JP2016008299A - Composition, adhesive, adhesive sheet, and laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition that can firmly adhere a rubber, particularly a vulcanized rubber, an adhesive and an adhesive sheet using the composition, and a laminate having a rubber layer adhered by using at least one of the adhesive and the adhesive sheet.SOLUTION: The composition is prepared by compounding a thioglycol acid ester (A1), a polythiol compound (A2) other than the thioglycol acid ester, an isocyanate group-containing compound (B), and a radical generator (C). A compounding ratio [(A1)/(A2)] of the thioglycol acid ester (A) to the polythiol compound (A2) other than the thioglycol acid ester is 10/90 to 65/35 by mass.

Description

  The present invention relates to a composition, an adhesive, an adhesive sheet, and a laminate, and more specifically, a composition suitable for bonding rubber members, an adhesive, and an adhesive sheet, and at least one of these compositions, adhesive, and adhesive sheet. It is related with the laminated body formed by adhere | attaching a rubber layer using.

  Conventionally, there has been a demand for a material having a good adhesive force with a vulcanized rubber member, but there has been no material capable of obtaining a sufficient adhesive force. As a method for adhering a vulcanized rubber member, for example, Patent Document 1 discloses that a vulcanized rubber member is surface-treated and another member is joined to the surface-treated surface via an adhesive.

JP-A-10-139901

However, the method described in Patent Document 1 takes time for surface treatment because the vulcanized rubber is surface-treated and then adhered to another material via an adhesive. In addition, since a polyurethane adhesive is used, its adhesive strength is insufficient.
The present invention relates to a composition, an adhesive and an adhesive sheet capable of strongly bonding a rubber member, particularly a vulcanized rubber member, and a rubber using at least one of these adhesive composition and adhesive sheet. The present invention relates to a laminate formed by adhering layers.

  In the composition formed by blending the polythiol compound, the isocyanate group-containing compound (B), and the radical generator (C) at a specific ratio, the present inventors have used thioglycolic acid ester (A1) and thiol as the polythiol compound. It has been found that the problems of the present invention can be solved by using a polythiol compound (A2) other than the glycolic acid ester compound and blending at a specific ratio, thereby completing the present invention.

That is, the present invention relates to the following [1] to [10].
[1] A blend of thioglycolic acid ester (A1), polythiol compound (A2) other than thioglycolic acid ester, isocyanate group-containing compound (B), and radical generator (C),
Composition whose blending ratio [(A1) / (A2)] of polythiol compound (A2) other than thioglycolic acid ester (A1) and thioglycolic acid ester is 10/90 to 65/35 in mass ratio object.
[2] The composition according to [1] above, wherein the blending ratio [(A1) / (A2)] is 30/70 to 65/35 by mass ratio.
[3] The composition according to [1] or [2] above, wherein the polythiol compound (A2) other than the thioglycolic acid ester is a mercapto fatty acid ester.
[4] The thioglycolic acid ester product (A1) is obtained by an esterification reaction between a polyhydric alcohol having 2 to 6 hydroxyl groups in the molecule and thioglycolic acid, Any one of the above [1] to [3], which is an alkanediol having 2 to 20 carbon atoms, poly (oxyalkylene) glycol, glycerol, diglycerol, trimethylolpropane, ditrimethylolpropane, pentaerythritol or dipentaerythritol. The composition according to one.
[5] The composition according to [4] above, wherein the polyhydric alcohol is pentaerythritol.
[6] Ratio of the total number of moles of isocyanate groups contained in the blended component (B) to the total number of moles of thiol groups contained in the blended components (A1) and (A2) (isocyanate group / thiol group) ) Is 0.2 or more and 0.78 or less, The composition as described in any one of said [1]-[5].
[7] The composition according to any one of [1] to [6], wherein the composition comprises a urethanization catalyst (D).
[8] An adhesive comprising the composition according to any one of [1] to [7].
[9] An adhesive sheet using the composition according to any one of [1] to [7].
[10] A laminate in which at least two layers are bonded,
At least one layer comprises a rubber layer,
A laminate in which at least one of the rubber layers is bonded to an adjacent layer via the adhesive according to [8] or the adhesive sheet according to [9].

According to the present invention, a composition capable of strongly bonding rubber, particularly vulcanized rubber, an adhesive and an adhesive sheet using the composition, and at least one of these adhesive and adhesive sheet are used. A laminate obtained by adhering a rubber layer can be provided.
In particular, the composition of the present invention includes a composition capable of maintaining high adhesiveness even at a high temperature (for example, 100 ° C. or higher, preferably 100 to 130 ° C.).

In the present specification, thioglycolic acid ester (A1), polythiol compound (A2) other than thioglycolic acid ester, isocyanate group-containing compound (B), radical generator (C), urethanization catalyst (D) and surface The regulator (E) may be referred to as component (A1), component (A2), component (B), component (C), component (D), and component (E), respectively.
Further, in the present specification, it is possible to arbitrarily select a rule that is preferable, and it can be said that a combination of rules that are preferable is more preferable.

[Composition]
The composition of the present invention comprises a thioglycolic acid ester (A1), a polythiol compound (A2) other than a thioglycolic acid ester, an isocyanate group-containing compound (B), and a radical generator (C).
Composition whose blending ratio [(A1) / (A2)] of polythiol compound (A2) other than thioglycolic acid ester (A1) and thioglycolic acid ester is 10/90 to 65/35 in mass ratio It is a thing.

According to the composition of the present invention, not only unvulcanized rubber but also vulcanized rubber can be strongly bonded. The reason is estimated as follows.
It is considered that the composition is firmly cured by causing a urethanization reaction between the component (A1) and a part of the component (A2) and the isocyanate group-containing compound (B). In addition, when another part of the component (A1) and the component (A2) 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. Conceivable. Such a thiol-ene reaction is considered to cause the composition to be strongly bonded to the rubber by chemically bonding the composition to the rubber. In particular, since carbon-carbon double bonds exist not only in unvulcanized rubber but also in vulcanized rubber, it is considered that rubber, particularly vulcanized rubber, can be strongly bonded according to the composition of the present invention.
Further, when the sulfur atom of the thiol group of component (A1) and component (A2) 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. Conceivable. Therefore, it is not always necessary to have a carbon-carbon double bond in the rubber.

<Thioglycolic acid ester (A1)>
Component (A1) is a thioglycolic acid esterified product obtained by an esterification reaction between a polyhydric alcohol having 2 to 6 hydroxyl groups in the molecule and thioglycolic acid. Thioglycolic acid has 2 carbon atoms and has a short chain length, which leads to improved adhesion, particularly at higher temperatures (for example, 100 ° C. or higher, preferably 100 to 130 ° C.).
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, pentaerythritol, And dipentaerythritol. The polyhydric alcohol is a polyvalent alcohol having 3 to 4 hydroxyl groups in the molecule from the viewpoint of improving adhesiveness, particularly from the viewpoint of improving adhesiveness at high temperatures (for example, 100 ° C. or higher, preferably 100 to 130 ° C.). Alcohol is preferable, trimethylolpropane and pentaerythritol are more preferable, and pentaerythritol is more preferable.

Examples of the thioglycolic acid ester (A1) include 1,4-butanediol bisthioglycolate, 1,6-hexanediol bisthioglycolate, trimethylolpropane tristhioglycolate (TMTG: see the following structure), Pentaerythritol tetrakisthioglycolate (PETG: see the following structure) and the like.
The following TMTG and PETG correspond to the case where the polyhydric alcohol is trimethylolpropane or pentaerythritol.

<Polythiol compound other than thioglycolic acid ester (A2)>
Component (A2) is a polythiol compound (polythiol compound (A2) other than a thioglycolic acid ester product (obtained by an esterification reaction between a polyhydric alcohol having 2 to 6 hydroxyl groups in the molecule and thioglycolic acid). )). Here, the “polythiol compound” refers to a compound having two or more thiol groups in one molecule. Moreover, all the following description regarding a component (A2) should be taken as what is excluded about a thioglycolic acid ester compound.
The polythiol compound (A2) is not particularly limited as long as it is other than a thioglycolic acid ester, but preferably has 2 to 6 thiol groups in one molecule from the viewpoint of improving adhesiveness.
The polythiol compound (A2) includes primary, secondary and tertiary compounds, but the primary is more preferable from the viewpoint of improving adhesiveness.
The molecular weight of the polythiol compound (A2) is preferably 3000 or less, more preferably 2000 or less, still more preferably 1000 or less, and still more preferably 900 or less, from the viewpoint of improving adhesiveness. More preferably, it is 800 or less. In addition, when a polythiol compound (A2) is a polymer, molecular weight means the number average molecular weight of styrene conversion.

Examples of the polythiol compound (A2) include aliphatic polythiols that may include heteroatoms and aromatic polythiols that may include heteroatoms. From the viewpoint of improving adhesiveness, the polythiol compound (A2) may include 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. Substituted with a thiol group, a polythiol composed of a hydrogen sulfide reaction product of a polyepoxide compound, 2 to 6 hydroxyl groups in the molecule (preferably 3 to 6, more preferably 4 to 6, more preferably 4 Mercapto fatty acid esterified product obtained by esterification reaction of mercapto fatty acid with a polyhydric alcohol having an acid), a thiol isocyanurate compound obtained by reacting an isocyanurate compound with a thiol, a thiol containing a polysulfide group, and a modified with a thiol group Modified with thiol group Silsesquioxane and the like.
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. The polyhydric alcohol is a polyvalent alcohol having 3 to 4 hydroxyl groups in the molecule from the viewpoint of improving adhesiveness, particularly from the viewpoint of improving adhesiveness at high temperatures (for example, 100 ° C. or higher, preferably 100 to 130 ° C.). Alcohol is preferable, trimethylolpropane, pentaerythritol, and dipentaerythritol are more preferable, and pentaerythritol is more preferable.

  Among these, from the viewpoint of improving adhesiveness, particularly from the viewpoint of improving adhesiveness at high temperatures (for example, 100 ° C. or higher, preferably 100 to 130 ° C.), a polythiol in which a portion other than a thiol group is an aliphatic hydrocarbon, More preferred are polythiols obtained by substituting halogen atoms of halohydrin adducts of alcohols with thiol groups, polythiols consisting of hydrogen sulfide reaction products of polyepoxide compounds, esterified thioglycolates, esterified mercapto fatty acids, and thiol isocyanurate compounds, Mercapto fatty acid esterified products and thiol isocyanurate compounds are more preferred, and mercapto fatty acid esterified products are even more preferred. 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.

(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. The mercapto fatty acid esterified product 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 6. 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: see structure below), pentaerythritol tetrakis (3-mercaptopropionate) (PEMP: see structure below), and dipentaerythritol hexakis (3-mercaptopropionate) (DPMP: see structure below). It is done. Among these, PEMP and DPMP are preferable, and PEMP is 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 silicones modified with a thiol group include trade names KF-2001, KF-2004, X-22-167B (Shin-Etsu Chemical), SMS042, SMS022 (Gelest), PS849, PS850 (UCT). .

(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) benzene, 1,2,4-tris (mercaptoethyl) benzene, 1,3,5-tris (mercapto) Ethyl) benzene, 2,5-tolue Dithiol, 3,4-toluenedithiol, 1,3-di (p-methoxyphenyl) propane-2,2-dithiol, 1,3-diphenylpropane-2,2-dithiol, phenylmethane-1,1-dithiol, 2,4-di (p-mercaptophenyl) pentane and the like can be mentioned.

<Isocyanate group-containing compound (B)>
Examples of the isocyanate group-containing compound (B) 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 (A2) is at least one of a mercapto fatty acid ester and a thiol isocyanurate compound, particularly when it is a mercapto fatty acid ester, the blended isocyanate group-containing compound (B) is: One or more of hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), tolylene diisocyanate (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, and isophorone diisocyanate (IPDI) is still 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.

The polythiol compound (A2) 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]. 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 one molecule, and more preferably tris- [ (3-mercaptopropionyloxy) -ethyl] -isocyanurate [TEMPIC].

<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, di (3,5,5-trimethylhexanoyl) peroxide, t-butylpero Cine Ode Kano benzoate, 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.

As the photoradical generator, known ones can be widely used and are not particularly limited.
For example, an intramolecular cleavage type photo radical generator may be mentioned, and benzoin alkyl ether photo radical generators such as benzoin ethyl ether, benzoin isobutyl ether and benzoin isopropyl ether; 2,2-diethoxyacetophenone, 4′-phenoxy-2 Acetophenone photoradical generators such as 2-dichloroacetophenone, 2-hydroxy-2-methylpropiophenone, 4′-isopropyl-2-hydroxy-2-methylpropiophenone, 4′-dodecyl-2-hydroxy- Propiophenone photoradical generators such as 2-methylpropiophenone; anthraquinone photoradical generators such as benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone and 2-ethylanthraquinone, 2-chloroanthraquinone; Sill phosphine oxide-based photo-radical generating agent, 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.

<Optional component>
The composition of the present invention may further contain optional components. Optional components include urethanization catalysts, surface conditioners, solvents, binders, fillers, pigment dispersants, conductivity imparting agents, UV absorbers, antioxidants, anti-drying agents, penetrants, pH adjusters, metal sequestering agents. , Fungicides, fungicides, surfactants, plasticizers, waxes, leveling agents and the like.

(Urethane catalyst (D))
Any urethanization catalyst can be used as the urethanization catalyst (D). Examples of the catalyst for urethanization reaction include dibutyltin dilaurate, dibutyltin diacetate, dibutyltin thiocarboxylate, dibutyltin dimaleate, dioctyltin thiocarboxylate, tin octenoate, monobutyltin oxide and the like; stannous chloride, etc. Inorganic tin compounds; organic lead compounds such as lead octenoate; bis (2-dimethylaminoethyl) ether, N, N, N ′, N′-tetramethylhexamethylenediamine, triethylenediamine (TEDA), benzyldimethylamine, Amines 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, lithium hydroxide, aluminum alcohol Acrylate, 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, the above amines are preferable, and triethylenediamine (TEDA) is more 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)
The solvent is not particularly limited as long as it does not react with other compounding components, and examples thereof include aromatic solvents and aliphatic solvents.
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 composition of the present invention, the mixing ratio [(A1) / (A2)] between the thioglycolic acid ester product (A1) and the polythiol compound (A2) other than the thioglycolic acid ester product is 10/90 to mass ratio. 65/35. If the compounding ratio of the component (A1) is 10/90 or more, the effect of improving the adhesiveness, particularly the effect of improving the adhesiveness at a high temperature (for example, 100 ° C or higher, preferably 100 to 130 ° C) is large. Moreover, if the compounding ratio of the component (A1) is 65/35 or less, the adhesive strength at 80 ° C. or lower is remarkably increased, and the adhesiveness at a high temperature (for example, 100 ° C. or higher, preferably 100 to 130 ° C.) is remarkably increased. Get higher. From the same viewpoint, the blending ratio [(A1) / (A2)] is a mass ratio, preferably 20/80 to 65/35, more preferably 35/65 to 65/35, and still more preferably 40/60. ~ 65/35. In particular, from the viewpoint of significantly improving the adhesiveness at a high temperature (for example, 100 ° C. or higher, preferably 100 to 130 ° C.), the compounding ratio of the component (A1) is preferably 20/80 or higher in terms of mass ratio. / 70 or more is more preferable.
Ratio of the total number of moles of isocyanate groups contained in the blended isocyanate group-containing compound (B) to the total number of moles of thiol groups contained in the blended component (A1) and component (A2) (isocyanate group / thiol group) ) Is preferably 0.20 or more and 0.78 or less. If the ratio (isocyanate group / thiol group) is 0.20 or more, the composition is sufficiently firmly cured, and there is no possibility that the adhesive strength is reduced. Further, if the ratio (isocyanate group / thiol group) is 0.78 or less, the thiol group is not decreased too much, and the thiol-ene reaction is sufficient between the thiol group and the carbon-carbon double bond of the rubber member. Since the composition can be firmly adhered to the rubber member, there is no possibility that the adhesive strength is reduced. From the same viewpoint, the ratio (isocyanate group / thiol group) is more preferably 0.3 or more and 0.7 or less, more preferably 0.4 or more and 0.7 or less, and further preferably 0. 0.5 or more and 0.7 or less, particularly preferably 0.55 or more and 0.70 or less.
Here, the total number of moles of thiol groups contained in the component (A1) and component (A2) to be blended is the same as the number of moles of the component (A1) and component (A2). (A2) It can obtain | require by adding both after multiplying the number of thiol groups which each 1 molecule has.
Moreover, the total mole number of the isocyanate group contained in the isocyanate group containing compound (B) mix | blended can be measured by JISK1603-1 B method.
Furthermore, the ratio of the number of moles (isocyanate group / thiol group) is the component to be blended with the total number of moles of isocyanate groups contained in the blended isocyanate group-containing compound (B) obtained as described above. It can be determined by dividing by the total number of moles of thiol groups contained in A1) and component (A2).

  The ratio (radical generator (C) / thiol group) of the total number of moles of the radical generator (C) to be blended with respect to the total number of moles of thiol groups contained in the blended component (A1) and component (A2) is 0.025 or more is preferable. 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.

As an optional component, a compound containing a carbon-carbon double bond may be blended. However, when the compounding quantity of the compound containing this carbon-carbon double bond increases, a component (A1) and a component (A2) will react with the compound containing this carbon-carbon double bond. Thereby, the thiol ene reaction between the component (A1) and the component (A2) 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 sulfur atom of the thiol group of component (A1) and component (A2) and the carbon atom of the carbon-carbon bond are chemically bonded by a hydrogen abstraction reaction from the carbon-carbon bond main chain of the rubber. It becomes difficult for the reaction to occur, and the adhesive strength of the composition to rubber may be reduced. Therefore, the total number of moles of carbon-carbon double bonds contained in the compound containing carbon-carbon double bonds to be blended with respect to the total number of moles of thiol groups contained in component (A1) and component (A2) to be blended. The ratio (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. Is more preferable, and it is still more preferable that it is 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.
In addition, the ratio of the number of moles (carbon-carbon double bond / thiol group) is determined by combining the component (A1) and the component ( It can be determined by dividing by the total number of moles of thiol groups contained in A2).

As described above, the composition according to the present invention may contain an optional component in addition to the essential component (A1), component (A2), component (B), and component (C). However, from the viewpoint of strongly bonding rubber, particularly vulcanized rubber, the total content of component (A1), component (A2), component (B) and component (C) in the composition is preferably 80% by mass. More preferably, it is 90% by mass or more, more preferably 95% by mass or more, and further preferably 98% by mass or more.
From the same viewpoint, the total content of the component (A1), the component (A2) and the components (B) to (E) is preferably 90% by mass or more, more preferably 95% by mass or more, and further preferably 99% by mass. As mentioned above, More preferably, it is 100 mass%.

[adhesive]
The adhesive of the present invention contains the above composition. This adhesive may contain components other than the above composition within a range not impairing the object of the present invention. However, from the viewpoint of satisfactorily expressing the effects of the present invention, the content of the composition in the adhesive is preferably 90% by mass or more, more preferably 95% by mass or more, still more preferably 99% by mass or more, and still more preferably. Is 100% by mass.

[Adhesive sheet]
The adhesive sheet of the present invention is formed using the above-described composition.
This adhesive sheet can be suitably manufactured by applying the composition onto a release sheet such as release paper or release film and maintaining the sheet shape. By this holding, it is considered that at least a part of the thiol group and the isocyanate group in the composition undergo a thiolurethane reaction to form a sheet shape. In addition, an adhesive sheet can be suitably manufactured by leaving it at normal temperature after application | coating. 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 standing or heating temperature after coating is preferably −30 to 60 ° C., more preferably −20 to 40 ° C., and still more preferably 0 to 40 ° C.
The total thickness of the release sheet and the composition thereon can be appropriately selected according to the object to be bonded, the required adhesive strength, and the like after application and before standing or heating. It is -1000 micrometers, Preferably it is 10-300 micrometers, More preferably, it is 30-200 micrometers.
The holding time can be adjusted by the amount of the urethanization catalyst. From the viewpoint of maintaining the sheet shape to the extent that the sheet shape can be maintained during the workability of the sheet formation and the bonding operation, it is preferably 1 minute or more, more preferably 3 minutes or more, still more preferably 30 minutes or more, Still more preferably, it is 60 minutes or more. 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.

The material of the release sheet is not particularly limited, but 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 In addition to ketone resins such as polythioether sulfone, sulfone resins such as polysulfone and polyether sulfone, polyether nitrile, polyarylate, polyetherimide, polyamideimide, polycarbonate, polymethyl methacrylate, triacetyl cellulose, polystyrene A transparent resin substrate mainly composed of an organic resin such as polyvinyl chloride can be suitably used.
Although the thickness of an adhesive sheet can be suitably selected according to the object to adhere | attach, the adhesive strength requested | required, etc., for example, it is 1-1000 micrometers, Preferably it is 10-300 micrometers, More preferably, it is 30-200 micrometers. It is. In addition, when using the said adhesive sheet, it can be used after peeling the said adhesive sheet from a peeling sheet or peeling.

[Laminate]
The laminate of the present invention is a laminate in which a plurality of layers are bonded, wherein at least one layer is composed of a rubber layer, and the rubber layer is adjacent to a layer adjacent via the above-described adhesive or adhesive sheet. It is bonded.
The plurality of layers may all be rubber layers or may include layers other than the rubber layer.
The dimensions and the number of layers of each layer can be appropriately selected according to the purpose.
In the laminate of the present invention, the carbon atoms in the rubber of the rubber layer in contact with the adhesive or the adhesive sheet are thiol groups of the components (A1) and (A2) contained in the adhesive or the adhesive sheet. It is considered that a strong adhesive force is expressed by forming a sulfur atom and a carbon-sulfur bond.
In this carbon-sulfur bond, the other part of the components (A1) and (A2) reacts with the radical generator (C) to generate a thiyl radical, which is a carbon-carbon double bond present in the rubber. The sulfur atom of the thiol group of the components (A1) and (A2) and the carbon-by hydrogen abstraction reaction from the carbon-carbon bond main chain present in the rubber It is thought that it was formed by chemically bonding to a carbon atom of a carbon bond.

<Rubber layer>
The rubber layer may be vulcanized rubber or unvulcanized rubber.
Moreover, it is preferable that the rubber which comprises a rubber layer has a carbon-carbon double bond. In this case, the carbon atom of the carbon-carbon double bond which the rubber layer which contacts the said adhesive agent or the said adhesive sheet has is sulfur of the thiol group of the component (A1) and the component (A2) which the said adhesive agent or said adhesive sheet has. Presumed to form a carbon-sulfur bond with the atom.
However, it is presumed that a laminate can be obtained even if the rubber constituting the rubber layer does not have a carbon-carbon double bond. In this case, the sulfur atom of the thiol group of the component (A1) and the component (A2) and the carbon − by the hydrogen abstraction reaction from the carbon-carbon bond main chain existing in the rubber by the component (A1) and the component (A2). It is assumed that the carbon atom of the carbon bond is chemically bonded. However, from the viewpoint of improving the adhesive strength, it is preferable that the rubber constituting the rubber layer has a carbon-carbon double bond.

  The material of the rubber layer is not particularly limited, and for example, natural rubber (NR); polyisoprene synthetic rubber (IR), polybutadiene rubber (BR), styrene-butadiene copolymer rubber (SBR), acrylonitrile butadiene rubber (NBR). ), Conjugated diene synthetic rubbers such as chloroprene rubber (CR) and 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. In particular, the combined use of natural rubber and conjugated diene synthetic rubber is more preferable, and the combined use of natural rubber and styrene-butadiene copolymer rubber is more preferable.

<Layers other than rubber layers>
Examples of the layer other than the rubber layer include a metal layer and a resin layer. According to the adhesive and adhesive sheet of the present invention, these metal layers and resin layers can also be strongly bonded.

<Method for producing laminate (when using adhesive)>
Next, a method for producing a laminate using an adhesive will be described.
The laminate of the present invention can be suitably obtained by adhering adjacent layers through the adhesive of the present invention.
For example, first, an adhesive is applied to the rubber layer or a layer other than the rubber layer facing the rubber layer. Next, after leaving for a predetermined time as required, another layer, that is, a layer other than the rubber layer facing the rubber layer or the rubber layer is brought into contact with the surface to which the adhesive is applied, and the layers are superimposed. Get the body. At this time, an adhesive may be applied to a layer other than the rubber layer facing the rubber layer or the rubber layer. That is, an adhesive may be applied to one side of the two opposing surfaces, and an adhesive may be applied to both sides. Next, if necessary, the laminated body can be suitably produced by curing the laminated body while applying a press pressure in the thickness direction thereof.

In the case of leaving for a predetermined time after coating, the standing time is preferably 0 to 30 minutes, more preferably 1 to 15 from the viewpoint of retaining the adhesive so that the adhesive does not leak from the laminated body during curing. Minutes.
In the case where a press pressure is applied to the laminated body, the press pressure is preferably 0 to 5 MPa, more preferably 0 to 0 m from the viewpoint of improving the adhesive force and preventing or suppressing the leakage of the adhesive from the laminate. 2.5 MPa, more preferably 0 to 1 MPa. From the same viewpoint, the pressing time is preferably 5 to 120 minutes, more preferably 10 to 60 minutes, and further preferably 15 to 45 minutes.

When the adhesive contains a thermal radical generator as a radical generator, curing is preferably performed by heating. The temperature at which the thermal radical generator efficiently generates radicals can be appropriately selected as the heating temperature, but is preferably about 1 minute half-life temperature of the thermal radical generator ± 30 ° C.
When the adhesive contains a photo radical generator as a radical generator, curing is preferably performed by light irradiation. From the viewpoint of improving adhesive force and reducing costs, the light source is at least one selected from electromagnetic waves such as ultraviolet rays, visible rays, infrared rays, and X-rays, and particle beams such as α rays, γ rays, and electron beams. It can be used suitably, and an ultraviolet lamp can be used more suitably. From the same viewpoint, the light irradiation time is preferably several seconds to several tens of seconds, more preferably 1 second to 40 seconds, and further preferably 3 seconds to 20 seconds.
It should be noted that the fact that a strong adhesive force can be obtained even when cured by heating is advantageous in that a heating method can be employed when it is difficult to sufficiently irradiate the adhesive.

<Method for producing laminate (when using adhesive sheet)>
Next, a method for producing a laminate using an adhesive sheet will be described.
The laminated body of this invention can be suitably obtained by adhere | attaching adjacent layers through the adhesive sheet of this invention.
For example, one or two or more (preferably one) adhesive sheets are interposed between adjacent layers to obtain an overlapped body. Further, for example, an adhesive sheet is interposed between at least one of the rubber layers and a layer (a rubber layer or a layer other than the rubber layer) facing the rubber layer to obtain an overlapped body. Next, if necessary, the laminated body can be suitably produced by curing the laminated body while applying a press pressure in the thickness direction thereof.
When applying a press pressure to the laminated body, from the viewpoint of improving the adhesive force, the press pressure is preferably 0.1 to 5 MPa, more preferably 0.2 to 4 MPa, and still more preferably 0.3 to It is 3 MPa, More preferably, it is 0.4-3 MPa, More preferably, it is 0.5-3 MPa.
The other pressing conditions (pressing time) and curing conditions (heating temperature, heating time, light source, and light irradiation time) are the same as in the case of using the adhesive described above.

[Application example of the adhesive of the present invention]
Although the suitable application example of the composition of this invention, an adhesive agent, an adhesive sheet, and a laminated body is shown below, this invention is not limited to the said application example.
The composition, adhesive, adhesive sheet and laminate of the present invention can be applied to a technique related to printing on tires, and specifically, can be applied to decoration and protective materials on tire surfaces. Thereby, the adhesiveness and adhesiveness of a tire surface, decoration, and a protective material can be improved.
Further, the composition and adhesive of the present invention can be used as an adhesive between a tread and a base tire when performing retreading (regeneration of a tread) of a tire such as an aircraft tire. Thereby, the sulfur transfer from the cushion rubber conventionally used as an adhesive agent to the base tire, and the sulfur transfer from the tread to the base tire can be suppressed.
Furthermore, when producing a retread tire, the composition, adhesive, adhesive sheet and laminate of the present invention can be applied. Thereby, the adhesiveness of a tread and a base tire can be improved.
The composition and adhesive of the present invention can also be applied to a pneumatic tire comprising a plug provided with a pump mechanism on the side surface of the tire.
This plug is mounted in a hole provided on the side surface of the tire. The plug includes a first plug that covers the tire inner opening of the hole, a second plug that covers the tire outer opening of the hole, a cavity formed inside the first and second plugs, A first flow path with a check valve that communicates between the cavity and the space inside the tire, a second flow path with a check valve that communicates between the cavity and the space outside the tire, and elasticity provided in the cavity And having a body. When the pneumatic tire is in a normal traveling state, a compressive force in the tire radial direction acts on the plug, and when the pneumatic tire is in a traveling state in which a high load is applied, a tensile force in the tire radial direction acts on the plug. When the plug receives a compressive force, the elastic body compresses, the air in the cavity is compressed, and the air is supplied into the tire. When the plug receives a tensile force, the elastic body expands and air flows into the cavity from the outside of the tire. For example, the composition of the present invention may be used as a material for the first plug and the second plug. Moreover, you may use the adhesive agent of this invention when adhere | attaching the 1st plug and the 2nd plug in the hole of a tire side surface.
Moreover, the composition and adhesive of the present invention can be used for vulcanization adhesion between an unvulcanized side rubber and a steel cord reinforcement layer when the side rubber reinforcement layer of a tire is adhered. Thereby, reduction of variation in adhesive strength and reduction of material loss can be achieved.
In addition, the composition, adhesive, adhesive sheet and laminate of the present invention can be used for repairing a puncture site of an off-the-road tire (mine vehicle tire or construction vehicle tire). For example, when repairing an off-the-road tire tire with vulcanized rubber, the puncture site and the vulcanized rubber can be bonded and repaired with the composition or adhesive of the present invention.

  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.

[Raw materials]
As raw materials, the following were used.
<Thioglycolic acid ester (A1)>
Trimethylolpropane tristhioglycolate (TMTG)
Pentaerythritol tetrakisthioglycolate (PETG)

<Polythiol compound other than thioglycolic acid ester (A2)>
Trimethylolpropane tris (3-mercaptopropionate) (TMMP): manufactured by SC Organic Chemical Co., Ltd., 3 thiol groups Pentaerythritol tetrakis (3-mercaptopropionate) (PEMP): manufactured by SC Organic Chemical Co., Ltd., thiol 4 groups Dipentaerythritol hexakis (3-mercaptopropionate) (DPMP): SC Organic Chemical Co., Ltd., 6 thiol groups Tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate (TEMPIC) : SC Organic Chemical Co., Ltd., trade name “TEMPIC”, 3 thiol groups

<Isocyanate group-containing compound (B)>
IPDI isocyanurate-modified isocyanate: manufactured by Sumika Bayer Urethane Co., Ltd., trade name “Desmodur Z4470BA”, NCO content 11.9%
HDI isocyanurate-modified isocyanate: manufactured by Nippon Polyurethane Industry Co., Ltd., trade name “Coronate HXLV”, NCO content 23.2%
H ₆ XDI isocyanurate-modified isocyanate: manufactured by Mitsui Chemicals Polyurethanes Co., Ltd., trade name “Takenate D-127N”, NCO content 13.5%
IPDI allophanate-modified isocyanate: manufactured by Sumika Bayer Urethane Co., Ltd., trade name “Desmodur XP2565”, NCO content 12.0%
IPDI adduct-modified isocyanate: manufactured by Mitsui Chemicals Polyurethanes Co., Ltd., trade name “Takenate D-140N”, NCO content 11%
TDI isocyanurate-modified isocyanate: manufactured by Mitsui Chemicals Polyurethanes Co., Ltd., trade name “Takenate D-204”, NCO content 7.5%
IPDI: manufactured by Evonik Degussa Japan Co., Ltd., trade name “VESTANAT IPDI”, functional group equivalent 111, NCO content 37.6%
HDI buret-modified isocyanate: manufactured by Sumitomo Bayer Urethane Co., Ltd., trade name “Desmodur N3200”, NCO content 23.0%

<Radical generator (C)>
t-butyl-2-ethylperoxyhexanoate: Nippon Oil & Fats Co., Ltd., trade name “Perbutyl O”

<Urethane catalyst (D)>
Triethylenediamine (TEDA): Product name “DABCO 33LV catalyst” manufactured by Air Products

<Surface conditioner (E)>
Silicone urethane acrylate: Product name “Miramer SIU2400” manufactured by MIWON

[Measurement of the number of thiol groups]
The total number of moles of thiol groups contained in the component (A1) and the component (A2) to be blended is obtained by dividing the blending amount by the theoretical molecular weight and calculating the number of thiol groups that each molecule of the component (A1) and component (A2) has. Calculated by multiplying each and then adding.

[Measurement of the number of isocyanate groups]
The total number of moles of isocyanate groups contained in the blended isocyanate group-containing compound (B) was measured by JIS K1603-1 B method.

[Manufacture of rubber members]
A rubber member (length 100 mm × width 25 mm × thickness 10 mm) was produced according to the formulation shown in Table 1 below.
Blending was performed as shown in Table 1 below, and the blend was rolled to 150 mm × 270 mm × 3.4 mmt to obtain a sheet. Three sheets were stacked and vulcanized in a 150 mm × 270 mm × 10 mmt mold at 150 ° C. for 45 minutes. The obtained vulcanizate was cut into a length of 100 mm and a width of 25 mm to obtain a test rubber member.

The details of each component in Table 1 are as follows.
・ Natural rubber (NR): RSS # 3
-Styrene-butadiene copolymer rubber (SBR): manufactured by JSR, trade name "JSR 1500"
Carbon black: Asahi Carbon Co., Ltd., trade name “Asahi # 70”
Anti-aging agent: N-phenyl-N ′-(1,3-dimethylbutyl) -p-phenylenediamine, manufactured by Ouchi Shinsei Chemical Co., Ltd., trade name “NOCRACK 6C”
Zinc Hana: No. 3 Zinc Hana, Vulcanization Accelerator 1: 1,3-Diphenylguanidine, manufactured by Ouchi Shinsei Chemical Co., Ltd., trade name “Noxeller D (DP)”
Vulcanization accelerator 2: Di-2-benzothiazolyl disulfide, manufactured by Ouchi Shinsei Chemical Industry Co., Ltd., trade name “Noxeller DM-P (DM)”

[Measurement method of adhesive strength of cured adhesive]
The laminate obtained in each example was pulled at a temperature of 25 ° C., 75 ° C., 100 ° C. or 120 ° C. in a direction of 180 ° at a tensile speed of 50 mm / min, and the peel strength (N / 25 mm) was measured. And used as an index of adhesion.
In the case of measurement at 25 ° C., the value of the adhesive force is preferably 300 N / 25 mm or more, more preferably 400 N / 25 mm or more, and further preferably 500 N / 25 mm or more. In addition, in the case of 500 N / 25 mm or more, destruction of the rubber member was confirmed. Further, it is more preferable that sufficient adhesion is maintained even when exposed to a high temperature environment. From this viewpoint, in the case of measurement at 100 ° C. or higher, it is preferably 200 N / 25 mm or more, and 300 N / More preferably, it is 25 mm or more.
On the other hand, when the force is less than 300 N / 25 mm, the reaction between the base material and the adhesive is not sufficient, and the peeled state at the interface or the cohesive force of the adhesive force is not sufficient, and the adhesive itself is cohesive. In such a state, it cannot be said that the adhesive strength is sufficient.

<Examples 1-9 and Comparative Examples 1-4>
As shown in Table 2 below (the numerical value of each component indicates the non-volatile content (part by mass)), the composition containing each component and, if necessary, the solvent (solvent) is added to the release sheet. The adhesive sheet having a thickness of 30 μm was obtained. In addition, as a solvent (solvent), methyl ethyl ketone (MEK) was used in order to maintain compatibility and solubility.
A laminated body is produced by sandwiching the obtained adhesive sheet between two test rubber members, and the laminated body is held for 30 minutes at a temperature of 120 ° C. while applying a pressing pressure of 0.6 MPa. A laminate was produced. It was 30 micrometers when the thickness of the contact bonding layer in the obtained laminated body was measured with the micrometer.
Using the laminate, the adhesive strength of the adhesive sheet was measured as described above. The results are shown in Table 2.

[Evaluation]
As shown in Table 2, in Examples 1 to 9, the adhesive strength at room temperature was extremely high. Furthermore, in Examples 1-2 and 4-9, the adhesive force was high not only at normal temperature but also at high temperature (100 ° C. or higher).
On the other hand, in Comparative Examples 1 to 4, the adhesive force was low in both cases of normal temperature and high temperature.

  The composition, adhesive and adhesive sheet of the present invention can be used for adhesion of rubber, particularly vulcanized rubber.

Claims (10)

Compounding thioglycolic acid ester (A1), polythiol compound (A2) other than thioglycolic acid ester, isocyanate group-containing compound (B), and radical generator (C),
Composition whose blending ratio [(A1) / (A2)] of polythiol compound (A2) other than thioglycolic acid ester (A1) and thioglycolic acid ester is 10/90 to 65/35 in mass ratio object.   The composition according to claim 1, wherein the blending ratio [(A1) / (A2)] is 30/70 to 65/35 by mass ratio.   The composition according to claim 1 or 2, wherein the polythiol compound (A2) other than the thioglycolic acid ester is a mercapto fatty acid ester.   The thioglycolic acid ester product (A1) is obtained by an esterification reaction between a polyhydric alcohol having 2 to 6 hydroxyl groups in the molecule and thioglycolic acid, and the polyhydric alcohol has 2 carbon atoms. The composition according to any one of claims 1 to 3, which is -20 alkanediol, poly (oxyalkylene) glycol, glycerol, diglycerol, trimethylolpropane, ditrimethylolpropane, pentaerythritol or dipentaerythritol. .   The composition according to claim 4, wherein the polyhydric alcohol is pentaerythritol.   The ratio (isocyanate group / thiol group) of the total moles of isocyanate groups contained in component (B) to the total moles of thiol groups contained in component (A1) and component (A2) to be blended is 0. The composition according to any one of claims 1 to 5, which is 2 or more and 0.78 or less.   The composition of any one of Claims 1-6 formed by mix | blending a urethanization catalyst (D).   The adhesive agent containing the composition of any one of Claims 1-7.   The adhesive sheet which uses the composition of any one of Claims 1-7. A laminate in which at least two layers are bonded,
At least one layer comprises a rubber layer,
A laminated body in which at least one of the rubber layers is bonded to an adjacent layer via the adhesive according to claim 8 or the adhesive sheet according to claim 9.