JP2014227499A - Composition, adhesive, adhesive sheet and laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: an adhesive capable of strongly adhering a rubber member, in particular, a vulcanized rubber member; an adhesive sheet; and a laminate in which a rubber layer is adhered using at least one of the adhesive composition and the adhesive sheet.SOLUTION: A composition comprises a polythiol compound (A), an isocyanate-group-containing compound (B) and a radical generator (C).

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. The present invention relates to a laminate formed by bonding 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.

  The present inventors have found that the problem of the present invention can be solved by blending only the polythiol compound (A), the isocyanate group-containing compound (B), and the radical generator (C). It came to complete.

That is, the present invention relates to the following [1] to [7].
[1] A composition comprising only the polythiol compound (A), the isocyanate group-containing compound (B), and the radical generator (C).
[2] 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 polythiol compound (A) (isocyanate group / thiol group) The composition according to [1], wherein is 0.2 or more and 0.78 or less.
[3] The composition according to [1] or [2], wherein the radical generator (C) is a thermal radical generator composed of a peroxide.
[4] The ratio of the total number of moles of the radical generator (C) to be blended to the total number of moles of thiol groups contained in the blended polythiol compound (A) (radical generator (C) / thiol group) is 0. The composition according to any one of [1] to [3], which is 0.025 or more.
[5] An adhesive comprising the composition according to any one of [1] to [4].
[6] An adhesive sheet comprising the composition according to any one of [1] to [4].
[7] A laminate in which at least two layers are bonded, wherein at least one layer is a rubber layer, and at least one of the rubber layers is the adhesive according to [5] or [6] A laminate formed by adhering to an adjacent layer through the adhesive sheet described in 1.

  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.

[Composition]
The composition of this invention is a composition (henceforth a composition) which mix | blends only a polythiol compound (A), an isocyanate group containing compound (B), and a radical generator (C). .

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 strongly cured by causing a urethanization reaction between a part of the polythiol compound (A) and the isocyanate group-containing 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 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, it is 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 existing in the rubber. Therefore, the carbon-carbon double bond does not necessarily exist in the rubber.
In addition, in this specification, a polythiol compound (A), an isocyanate group containing compound (B), and a radical generator (C) may be called a component (A), a component (B), and a component (C), respectively.

  In the composition of the present invention, the reason why only the component (A), the component (B), and the component (C) are blended and the other components are not blended is the reason described below.

For example, when a compound other than the component (B) that reacts with the polythiol compound (A), such as a compound having a carbon-carbon double bond such as various rubber components, is contained, the polythiol compound (A) and the compound [component ( As a result, the thiol group of the polythiol compound (A) may decrease or disappear. In such a state, when used as an adhesive such as rubber, the thiol-ene reaction between the polythiol compound (A) and the carbon-carbon double bond in the rubber becomes difficult to occur, and the composition adheres to the rubber. The power may be reduced. Alternatively, it is a competitive reaction between the reaction between the thiol group of component (A) and the isocyanate group of component (B) and the reaction of the thiol group of component (A) and the compound [compound other than component (B)] Since it is a two-step reaction, it is difficult to form a film as a uniform adhesive layer, and there is a risk of adverse effects such as inferior film properties of the adhesive layer.
Further, the hydrogen abstraction reaction from the carbon-carbon bond main chain of the rubber makes it difficult for 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, and the rubber There exists a possibility that the adhesive force of the composition with respect to may fall.
Moreover, when the concentration of the thiol group in the composition is lowered, the adhesion reaction between the component (A) and the vulcanized rubber is difficult to occur, and the adhesive force may be reduced.

In addition, when a compound that does not react with component (A) [compound other than component (C)] is contained, formation of an adhesive layer due to the reaction between the thiol group and the isocyanate group is inhibited, or the compound itself that does not react with component (A) is plasticized. There is concern that the film physical properties of the adhesive layer itself are inferior (softened).
Furthermore, the reaction between the component (A) and the component (B) is less likely to occur due to the decrease in the concentration of thiol groups and isocyanate groups in the composition, and there is a possibility that it takes time to form a sheet (curing of the adhesive layer), Even when sheeting (curing of the adhesive layer) is performed, the film strength may decrease.

<Polythiol compound (A)>
In the present invention, the polythiol compound (A) refers to a compound having two or more thiol groups in one molecule.
Although there is no restriction | limiting in particular in a polythiol compound (A), From a viewpoint of improving adhesiveness, what has 2-6 thiol groups in 1 molecule is preferable.
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.
The polyhydric alcohols having 2 to 6 hydroxyl groups in the molecule include alkanediol having 2 to 20 carbon atoms, poly (oxyalkylene) glycol, glycerol, diglycerol, trimethylolpropane, ditrimethylolpropane, Examples include pentaerythritol 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. 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), pentaerythritol tetrakis (3-mercaptopropionate) (PEMP), and dipentaerythritol hexakis (3-mercaptopropionate) (DPMP). 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 (mercaptoe) L) benzene, 1,3,5-tris (mercaptoethyl) benzene, 2,5-toluenedithiol, 3,4-toluenedithiol, 1,3-di (p-methoxyphenyl) propane-2,2-dithiol, Examples include 1,3-diphenylpropane-2,2-dithiol, phenylmethane-1,1-dithiol, 2,4-di (p-mercaptophenyl) pentane.

<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 (A) is a mercapto fatty acid ester and a thiol isocyanurate compound, the blended isocyanate group-containing compound (B) is hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), tri One or more of 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.

  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 (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 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-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.

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.

<Amount of each component>
[About the compounding quantity of the component (A) and the component (B) of a composition]
The 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 polythiol compound (A) (isocyanate group / thiol group) is Although not limited, it is preferably 0.20 or more and 0.78 or less. When the ratio (isocyanate group / thiol group) is 0.20 or more, the composition is sufficiently firmly cured and the adhesive strength is increased. In addition, when the ratio (isocyanate group / thiol group) is 0.78 or less, the thiol-ene reaction is sufficiently performed between the thiol group and the carbon-carbon double bond of the rubber member because there are many thiol groups. The composition can be firmly adhered to the rubber member, and the adhesive strength is increased. The ratio (isocyanate group / thiol group) is more preferably 0.3 or more, more preferably 0.7 or less, and still more preferably 0.4 to 0.7.
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 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 polythiol compound 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 (A).

[About the compounding quantity of the component (A) and the component (C) of a composition]
The ratio of the total number of moles of the radical generator (C) to be blended to the total number of moles of thiol groups contained in the blended polythiol compound (A) (radical generator (C) / thiol group) is 0.025. The above 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 described above, the composition according to the present invention provides a composition comprising only component (A), component (B) and component (C). However, in the composition of the present invention, in addition to the component (A), the component (B) and the component (C), the urethanization catalyst (D) and / or the surface conditioner (E) is included exceptionally. Also good. For this reason, this urethanization catalyst is basically for accelerating the reaction between the polythiol compound (A) and the isocyanate group-containing compound (B), and the urethanization catalyst remaining after the urethanization reaction is: This is because it is not intended to be directly related to the properties of the composition. Further, the surface conditioner (E) is also used for the purpose of appropriately maintaining the compatibility and surface tension in the composition, and is not for directly participating in the properties of the composition.

  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 lead 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 Beam, 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, the above amines are preferable, and triethylenediamine (TEDA) is more preferable. These catalysts may be used alone or in combination of two or more. In addition, when using a urethanization catalyst (D), it mix | blends in the range of about 0.0001-0.02 mass% normally with respect to the total amount of a polythiol compound (A) and an isocyanate group containing compound (B). can do.

  As the surface conditioner (E), any surface conditioner can be used. 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. It is preferable to mix | blend a surface adjuster (E) so that it may become 0.05-5 mass% in a composition. By mix | blending within this range, compatibility with each component can be improved and a uniform composition can be obtained.

  Moreover, the said each component (A), component (B), component (C), component (D), and component (E) may contain the solvent used as needed. As the solvent used for each component, various organic solvents, water, and the like are used. However, when the composition of the present invention is used as an adhesive or an adhesive sheet, the solvent is hardly lost due to volatilization or the like, and the adhesiveness is increased. This is because it has almost no effect.

[adhesive]
The adhesive of the present invention contains the above composition. The thickness of the adhesive can be appropriately selected according to the object to be bonded, the required adhesive strength, and the like, and is, for example, 1 to 1000 μm, preferably 10 to 300 μm, more preferably 30 to 200 μm. It is.

[Adhesive sheet]
The adhesive sheet of the present invention is formed using the above 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 holding time can be adjusted by the amount of the urethanization 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, the standing temperature or heating temperature after coating is preferably −30 to 60 ° C., more preferably −20 to 40 ° C., and further preferably 0 to 40 ° C.
The holding time can be adjusted by the amount of the urethanization 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 30 minutes or longer, more preferably 60 minutes or longer.

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 20-300 micrometers, More preferably, it is 30-200 micrometers. It is.

[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.

<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 that the rubber layer in contact with the adhesive or the adhesive sheet has is the carbon atom of the sulfur atom of the thiol group of the polythiol compound (A) that the adhesive or the adhesive sheet has. Presumed to form sulfur bonds.
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 polythiol compound (A) and the carbon atom of the carbon-carbon bond are chemically generated by a hydrogen abstraction reaction from the carbon-carbon bond main chain present in the rubber by the polythiol compound (A). It is speculated that it will be combined. 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.

  Also, the material of the rubber layer is not particularly limited. For example, natural rubber; polyisoprene synthetic rubber (IR), polybutadiene rubber (BR), styrene-butadiene copolymer rubber (SBR), acrylonitrile butadiene rubber (NBR), chloroprene. Conjugated diene-based synthetic rubbers such as 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.

<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 the adhesive sheet of the present invention, these metal layers and resin layers can be strongly bonded. It is presumed that the thiol group acts as a base and easily forms a strong bond with the metal compound, and is also assumed to form a bond with the resin compound by a hydrogen abstraction reaction.

<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 being allowed to stand for a predetermined time as required, another layer is brought into contact with the surface to which the adhesive is applied to obtain an overlapped body. At this time, an adhesive may be applied to one surface of the two opposing surfaces, or an adhesive may be applied to both surfaces. 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 ± 30 ° C. of the thermal radical generator.
When the adhesive contains a photo radical generator as a radical generator, curing is preferably performed by light irradiation. As the light, 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 can be preferably used. Among these, ultraviolet rays are preferable as light. From the viewpoint of improving the adhesive force and reducing the cost, an ultraviolet lamp can be suitably used as the light source. From the same viewpoint, the light irradiation time is preferably several seconds to several tens of seconds, more preferably 1 to 40 seconds, and further preferably 3 to 20 seconds.
In any operation of heating and light irradiation, as long as heat energy or light energy is transmitted to the adhesive, there is no particular limitation on the part to be heated or the part to be irradiated with light. Also good. That is, the adhesive may be directly heated or irradiated with light, or the adhesive may be heated or irradiated with light through a rubber and / or an adherend.
The fact that a strong adhesive force can be obtained even when cured by heating is beneficial in that a heating method can be employed when it is difficult to sufficiently irradiate the adhesive with light, and the laminated body. It is preferable because it can be easily operated even if it is heated and / or irradiated with light to any part of the throat.

<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. The laminate may be obtained via one adhesive sheet or may be obtained via two or more adhesive sheets.
For example, first, one or two or more adhesive sheets are interposed between adjacent layers 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 5.0 MPa, more preferably 0.2 to 4.0 MPa, still more preferably. 0.3 to 3.0 MPa, particularly preferably 0.4 to 3.0 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.
In any operation of heating and light irradiation, if heat energy or light energy is transmitted to the adhesive sheet, there is no particular limitation on the part to be heated or the part to be irradiated with light. Also good. That is, the adhesive sheet may be directly heated or irradiated with light, or the adhesive sheet may be heated or irradiated with light through a rubber and / or an adherend.
In addition, as described above, the fact that a strong adhesive force can be obtained even when cured by heating is beneficial in that a heating method can be employed when it is difficult to sufficiently irradiate the adhesive with light, and It is preferable because it is easy to operate because it can be strongly bonded to any part of the superposed body by heating and / or light irradiation.

  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.
<Polythiol Compound (A) (Component (A))>
Pentaerythritol tetrakis (3-mercaptopropionate) (PEMP): manufactured by SC Organic Chemical Co., Ltd., four thiol groups Dipentaerythritol hexakis (3-mercaptopropionate) (DPMP): manufactured by SC Organic Chemical Co., Ltd. 6 thiol groups Tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate (TEMPIC): manufactured by SC Organic Chemical Co., Ltd., trade name “TEMPIC”, 3 thiol groups

<Isocyanate group-containing compound (B) (component (B))>
HDI burette-modified isocyanate: manufactured by Sumitomo Bayer Urethane Co., Ltd., trade name “Desmodur N3200”, NCO content: 23.0% by mass
HDI isocyanurate-modified isocyanate: manufactured by Nippon Polyurethane Industry Co., Ltd., trade name “Coronate HXLV”, NCO content: 23.2% by mass
IPDI isocyanurate-modified isocyanate: manufactured by Sumika Bayer Urethane Co., Ltd., trade name “Desmodur Z4470BA”, NCO content: 11.9% by mass
IPDI allophanate-modified isocyanate: manufactured by Sumika Bayer Urethane Co., Ltd., trade name “Desmodur XP2565”, NCO content: 12.0% by mass
TDI TMP adduct-modified isocyanate: manufactured by Sumika Bayer Urethane Co., Ltd., trade name “Desmodur L75 (C)”, NCO content: 13.3% by mass
TDI isocyanurate-modified isocyanate: manufactured by Mitsui Chemicals Polyurethanes Co., Ltd., trade name “D-204”, NCO content: 7.5% by mass
XDI TMP adduct-modified isocyanate: manufactured by Mitsui Chemicals Polyurethanes Co., Ltd., trade name “D-110N”, NCO content: 11.5% by mass
H ₆ XDI TMP adduct-modified isocyanate: manufactured by Mitsui Chemicals Polyurethanes Co., Ltd., trade name “D-120N”, NCO content: 11.0% by mass
H ₆ XDI isocyanurate-modified isocyanate: manufactured by Mitsui Chemicals Polyurethanes Co., Ltd., trade name “D-127N”, NCO content: 13.5% by mass
IPDI: Evonik Degussa Japan Co., Ltd., trade name “VESTANAT IPDI”, NCO content: 37.6% by mass

<Radical generator (C) (component (C))>
t-butyl-2-ethylperoxyhexanoate: Nippon Oil & Fats Co., Ltd., trade name “Perbutyl O”
Dilauroyl peroxide: manufactured by Nippon Oil & Fats Co., Ltd., trade name “PAROIL L”
1,1,3,3-Tetramethylbutylperoxy-2-ethylhexanoate: Nippon Oil & Fats Co., Ltd., trade name “Perocta O”
1,1-di (t-hexylperoxy) cyclohexanone: manufactured by NOF Corporation, trade name “Perhexa HC”
Di-t-butyl peroxide: manufactured by Nippon Oil & Fats Co., Ltd., trade name “Perbutyl D”
t-Butyl cumyl peroxide: manufactured by Nippon Oil & Fats Co., Ltd., trade name “Perbutyl C”

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

<Surface Conditioner (E) (Component (E))>
Mixture of polyether-modified polydimethylsiloxane and polyether: manufactured by Big Chemie Japan, trade name “BYK-307”, content: 100%

[Measurement of the number of thiol groups]
The total number of moles of thiol groups contained in the blended polythiol compound (A) was calculated by dividing the blended amount by the theoretical molecular weight and multiplying by the number of thiol groups possessed by one molecule of the polythiol compound (A). .

[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 sheet rolled to 150 mm × 270 mm × thickness 3.4 mm is manufactured in accordance with the composition shown in Table 1 below. Three sheets of this sheet are stacked and added in a 150 mm × 270 mm × 10 mm mold at 150 ° C. for 45 minutes. Sulfur was performed. Next, the vulcanized sheet taken out from the mold was cut into a length of 100 mm and a width of 25 mm to produce a rubber member (length 100 mm × width 25 mm × thickness 10 mm) as a sample for a tensile test.

The details of each component in Table 1 are as follows.
Natural rubber (NR): RSS # 3
Polybutadiene rubber (BR): Product name “JSR BRO1” manufactured by JSR Corporation
Styrene-butadiene copolymer rubber (SBR): Product name “JSR 1500” manufactured by JSR Corporation
Polyisoprene synthetic rubber (IR): manufactured by JSR, trade name “JSR IR2200”
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”
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)”

(steel sheet)
As the steel plate, SPCC-SD manufactured by Test Piece Co., Ltd. was used.

[Measurement method of adhesive strength of cured adhesive]
The adhesive was applied to two rubber members so as to have a thickness of 30 μm, and the coated surfaces were bonded and cured. 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.
[Measurement method of adhesive strength of cured adhesive sheet]
An adhesive sheet having a thickness of 30 μm was sandwiched between rubber members and cured. Curing was performed by holding at a temperature of 150 ° C. for 30 minutes while applying a press pressure of 2.5 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.
As the value of the adhesive strength, if the force is 100 N / 25 mm or more, the adhesive strength is sufficient to destroy the rubber substrate. Preferably it is 300 N / 25 mm or more. Moreover, even when it is 50 N / 25 mm or more and less than 100 N / 25 mm, it has a level of adhesive strength at which rubber breakage is partially observed, and can be used sufficiently depending on the application. On the other hand, when the force is less than 50 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 1-7 and Comparative Examples 1-2 and Examples 8-14 and Comparative Examples 3-4]
In Examples 1 to 7 and Comparative Examples 1 to 2 (adhesives), the isocyanate contained in the blended isocyanate group-containing compound (B) with respect to the total number of moles of thiol groups contained in the blended polythiol compound (A) By changing the ratio of the total number of moles of groups (isocyanate group / thiol group), the relationship between the ratio (isocyanate group / thiol group) and adhesive force was examined.
In Examples 8 to 14 and Comparative Examples 3 to 4 (adhesive sheets), the adhesives of Examples 1 to 7 and Comparative Examples 1 to 2 (adhesives) were changed to adhesive sheets in the same manner. The relationship between the ratio (isocyanate group / thiol group) and adhesive force was examined.
Next, these examples and comparative examples will be specifically described.

<Examples 1-7, Comparative Examples 1-2 (adhesive composition)>
As shown in the following Table 2 (the numerical value of each component indicates part by mass), each component was blended to obtain a composition, and the composition was used as an adhesive.
The obtained adhesive was cured as described above, and the adhesive strength of the cured adhesive was measured as described above. NR / BR was used as the rubber member. The results are shown in Table 3.
In Table 2, and Table 4, Table 6, Table 8, Table 10, and Table 12, which will be described later, the thiol functional group concentration is the concentration of thiol groups relative to the total amount of each component of the adhesive or adhesive sheet (mmol / g). Further, the NCO functional group concentration means the concentration (mmol / g) of an isocyanate group with respect to the total amount of each component of the adhesive or the adhesive sheet. Furthermore, the generator concentration refers to the concentration (mmol / g) of the radical generator with respect to the total amount of each component of the adhesive or adhesive sheet. However, since each component may react with each other or decompose, each value is a value calculated before each component reacts or decomposes, in other words, each component immediately before mixing. A theoretical value calculated from the amount of the component was used.

<Examples 8 to 14 and Comparative Examples 3 to 4 (adhesive sheets)>
As shown in Table 2, in Examples 8-14 and Comparative Examples 3-4, the same adhesives as Examples 1-7 and Comparative Examples 1-2 were prepared, respectively.
The adhesive was applied onto a PET release sheet and held at room temperature for 30 minutes to obtain an adhesive sheet having a length of 100 mm, a width of 25 mm, and a thickness of 30 μm.
The obtained adhesive sheet was cured as described above, and the adhesive strength of the cured adhesive sheet was measured as described above. As the rubber member, NR / BR was used as in Example 1. The results are shown in Table 3.

[Examples 15 to 20 and Comparative Example 5 and Examples 21 to 26 and Comparative Example 6]
In Examples 15 to 20 and Comparative Example 5 (adhesive), 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 polythiol compound (A) to be blended mainly. By changing the ratio (radical generator (C) / thiol group), the relationship between the ratio (radical generator (C) / thiol group) and adhesive force was examined.
Further, in Examples 21 to 26 and Comparative Example 6 (adhesive sheet), the ratio (radical) was changed in the same manner except that the adhesives of Examples 15 to 20 and Comparative Example 5 (adhesive) were changed to adhesive sheets. The relationship between the generator (C) / thiol group) and the adhesive force was examined.
Next, these examples and comparative examples will be specifically described.

<Examples 15 to 20 and Comparative Example 5>
The same operation as in Example 1 was performed except that the formulation shown in Table 4 was used. The results are shown in Table 5.

<Examples 21 to 26 and Comparative Example 6>
The same operation as in Example 8 was performed except that the formulation shown in Table 4 was used. The results are shown in Table 5.

[Examples 27 to 32 and Examples 33 to 38]
In Examples 27 to 32 (adhesives), the relationship between the type of rubber that is the object to be bonded and the adhesive force was examined by changing the type of rubber that was the object to be bonded.
Moreover, in Examples 33-38 (adhesive sheet), except that the adhesives of Examples 27-32 (adhesive) were changed to adhesive sheets, the type of rubber that is the object to be bonded and the adhesive strength The relationship was examined.
Next, these examples will be described in detail.

<Examples 27 to 32>
The same operation as in Example 1 was carried out except that the composition shown in Table 6 was used and the rubber member shown in Table 7 was used. The results are shown in Table 7.

<Examples 33 to 38>
The same operation as in Example 8 was carried out except that the composition shown in Table 6 was used and the rubber member shown in Table 7 was used. The results are shown in Table 7.

[Examples 39 to 40 and Examples 41 to 42]
In Examples 39 to 40 (adhesives), the relationship between the polythiol compound (A) and the adhesive force was examined by changing the type of the polythiol compound (A) to be blended.
Moreover, in Examples 41-42 (adhesive sheet), except having used the adhesive agent of the said Examples 39-40 (adhesive) as the adhesive sheet, it is the same and it is the kind of polythiol compound (A), and adhesive force. The relationship was examined.
Next, these examples will be described in detail.

<Examples 39 to 40 (adhesive)>
The same operations as in Example 1 were performed except that the formulation shown in Table 8 was used and the polythiol compound (A) shown in Table 9 was used. The results are shown in Table 9.

<Examples 41 to 42 (adhesive sheet)>
The same operations as in Example 8 were performed except that the formulation shown in Table 8 was used and the polythiol compound (A) shown in Table 9 was used. The results are shown in Table 9.

[Examples 43 to 51 and Examples 52 to 60]
In Examples 43 to 51 (adhesive), the relationship between the type of the isocyanate group-containing compound (B) and the adhesive force was examined by changing the type of the isocyanate group-containing compound (B) to be blended.
In Examples 52 to 60 (adhesive sheets), the relationship with the isocyanate group-containing compound (B) was examined in the same manner except that the adhesives of Examples 43 to 51 (adhesives) were changed to adhesive sheets. did.
Next, these examples will be described in detail.

<Examples 43 to 51 (adhesive)>
The same operations as in Example 1 were carried out except that the composition shown in Table 10 was used and the isocyanate group-containing compound (B) shown in Table 11 was used. The results are shown in Table 11.

<Examples 52 to 60 (adhesive sheet)>
The same operation as in Example 8 was carried out except that the composition shown in Table 10 was used and the isocyanate group-containing compound (B) shown in Table 11 was used. The results are shown in Table 11.

[Examples 61 to 65 and Examples 66 to 70]
In Examples 61 to 65 (adhesive), the relationship between the type of radical generator (C) and the adhesive force was examined by changing the type of radical generator (C) to be blended.
Moreover, in Examples 66-70 (adhesive sheet), except having changed the adhesive of the said Examples 61-65 (adhesive composition) into the adhesive sheet similarly, the kind and adhesion | attachment of the rubber | gum which are objects to be bonded The relationship with force was examined.
Next, these examples will be described in detail.

<Examples 61 to 65 (adhesive)>
The same operation as in Example 1 was carried out except that the composition shown in Table 12 was used and the radical generator (C) shown in Table 13 was used. The results are shown in Table 13.

<Examples 66 to 70 (adhesive sheet)>
The same operations as in Example 8 were performed except that the composition shown in Table 12 was used and the radical generator (C) shown in Table 13 was used. The results are shown in Table 13.

<Examples 71-80 and Comparative Examples 7-12 (adhesive composition)>
As shown in the following Table 14 (the numerical value of each component indicates mass%), each component was blended to obtain a composition, and the composition was used as an adhesive.

<Examples 81 to 90, Comparative Examples 13 to 18 (adhesive sheets)>
As shown in Table 14, in Examples 81-90 and Comparative Examples 13-18, the same adhesives as Examples 71-80 and Comparative Examples 7-12 were prepared.
The adhesive was applied onto a PET release sheet and held at room temperature for 30 minutes to obtain an adhesive sheet having a length of 100 mm, a width of 25 mm, and a thickness of 30 μm.
The obtained adhesive sheet was cured as described above, and the adhesive strength of the cured adhesive sheet was measured as described above. As the rubber member, NR / BR was used as in Example 1. The results are shown in Table 15.

The curing times in Table 15 are as follows.
○: Cured in less than 2 hours.
Δ: Cured in 2 to 5 hours.
X: It does not harden even if it exceeds 5 hours.
The details of the other components in Table 15 are as follows.
GP3000: Polyether polyol manufactured by Sanyo Chemical Co., Ltd. Poly bd: Hydroxyl-terminated liquid polybutadiene manufactured by Idemitsu Kosan Co., Ltd. TAIC: Triallyl isocyanurate manufactured by Nippon Kasei Co., Ltd.

[Evaluation]
As shown in Tables 2 to 15, Examples 1 to 90 include components (A), (B) and (C),
Since the compound (other components) containing a carbon-carbon double bond (a compound other than the component (B) that reacts with the component (A)) was not included, the adhesive strength was high. On the other hand, Comparative Examples 1 and 3 do not contain the component (B), Comparative Examples 2 and 4 do not contain the component (A), and Comparative Example 5 does not contain the component (C). It was low.
On the other hand, since the composition of Comparative Examples 7-9 does not contain any of the components (A), (B), and (C), as shown in Comparative Examples 13-15, When it was done, it did not harden and the adhesive strength could not be measured.
Furthermore, since the composition of Comparative Examples 10-12 contains components (other components) other than components (A), (B), and (C), as shown in Comparative Examples 16-18, adhesion When used as a sheet, the adhesive strength was low.

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

Claims (7)

  A composition comprising only the polythiol compound (A), the isocyanate group-containing compound (B), and the radical generator (C).   The ratio (isocyanate group / thiol group) of the total number 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 polythiol compound (A) is 0.00. The composition of Claim 1 which is 2 or more and 0.78 or less.   The composition according to claim 1 or 2, wherein the radical generator (C) is a thermal radical generator comprising a peroxide.   The ratio 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 polythiol compound (A) (radical generator (C) / thiol group) is 0.025 or more. The composition according to any one of claims 1 to 3, wherein   The adhesive agent containing the composition in any one of Claims 1-4.   The adhesive sheet which uses the composition in any one of Claims 1-4. 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 claim 5 or the adhesive sheet according to claim 6.