conveyor, a packing, etc. It can be used for various industrial rubber products. Moreover, it can utilize especially for adhesion | attachment with the base tire and tread member in a retreaded tire.

Claims (14)

A laminated body for rubber bonding in which a vulcanized rubber adhesive layer and an unvulcanized rubber adhesive layer are arranged in this order,
The vulcanized rubber adhesive layer includes a polythiol compound (A) containing a plurality of thiol groups, a thiol-reactive compound (B) containing a group having reactivity with the thiol groups, and a radical generator (C). A rubber-bonded laminate having a vulcanized rubber adhesive composition comprising   The thiol-reactive compound (B) has an isocyanate group-containing compound, a monoacrylate having one acryloyl group, a polyacrylate having two or more acryloyl groups, a polymethacrylate having two or more methacryloyl groups, and two or more epoxy groups. At least one selected from an epoxy compound, a vinyl compound having two or more vinyl groups, a vinyl ether compound having two or more vinyloxy groups, an allyl compound having two or more allyl groups, and an allyl ether compound having two or more allyloxy groups The laminated body for rubber bonding according to claim 1, which is one compound.   The laminate for rubber adhesion according to claim 2, wherein the thiol-reactive compound (B) is at least one compound selected from the isocyanate group-containing compound, the monoacrylate, the polyacrylate, the polymethacrylate, and the epoxy compound. body.   The laminated body for rubber bonding according to any one of claims 1 to 3, wherein the vulcanized rubber adhesive layer is processed into a sheet shape.   The laminated body for rubber bonding according to any one of claims 1 to 4, wherein the vulcanized rubber adhesive composition contains a catalyst (D).   The catalyst (D) is an amine catalyst, and the thiol-reactive compound (B) is at least one compound selected from the isocyanate group-containing compound, the monoacrylate, the polyacrylate, and the epoxy compound. The laminated body for rubber bonding according to claim 5.   The laminated body for rubber bonding according to any one of claims 1 to 6, wherein the radical generator (C) is a thermal radical generator.   The laminate for rubber bonding according to claim 7, wherein the thermal radical generator is a peroxide.   The laminated body for rubber bonding according to claim 8, wherein the peroxide is an organic peroxide.   The laminated body for rubber bonding according to any one of claims 1 to 6, wherein the radical generator (C) is a photo radical generator.   The radical generator (C) is a photo radical generator, and the thiol-reactive compound (B) is at least one selected from acrylate compounds, methacrylate compounds, allyl compounds, vinyl compounds, allyl ether compounds, and vinyl ether compounds. The laminate for rubber bonding according to claim 10, which is a compound.   The ratio of the total number of moles of the thiol-reactive group contained in the thiol-reactive compound (B) to the total number of moles of the thiol group contained in the polythiol compound (A) (thiol-reactive group / thiol group) is 0. The laminate for rubber bonding according to any one of claims 1 to 11, which is 20 or more and 0.78 or less.   The ratio of the total number of moles of the thiol-reactive group contained in the thiol-reactive compound (B) to the total number of moles of the thiol group contained in the polythiol compound (A) (thiol-reactive group / thiol group) is 0. It is 30 or more and 0.60 or less, The laminated body for rubber bonding of any one of Claims 1-11.   The laminated body for rubber bonding according to any one of claims 1 to 13, wherein a main component of the unvulcanized rubber adhesive composition forming the unvulcanized rubber adhesive layer is chlorinated rubber or chlorosulfonated polyethylene. .