JP2014148665A - Composition, adhesive, adhesive sheet, and laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive and an adhesive sheet capable of strongly bonding a rubber member, particularly a vulcanized rubber member, and to provide a laminate formed by bonding a rubber layer using at least one of the adhesive and the adhesive sheet.SOLUTION: A composition is obtained by blending a polythiol compound (A), an isocyanate group-containing compound (B), and a radical generator (C). The ratio (isocyanate groups/thiol groups) of the total number of moles of isocyanate groups contained in the isocyanate group-containing compound (B) to the total number of moles of thiol groups contained in the polythiol compound (A) is 0.2 to 0.78 (inclusive).

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.

  The present inventors have found that the problem of the present invention can be solved by blending the polythiol compound (A), the isocyanate group-containing compound (B), and the radical generator (C) at a specific ratio, The present invention has been completed.

That is, the present invention relates to the following [1] to [7].
[1] Blending of polythiol compound (A), isocyanate group-containing compound (B), and radical generator (C), blending with respect to the total number of moles of thiol groups contained in blended polythiol compound (A) The composition whose ratio (isocyanate group / thiol group) of the total number of isocyanate groups contained in the isocyanate group-containing compound (B) is 0.2 or more and 0.78 or less.
[2] The composition according to [1], wherein the radical generator (C) is a thermal radical generator composed of a peroxide.
[3] 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) is 0 (radical generator (C) / thiol group). The composition according to [1] or [2], which is 0.025 or more.
[4] The composition according to any one of [1] to [3], wherein the composition comprises a urethanization catalyst (D).
[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 the present invention comprises a polythiol compound (A), an isocyanate group-containing compound (B), and a radical generator (C). The total mole of thiol groups contained in the blended polythiol compound (A). It is a composition whose ratio (isocyanate group / thiol group) of the total mole number of isocyanate groups contained in the isocyanate group-containing compound (B) to be blended is 0.2 or more and 0.78 or less.

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 the present specification, the polythiol compound (A), the isocyanate group-containing compound (B), the radical generator (C), the urethanization catalyst (D) and the surface conditioner (E) are respectively added to the component (A), It may be called a component (B), a component (C), a component (D), and a component (E).

<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.

<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 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 Aluminum alcoholates, 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>
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 0. 20 or more and 0.78 or less. When the ratio (isocyanate group / thiol group) is less than 0.20, the composition is not sufficiently hardened and the adhesive strength is reduced. Further, when the ratio (isocyanate group / thiol group) is larger than 0.78, the thiol-ene reaction is sufficiently performed between the thiol group and the carbon-carbon double bond of the rubber member because there are few thiol groups. Otherwise, the composition cannot be firmly bonded to the rubber member, and the adhesive strength is reduced. Therefore, the ratio (isocyanate group / thiol group) is preferably 0.3 or more, preferably 0.7 or less, and 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).

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

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

[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 does not cleave. 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 atom in the rubber of the rubber layer in contact with the adhesive or the adhesive sheet is the sulfur atom of the thiol group of the polythiol compound (A) contained in the adhesive or the adhesive sheet. By forming a carbon-sulfur bond, it is considered that a strong adhesive force is expressed.
In this carbon-sulfur bond, another part of the polythiol compound (A) reacts with the radical generator (C) to generate a thiyl radical, which reacts with a carbon-carbon double bond present in the rubber. Or the sulfur atom of the thiol group of the polythiol compound (A) and the carbon atom of the carbon-carbon bond by a hydrogen abstraction reaction from the carbon-carbon bond main chain present in the rubber. Is considered to be formed by chemically bonding.

<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.

<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 ± 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. 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, first, one or two or more adhesive sheets are interposed between adjacent layers to obtain an overlapped body. For example, an adhesive sheet is interposed between at least one of the rubber layers and a layer facing the rubber layer (a rubber layer or a layer other than 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 5.0 MPa, more preferably 0.2 to 4.0 MPa, still more preferably. It is 0.3-3.0 MPa, More preferably, it is 0.4-3.0 MPa, More preferably, it is 0.5-3.0 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.

[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.
<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 buret-modified isocyanate: manufactured by Sumitomo Bayer Urethane Co., Ltd., trade name “Desmodur N3200”, NCO content 23.0%
HDI isocyanurate-modified isocyanate: manufactured by Nippon Polyurethane Industry Co., Ltd., trade name “Coronate HXLV”, NCO content 23.2%
IPDI isocyanurate-modified isocyanate: manufactured by Sumika Bayer Urethane Co., Ltd., trade name “Desmodur Z4470BA”, NCO content 11.9%
IPDI allophanate-modified isocyanate: manufactured by Sumika Bayer Urethane Co., Ltd., trade name “Desmodur XP2565”, NCO content 12.0%
TDI TMP adduct-modified isocyanate: manufactured by Sumika Bayer Urethane Co., Ltd., trade name “Desmodur L75 (C)”, NCO content: 13.3%
TDI isocyanurate-modified isocyanate: manufactured by Mitsui Chemicals Polyurethanes Co., Ltd., trade name “D-204”, NCO content 7.5%
XDI TMP adduct-modified isocyanate: manufactured by Mitsui Chemicals Polyurethanes Co., Ltd., trade name “D-110N”, NCO content 11.5%
H ₆ XDI TMP adduct-modified isocyanate: manufactured by Mitsui Chemicals Polyurethanes Co., Ltd., trade name “D-120N”, NCO content 11.0%
H ₆ XDI isocyanurate-modified isocyanate: manufactured by Mitsui Chemicals Polyurethanes Co., Ltd., trade name “D-127N”, NCO content 13.5%
IPDI: manufactured by Evonik Degussa Japan Co., Ltd., trade name “VESTANAT IPDI”, functional group equivalent 111, NCO content 37.6%

<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 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 vulcanized product was cut into a length of 100 mm and a width of 25 mm to obtain 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. On the other hand, when the force is less than 100 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 cohesively breaks. In such a state, it cannot be said that the adhesive strength is sufficient.

[Examples 1-7 and Comparative Examples 1-7 and Examples 8-14 and Comparative Examples 8-14]
In Examples 1 to 7 and Comparative Examples 1 to 7 (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.
Moreover, in Examples 8-14 and Comparative Examples 8-14 (adhesive sheets), except that the adhesives of Examples 1-7 and Comparative Examples 1-7 (adhesives) were used as adhesive sheets, 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 1-7 (adhesive)>
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. The values of the thiol functional group concentration, the NCO functional group concentration, and the generator concentration are theoretical values when it is assumed that each functional group of each component of the adhesive or the adhesive sheet does not react.

<Examples 8-14, Comparative Examples 8-14 (Adhesive Sheet)>
As shown in Table 2, in Examples 8 to 14 and Comparative Examples 8 to 14, the same adhesives as Examples 1 to 7 and Comparative Examples 1 to 7 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 15 and Examples 21 to 26 and Comparative Example 16]
In Examples 15 to 20 and Comparative Example 15 (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 16 (adhesive sheet), the ratio (radical) was similarly changed except that the adhesives of Examples 15 to 20 and Comparative Example 15 (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 15>
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 16>
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 of adhesion | attachment are carried out. 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.

[Evaluation]
As shown in Tables 2 to 13, Examples 1 to 70 include components (A) to (C) and are included in the component (B) with respect to the total number of moles of thiol groups included in the component (A). Since the ratio of the total number of moles of isocyanate groups (isocyanate group / thiol group) was 0.2 or more and 0.78 or less, the adhesive strength was high.
On the other hand, Comparative Examples 1 to 14 had low adhesive strength because the ratio (isocyanate group / thiol group) was outside the scope of the present invention.
Moreover, since the comparative examples 15 and 16 did not mix | blend the radical generating agent (C), the adhesive force was low.

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

Claims (7)

Compounding polythiol compound (A), isocyanate group-containing compound (B), and 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 which is 2 or more and 0.78 or less.   The composition according to claim 1, wherein the radical generator (C) is a thermal radical generator composed of 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 claim 1 or 2, wherein   The composition in any one of Claims 1-3 formed by mix | blending a urethanization catalyst (D).   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.