JP6466935B2 - Laminated body, manufacturing method of laminated body, laminated body, and adhesive composition film - Google Patents

Description

  The present invention relates to a laminated body, a method for producing a laminated body, a laminated body, and an adhesive composition film, and more specifically, for example, a laminated body using unvulcanized rubber, and a laminated body using the laminated body. The present invention relates to a production method and a laminate, and an adhesive composition film suitable for bonding unvulcanized rubber and vulcanized rubber.

Conventionally, a material having a good adhesion to rubber has been demanded, but there has been no material capable of obtaining a sufficient adhesion to rubber.
A method of bonding unvulcanized rubber and vulcanized rubber is disclosed in, for example, Japanese Patent Application Laid-Open No. 2007-217559. In this method, after surface treatment of a vulcanized rubber member, the surface treated surface is applied. Unvulcanized rubber member is vulcanized and bonded.
Japanese Patent Application Laid-Open No. 2005-75010 discloses that a diene rubber can be vulcanized in a laminate obtained by bonding and vulcanizing a thermoplastic resin or a thermoplastic resin laminate and an unvulcanized rubber composition. The use of an unvulcanized rubber composition containing a polysulfide-containing organic compound is disclosed.

However, the methods described in these patent documents still have room for improvement in adhesive strength.
Therefore, the present disclosure provides, for example, a laminated body in which the first layer and the second layer are bonded with high adhesion by applying energy, a method of manufacturing a laminated body using the laminated body, and the laminated body It aims at providing the laminated body manufactured by the manufacturing method.
Another object of the present disclosure is to provide an adhesive composition film that exhibits a high adhesive force in bonding an unvulcanized rubber and a vulcanized rubber, for example.

In order to achieve the above object, according to an aspect of the present invention, a first layer containing unvulcanized rubber, a polythiol compound, a compound having a functional group that reacts with a thiol group, and a radical generator, Ratio of the total number of moles (FG) of the functional groups reacting with the thiol group contained in the compound having a functional group that reacts with the thiol group to the total number of moles (SH) of the thiol groups contained in the polythiol compound (FG) / SH) is formed using the composition (X) containing 0.15 or more and 0.25 or less, and a laminated body having a second layer in contact with the first layer is provided.
Further, according to another aspect of the present invention, the polythiol compound, the compound having a functional group that reacts with a thiol group, and a radical generator, the thiol group with respect to the total number of moles (SH) of thiol groups contained in the polythiol compound. Of the composition (X) in which the ratio (FG / SH) of the total number of moles (FG) of the functional group reacting with the thiol group contained in the compound having the functional group that reacts with FG is 0.15 or more and 0.25 or less. A coating film, a polythiol compound, a compound having a functional group that reacts with a thiol group, and a radical generator having a functional group that reacts with the thiol group with respect to the total number of moles (SH ′) of thiol groups contained in the polythiol compound The ratio (FG ′ / SH ′) of the total number of moles (FG ′) of the functional groups that react with the thiol group contained in the compound is greater than 0.25 and greater than or equal to 1.20. Polymerization of the polythiol compound and the compound having a functional group that reacts with the thiol group in the coating film of the composition (X) and the composition in a state where the coating film of the composition (Y) included below is in contact The coating film of the composition (X) and the coating film of the composition (Y) are formed into a film by polymerization of the polythiol compound in the coating film of the product (Y) and a compound having a functional group that reacts with the thiol group. Provided is an adhesive composition film.

According to an embodiment of the present invention, a stacked body in which the first layer and the second layer are bonded with high adhesion by applying energy, a method of manufacturing a stacked body using the stacked body, and the stacked body The laminated body manufactured by the manufacturing method of can be provided.
In addition, according to the embodiment of the present invention, it is possible to provide an adhesive composition film that exhibits a high adhesive force in bonding between an unvulcanized rubber and a vulcanized rubber.

[Superposition]
The laminated body in one embodiment of the present invention includes a first layer containing unvulcanized rubber and a polythiol compound (hereinafter, the polythiol compound used in the composition (X) is also referred to as “polythiol compound (A)”). , A compound having a functional group that reacts with a thiol group (hereinafter, a compound having a functional group that reacts with a thiol group used in the composition (X) is referred to as “a compound having a functional group that reacts with a thiol group (B)” or “ Compound (B) ”and a radical generator (hereinafter, the radical generator used in the composition (X) is also referred to as“ radical generator (C) ”) are included in the polythiol compound (A). The ratio (FG / SH) of the total number of moles (FG) of the functional group reacting with the thiol group contained in the compound (B) to the total number of moles (SH) of the thiol group (FG / SH) is 0.15 or more. .25 is formed using a composition (X) contained in the following, having a second layer in contact with said first layer.

  Throughout this specification, “SH” represents the total number of moles of thiol groups contained in the polythiol compound (A), and “FG” is contained in the compound (B) having a functional group that reacts with the thiol groups. The total number of moles of the functional group that reacts with the thiol group is shown. Further, the “ratio (FG / SH)” is the thiol group contained in the compound (B) having a functional group that reacts with the thiol group with respect to the total number of moles (SH) of the thiol group contained in the polythiol compound (A). The ratio of the total number of moles (FG) of the functional groups to be reacted is shown (that is, “ratio (FG / SH) = FG ÷ SH”).

Throughout the present specification, the polythiol compound (A), the compound (B) having a functional group that reacts with the thiol group, the radical generator (C), and the catalyst (D) and the surface conditioner (E) described later are included. , Component (A), component (B), component (C), component (D), and component (E), respectively.
Further, the “functional group that reacts with the thiol group” contained in the component (B) may be referred to as “reactive functional group”.

In the embodiment of the present invention, as described above, the second layer formed using the composition (X) having a ratio (FG / SH) of 0.15 or more and 0.25 or less is made of unvulcanized rubber. The first layer is provided in contact with the first layer.
Examples of the “second layer formed using the composition (X)” include, in addition to a layer of a coating film obtained by applying the composition (X), a composition ( Examples thereof include a layer of an adhesive composition film in which the component (A) and the component (B) in X) are polymerized to form a film of the composition (X).

Here, “to form a film” means that the composition (X) is formed into a film and the components (A) and (B) in the composition (X) are polymerized and cured to maintain the shape. It means that sex is imparted. However, the film formation of the composition (X) is not limited to film formation only by copolymerization of the component (A) and the component (B), and the homopolymerization of the component (B) contributes to film formation. Also good. In the present specification, the second layer that is not formed into a film is referred to as a “coating layer”.
That is, the “coating layer” is a state before the composition (X) is formed into a film, and there are an unpolymerized component (A) and a component (B). Therefore, in the laminated body using the second layer that is the “coating layer”, the component (A) in the composition (X) is determined by the energy imparted when the laminated body is produced using the laminated body. ) And component (B) are polymerized (filmed).

In both cases where the second layer is a “coating layer” and the second layer is an “adhesive composition film layer”, the superposed body is formed by applying energy to the first layer. And the second layer are bonded with high adhesive strength.
Specifically, the second layer becomes an adhesive layer by applying energy for activating the component (C) contained in the second layer to the second layer of the superposed body. A layered product in which a layer derived from the layer and the adhesive layer are bonded with high adhesive strength is obtained.
The reason is not clear, but is presumed as follows.

As described above, the second layer is a layer provided in contact with the first layer and formed using the composition (X).
Therefore, first, in the process of forming the second layer or the process of applying energy to the superposed body, the reactivity of a part of the thiol groups of the component (A) and the component (B) contained in the composition (X) Polymerization of component (A) and component (B) occurs due to the reaction of the functional group.

  On the other hand, the component (C) contained in the second layer is activated by applying energy for activating the component (C) to the superposed body. The activated component (C) acts on another thiol group in the component (A) (that is, a thiol group not reacted with the reactive functional group of the component (B)) to generate a thiyl radical. The generated thiyl radical causes a carbon-carbon double bond and a thiol-ene reaction contained in the unvulcanized rubber of the first layer (unvulcanized rubber in contact with the second layer). Thus, chemical bonding occurs at the interface between the first layer and the second layer.

In particular, in the embodiment of the present invention, the ratio (FG / SH) of the composition (X) is in the above range, so that the film strength due to polymerization of the component (A) and the component (B) can be increased. And the interfacial adhesive force due to chemical bonding at the interface between the second layer and the second layer are good. Therefore, it is presumed that a laminated body in which the first layer and the second layer are bonded with high adhesive strength can be obtained.
Hereinafter, when simply referred to as “adhesive strength” in the present specification, it means a total adhesive strength including a balance between the interfacial adhesive strength and the film strength.

The superposition body may have a third layer in addition to the first layer and the second layer. Specifically, the superposed body may be a superposed body having a first layer, a second layer, and a third layer in this order.
Examples of the third layer include a layer containing at least one selected from unvulcanized rubber, vulcanized rubber, resin, and metal. That is, in the superposed body, the third layer may include an unvulcanized rubber (first embodiment), and the third layer may be referred to as at least one of resin and metal (hereinafter referred to as “resin etc.”). ) (Second embodiment) and the third layer includes vulcanized rubber (third embodiment).
In the following, “at least one of resin and metal” may be referred to as “resin and the like”.

<Composition (X)>
First, the composition (X) used in common in all the embodiments will be described.
As described above, the composition (X) includes the polythiol compound (A), the compound (B) having a functional group that reacts with a thiol group, and the radical generator (C), and is included in the polythiol compound (A). Ratio (FG / SH) of the total mole number (FG) of the functional group reacting with the thiol group contained in the compound (B) having the functional group reacting with the thiol group with respect to the total mole number (SH) of the thiol group Is 0.15 or more and 0.25 or less.
Hereinafter, each component of the composition (X) will be described in detail.

<< Polythiol Compound (A) >>
In the present invention, the polythiol compound means a compound having two or more thiol groups in one molecule. As a component (A), only 1 type of polythiol compounds may be used and 2 or more types of polythiol compounds may be used together.
Regarding the polythiol compound (A), the number of thiol groups in one molecule is not particularly limited as long as it satisfies the relationship with the total number of moles of (meth) acryloyl groups in the component (B) described above, From the viewpoint of improvement, those having three or more thiol groups in one molecule are preferable. The upper limit of the number of thiol groups in one molecule of the polythiol compound (A) is not particularly limited, and can be appropriately selected as long as the effect of the present invention is not inhibited. Regarding the polythiol compound (A), the number of thiol groups in one molecule may differ depending on, for example, a low molecular compound and a high molecular compound, but is usually 2 to 7, preferably 3 to 6, More preferably, it can be suitably determined within the range of 3-4. However, this range does not limit the scope of the present invention.
The polythiol compound (A) includes primary, secondary, and tertiary thiols, but primary thiols are preferred from the viewpoint of improving adhesive strength.
The molecular weight of the polythiol compound (A) is preferably 3000 or less, more preferably 2000 or less, still more preferably 1000 or less, even more preferably 900 or less, particularly from the viewpoint of improving the adhesive force. Preferably it is 800 or less. The lower limit of the molecular weight of the polythiol compound (A) is not particularly limited, but is preferably 200 or more, and more preferably 300 or more. 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 an aliphatic polythiol that may contain a heteroatom and an aromatic polythiol that may contain a heteroatom. From the viewpoint of improving adhesion, the polythiol compound (A) contains a heteroatom. Aliphatic polythiols that may be present are preferred.
Here, the “aliphatic polythiol optionally containing a heteroatom” means an aliphatic compound having a heteroatom having two or more thiol groups in one molecule. The “aromatic polythiol optionally containing a heteroatom” refers to an aromatic compound which may contain a heteroatom having two or more thiol groups in one molecule.
The heteroatom is preferably at least one selected from oxygen, nitrogen, sulfur, phosphorus, halogen, and silicon, more preferably oxygen, nitrogen, sulfur, phosphorus, and the like, from the viewpoint of improving adhesive strength. At least one selected from halogen, particularly preferably at least one selected from oxygen, nitrogen, and sulfur.

(Aliphatic polythiol optionally containing heteroatoms)
Examples of the aliphatic polythiol that may contain a heteroatom include polythiols in which a portion other than a thiol group is an aliphatic hydrocarbon such as alkanedithiol having 2 to 20 carbon atoms, and halogens of halohydrin adducts of alcohols. Polythiol formed by substituting atoms with thiol groups, polythiol composed of hydrogen sulfide reaction products of polyepoxide compounds, thioglycolic acid obtained by esterification of polyhydric alcohol having 2 to 6 hydroxyl groups in the molecule with thioglycolic acid An esterified product, 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, a polysulfide group Contains thio Le, silicones modified with thiol groups, modified silsesquioxane and the like with a thiol group.
Examples of the polyhydric alcohol having 2 to 6 hydroxyl groups in the molecule include alkanediol having 2 to 20 carbon atoms, poly (oxyalkylene) glycol, glycerol, diglycerol, trimethylolpropane, ditrimethylolpropane, Examples include pentaerythritol and dipentaerythritol.

  Among the examples of the aliphatic polythiol that may contain a heteroatom, the polythiol other than the thiol group is an aliphatic hydrocarbon, and the halogen atom of the halohydrin adduct of alcohol is a thiol group from the viewpoint of improving adhesive strength. Preferred are polythiols substituted with hydrogen sulfide, polythiols consisting of hydrogen sulfide reaction products of polyepoxide compounds, thioglycolic acid esterified products, mercapto fatty acid esterified products, and thiol isocyanurate compounds, and more preferred are mercapto fatty acid esterified products and thiol isocyanurate compounds. Mercapto fatty acid esterified products are particularly preferred. From the same viewpoint, a thiol containing no polysulfide group or siloxane bond is also preferred.

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

  The β-mercaptopropionate esterified product having a primary thiol group is preferably tetraethylene glycol bis (3-mercaptopropionate) [EGMP-4], trimethylolpropane tris (3-mercaptopropionate) [ TMMP], pentaerythritol tetrakis (3-mercaptopropionate) [PEMP], 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 having a primary thiol group, the number of thiol groups in one molecule is preferably 2 to 4 and more preferably 3 from the viewpoint of improving adhesive strength. .
The thiol isocyanurate compound having a primary thiol group is preferably tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate (TEMPIC).

(Silicone modified with thiol group)
Examples of silicones modified with thiol groups include mercapto-modified silicone oils (for example, trade names KF-2001, KF-2004, X-22-167B (Shin-Etsu Chemical Co., Ltd.), SMS042, SMS022 (Gelest), PS849, PS850 ( UCT))) and the like.

(Aromatic polythiols that may contain heteroatoms)
Examples of the aromatic polythiol that can be used as the polythiol compound (A) include aromatic polythiols exemplified below. As mentioned above, these aromatic polythiols may contain heteroatoms. Aromatic polythiols include 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis (mercaptomethyl) benzene, 1,3-bis (mercaptomethyl) Benzene, 1,4-bis (mercaptomethyl) benzene, 1,2-bis (mercaptoethyl) benzene, 1,3-bis (mercaptoethyl) benzene, 1,4-bis (mercaptoethyl) benzene, 1,2, 3-trimercaptobenzene, 1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene, 1,2,3-tris (mercaptomethyl) benzene, 1,2,4-tris (mercaptomethyl) Benzene, 1,3,5-tris (mercaptomethyl) benzene, 1,2,3-tris (mercaptoethyl) benze 1,2,4-tris (mercaptoethyl) benzene, 1,3,5-tris (mercaptoethyl) benzene, 2,5-toluenedithiol, 3,4-toluenedithiol, 1,3-di (p-methoxy) Phenyl) propane-2,2-dithiol, 1,3-diphenylpropane-2,2-dithiol, phenylmethane-1,1-dithiol, 2,4-di (p-mercaptophenyl) pentane and the like.

<< Compound (B) having a functional group that reacts with a thiol group >>
In the present invention, the compound having a functional group that reacts with a thiol group refers to a compound that has at least one functional group (reactive functional group) that reacts with a thiol group in the molecule.

Examples of the reactive functional group include an isocyanate group, an acryloyl group, a methacryloyl group, an epoxy group, an allyl group, a vinyl group, an allyloxy group, a vinyloxy group, and a group having a norbornene skeleton.
Examples of the group having a norbornene skeleton include an unsubstituted norbornenyl group.
Component (B) may be a compound containing only one type of reactive functional group in one molecule, or a compound containing two or more types.

Regarding the component (B), the number of reactive functional groups in one molecule is not particularly limited as long as the relationship with the total number of moles of thiol groups in the component (A) is satisfied.
For example, when the component (B) contains an acryloyl group as a reactive functional group, the number of reactive functional groups in one molecule is, for example, a low molecular compound and a high molecular compound (eg, oligomer, polymer, etc.) However, from the viewpoint of increasing the adhesive force, 1 or more and 70 or less are mentioned, 1 or more and 20 or less are preferable, 2 or more and 10 or less are more preferable, and 3 or more and 7 or less are more preferable.
On the other hand, when all the reactive functional groups contained in the component (B) are functional groups other than acryloyl groups (that is, they do not contain acryloyl groups), the number of terminal double bonds in one molecule is, for example, a low molecular weight Although it may differ depending on the case of a compound and a polymer compound (for example, oligomer, polymer, etc.), from the viewpoint of enhancing the adhesive strength, it is 2 or more and 70 or less, preferably 2 or more and 10 or less, and preferably 3 or more and 7 or less Is more preferable.

  That is, since a compound containing an acryloyl group has high reactivity and is easily polymerized by application of energy, a compound having only one acryloyl group in one molecule is also preferably used as the component (B). On the other hand, since a compound containing no acryloyl group has a lower reactivity than a compound containing an acryloyl group, a compound having 2 or more reactive functional groups in one molecule is preferably used as the component (B). It is done.

  In addition, when a component (B) is a high molecular compound, as a number average molecular weight of a component (B), from a viewpoint of improving adhesive force, for example, 50000 or less is mentioned, Preferably it is 40000 or less, More preferably 35000 or less. Although the minimum of the number average molecular weight of a component (B) is not specifically limited, As a number average molecular weight of a component (B), 2000 or more is mentioned, for example.

Examples of the component (B) include polyisocyanates having two or more isocyanate groups, monoacrylates having one acryloyl group, polyacrylates having two or more acryloyl groups, polymethacrylates having two or more methacryloyl groups, and epoxy groups. Epoxy compounds having two or more, allyl compounds having two or more allyl groups, vinyl compounds having two or more vinyl groups, allyl ether compounds or allyl ester compounds having two or more allyloxy groups, two or more vinyloxy groups Examples thereof include vinyl ether compounds or vinyl ester compounds, norbornene compounds having two or more norbornenyl groups.
In addition, as a component (B), only 1 type of the compound which has a functional group which reacts with a thiol group may be used, and 2 or more types of compounds which have a functional group which reacts with a thiol group may be used together.

As the component (B), from the viewpoint of obtaining a laminate having high heat resistance, a compound having a cyclic structure in the molecule in addition to the reactive functional group is preferable.
The cyclic structure is not particularly limited as long as it constitutes a ring, and examples of the cyclic structure include an aliphatic ring structure, an aromatic ring structure, and a heterocyclic structure.

Examples of the aliphatic ring structure include those other than the aromatic ring structure among the ring structures composed of carbon. The aliphatic ring structure is an unsaturated aliphatic ring structure even if it is a saturated aliphatic ring structure. May be.
Specific examples of the aliphatic ring structure include a monocyclic aliphatic ring structure, and more specifically, a cycloalkane structure such as cyclohexane or a cycloalkene structure such as cyclohexene. . The number of carbon atoms constituting the monocyclic aliphatic ring structure is, for example, in the range of 3 or more and 20 or less, preferably 4 or more and 12 or less, more preferably 5 or more and 8 or less, and most preferably 6.

  The aliphatic ring structure is not limited to a monocyclic structure, and may be a polycyclic aliphatic ring structure. Examples of the polycyclic aliphatic ring structure include a structure of a polycyclic cycloalkane such as decalin or a structure of a polycyclic cycloalkene such as norbornene. In the polycyclic aliphatic ring structure, the number of carbon atoms constituting each ring is, for example, in the range of 3 to 20 and preferably in the range of 4 to 12 and more preferably in the range of 5 to 8. More preferably, the polycyclic aliphatic ring structure has a 6-membered ring.

  Examples of the aromatic ring structure include an unsaturated ring structure in which carbons having π electrons are arranged in a ring. Specific examples of the aromatic ring structure include, for example, monocyclic aromatic ring structures such as benzene and [4n + 2] annulene (where n is 1 to 4), naphthalene, azulene, indene, fluorene, anthracene. And other polycyclic aromatic ring structures. Of the above, the aromatic ring structure is preferably a monocyclic or polycyclic aromatic ring structure having a benzene ring (aromatic ring having 6 carbon atoms), and most preferably a monocyclic benzene ring structure.

A heterocyclic structure is a heterocyclic structure comprising one or more heteroatoms, which may be monocyclic or polycyclic, aliphatic or aromatic. Also good. A hetero atom is an atom other than carbon that forms a ring structure, and specific examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom.
Specific examples of the heterocyclic structure include a structure in which one or more (specifically, for example, one or more and three or less) carbon atoms of the aliphatic ring structure or the aromatic ring structure are replaced with a hetero atom. Is mentioned. Examples of the number of atoms constituting the monocyclic heterocyclic structure include 3 or more and 10 or less, preferably 5 or more and 8 or less, and most preferably 6. In the polycyclic heterocyclic structure, the number of atoms constituting each ring is, for example, 3 or more and 10 or less, and preferably 5 or more and 8 or less. Moreover, what has a 6-membered ring as a polycyclic heterocyclic structure is mentioned further more preferably.

Note that the aliphatic ring structure, aromatic ring structure, and heterocyclic structure may further have a substituent. As said substituent, an oxygen atom (= O), a hydroxyl group, an alkyl group, an alkoxy group, an amino group etc. other than (meth) acryloyl group are mentioned, for example.
Moreover, the said substituent may be directly introduce | transduced into the atom which comprises a cyclic structure, and may be introduce | transduced via the coupling group. In addition, when one molecule of component (B) has two or more cyclic structures, the atoms constituting one cyclic structure and the atoms constituting the other cyclic structure may be bonded by a single bond. You may couple | bond together through group. Examples of the linking group include an alkylene group, a carbonyl group, an ether bond, an ester bond, a sulfide bond, an amide bond, a urethane bond, and a urea bond.

Component (B) may contain only one kind of the above cyclic structure in one molecule, or may contain two or more kinds. In addition, the component (B) may contain only a monocyclic ring structure or only a polycyclic ring structure in one molecule, and may contain both a monocyclic ring structure and a polycyclic ring structure. May be included.
The number of rings contained in one molecule of component (B) may differ depending on whether it is a low molecular compound or a high molecular compound. For example, it may be 1 or more and 100 or less, and 1 or more and 50 or less. Among these, 1 or more and 20 or less are preferable, and 2 or more and 10 or less are more preferable.
When a polycyclic ring structure is included, the number of each ring is counted as the “number of rings”. Specifically, for example, when the molecule has only one anthracene structure as a cyclic structure, the “number of rings” is 3.

Moreover, as a component (B), the compound which has a nitrogen atom from a viewpoint of obtaining the laminated body which has an adhesive layer with high film | membrane intensity | strength is preferable.
Examples of the compound having a nitrogen atom include a compound having a heterocyclic structure containing a nitrogen atom as a heteroatom as a cyclic structure, and a compound in which a substituent or linking group containing a nitrogen atom is bonded to an atom constituting the cyclic structure. It is done. In addition, the nitrogen atom contained in the substituent or the linking group may be directly bonded to the atom constituting the cyclic structure.
Specific examples of the compound having a nitrogen atom include compounds having at least one of a urethane skeleton and an isocyanurate ring. In addition, the compound having a nitrogen atom is preferably a compound having both an isocyanurate ring and a urethane bond from the viewpoint of achieving both adhesiveness and heat resistance of the adhesive layer.

Examples of the compound having a urethane skeleton include a urethane compound obtained by reacting an organic isocyanate compound with a hydroxy group-containing compound having one or more reactive functional groups and one hydroxy group in the molecule. In addition, the compound having a urethane skeleton is obtained by adding, to the organic isocyanate compound, a hydroxy group-containing compound and, if necessary, at least one diol selected from alkane diol, polyether diol, polybutadiene diol, polyester diol, polycarbonate diol, and amide diol. It may be a reacted compound.
As a method of obtaining a urethane compound by reacting an organic isocyanate compound with a hydroxy-containing compound, a known method can be used.

  Examples of the organic isocyanate compound include aromatic diisocyanates such as toluene diisocyanate, diphenylmethane diisocyanate, diphenyldimethylmethane diisocyanate, dibenzyl diisocyanate, naphthylene diisocyanate, phenylene diisocyanate, xylene diisocyanate, tetramethylxylylene diisocyanate; tetramethylene diisocyanate, hexamethylene Aliphatic diisocyanates such as diisocyanate, lysine diisocyanate, 2-methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate, 2,2,4-trimethylhexamethylene-1,6-diisocyanate; isophorone diisocyanate , Cyclohexane diisocyanate, hydrogenated xylylene diiso Aneto, hydrogenated diphenylmethane diisocyanate, is alicyclic diisocyanates such as hydrogenated trimethyl xylylene diisocyanate. Furthermore, modified products such as these adduct modified products, carbodiimide modified products, allophanate modified products, biuret modified products, uretdione modified products, uretoimine modified products, and isocyanurate modified products are also included.

  As the hydroxy group-containing compound, for example, when the urethane compound is methacrylate, for example, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, glycerin dimethacrylate, trimethylolpropane dimethacrylate, pentaerythritol trimethacrylate And hydroxy group-containing methacrylates such as dipentaerythritol pentamethacrylate.

  Even when the urethane compound is a compound other than methacrylate, as the hydroxy group-containing compound, a compound corresponding to the hydroxy group-containing methacrylate (that is, a compound in which the methacryloyl group of the hydroxy group-containing methacrylate is replaced with each corresponding reactive functional group) ) Can be used.

Examples of the compound having an isocyanurate ring include those obtained by reacting a compound having an isocyanurate ring and a hydroxy group with a compound having a reactive functional group and reacting with a hydroxy group (such as methacrylic acid). Can be mentioned.
Examples of the compound having an isocyanurate ring and a hydroxy group include tris (2-hydroxyethyl) isocyanurate, tris (hydroxymethyl) isocyanurate, and the like.

  Specific examples of the compound having at least one of a urethane skeleton and an isocyanurate ring include, for example, compounds represented by the following structural formulas (1) to (3) and compounds represented by the following general formulas (4) to (6). Although it is mentioned, it is not limited to these.

In the general formulas (4) to (6), R ^{1 to} R ⁹ each independently represent an acryloyl group, a methacryloyl group, an epoxy group, a vinyl group, or a norbornenyl group, and L ^{1 to} L ⁹ are each independently Represents an alkylene group having 1 to 4 carbon atoms.

In the compounds represented by the general formulas (4) to (6), R ^{1 to} R ³ , R ^{4 to} R ⁶ , and R ^{7 to} R ⁹ are the same groups from the viewpoint of the film strength of the adhesive layer ( That is, it is preferable that there is only one type of reactive functional group present in one molecule.
In addition, L ^{1 to} L ⁹ in the above general formulas (4) to (6) preferably have a smaller number of carbon atoms from the viewpoint of heat resistance of the laminate, and more preferably an alkylene group having 1 to 2 carbon atoms. preferable.

In addition, a component (B) is not limited to the said compound, Other compounds may be sufficient if it is a compound which has a reactive functional group.
Hereinafter, although the other compound which has a reactive functional group is illustrated, it is not limited to these.

(Compound having an isocyanate group)
Examples of the polyisocyanate having two or more isocyanate groups include the aforementioned organic isocyanate compounds.

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

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

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

(Compound having acryloyl group)
Specific examples of monoacrylates include, for example, linear alkanol acrylates such as hexyl acrylate and stearyl acrylate, alkanol acrylates having a branched structure such as 2-ethylhexyl acrylate, and ring structures such as cyclohexyl acrylate and isobornyl acrylate. Examples include acrylates of aliphatic alkanols, acrylates of aromatic alcohols such as benzyl acrylate, and others, acrylates of halogenated alcohols such as 2-chloroethyl acrylate, acrylates of alkoxy alcohols such as 3-methoxybutyl acrylate, etc. Also mentioned.
Specific examples of the polyacrylate having two or more acryloyl groups include compounds in which the methacryloyl group of the dimethacrylate and polyfunctional methacrylate is replaced with an acryloyl group.

(Compound having an epoxy group)
Examples of the epoxy compound having two or more epoxy groups include aromatic epoxides, aliphatic epoxides, alicyclic epoxides, and modified products thereof.
Examples of aromatic epoxides include bisphenol A type epoxy compounds such as compounds represented by the following structural formula (7) or structural formula (8), bisphenol F type epoxy compounds, bisphenol S type epoxy compounds, phenol novolac type epoxy compounds, Examples include cresol novolac type epoxy compounds such as compounds represented by the following structural formula (9), polyphenol type epoxy compounds, biphenyl type epoxy compounds, naphthalene ring-containing epoxy compounds, fluorene type epoxy compounds, and the like.

Examples of the aliphatic epoxide include polyalkylene glycol diglycidyl ether such as trimethylolpropane triglycidyl ether, glycerol polyglycidyl ether, and the like.
Examples of the alicyclic epoxide include cyclohexane dimethanol diglycidyl ether.
Examples of modified aromatic epoxides, aliphatic epoxides, and alicyclic epoxides include hydrogenated bisphenol A type epoxy compounds, hydrogenated bisphenol F type epoxy compounds, hydrogenated compounds such as compounds represented by the following structural formula (10) Biphenyl type epoxy compounds, brominated bisphenol type epoxy compounds and the like can be mentioned.

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

(Allyl group-containing compound, vinyloxy group-containing compound, and vinyl group-containing compound)
Specific examples of an allyl compound having two or more allyl groups, a vinyl ether compound having two or more vinyloxy groups, and a vinyl compound having two or more vinyl groups include an allyloxy group of the allyl ether compound, an allyl group, Examples thereof include vinyloxy groups and compounds substituted for vinyl groups.
Moreover, as a vinyl ester compound which has a 2 or more vinyloxy group, the compound which replaced the allyloxy group of the said allyl ester compound with the vinyloxy group is mentioned.

(Norbornene compound having norbornenyl group)
Specific examples of the norbornene compound having two or more norbornenyl groups include, for example, a compound represented by the following structural formula (11) (PEG-tetranorbornene), a compound represented by the following structural formula (12) (tri- (norborn-2) -ene-5-carboxylate), TMPTN), a compound represented by the following structural formula (13) (pentaerythritol tetra- (norborn-2-ene-5-carboxylate), PTN4), a compound represented by the following structural formula (14) (Pentaerythritol tri- (norborn-2-ene-5-carboxylate), PTN3), and a compound represented by the following structural formula (15) (di (trimethylolpropane) tetra- (norborn-2-ene-5-carboxylate), DTTN ) And the like.

<< Radical generator (C) >>
The radical generator is a compound that generates radicals by applying energy such as heat or light. Specifically, after being activated by heat or light, the radical generator is added to the thiol group of the polythiol compound (A). It is a compound that acts to generate thiyl radicals. That is, component (C) is a component that contributes to the reaction at the interface between the first layer and the second layer of the superposed body in the energy application step.
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 adhesiveness, a thermal radical generator is preferable, and a thermal radical generator composed of peroxide is more preferable. Examples of the thermal radical generator composed of a peroxide include a thermal radical generator composed of an organic peroxide and a thermal radical generator composed of an inorganic peroxide, and among them, a thermal radical generator composed of an organic peroxide includes Further preferred.
Hereinafter, although the specific example of a component (C) is shown, a component (C) is not limited to these.

  Examples of the thermal radical generator composed of an organic peroxide include t-butyl = 2-ethylperoxyhexanoate, dilauroyl peroxide, 1,1,3,3-tetramethylbutyl = peroxy-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-amyl = peroxy-2-ethylhexanoate, di (2-t-butylperoxyisopropyl) benzene, di (t-butyl) peroxide, 1,1'-di (2-t- Butylperoxyisopropyl) benzene, benzoyl peroxide, 1,1′-di (t-butylperoxy) cyclohexane, di ( , 5,5-trimethyl hexanoyl) peroxide, t- butyl = peroxy neodecanoate, t-hexyl = peroxy neodecanoate, dicumyl peroxide and the like. Among these, preferably t-butyl = 2-ethylperoxyhexanoate, dilauroyl peroxide, 1,1,3,3-tetramethylbutyl = peroxy-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 peroxide 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-based photoradical generator and those obtained by adding a double bond of an acrylic group to benzophenone.
These photo radical generators can be used alone or in combination of two or more.

  In addition, the said composition (X) may contain other radical generators, such as a radical generator for accelerating film-forming of the composition (X) other than a component (C), for example. When the radical generator used as the component (C) and the other radical generator are used in combination, the same types of energy required for activation may be used in combination. Different types may be used in combination.

  Specifically, for example, when the reactive functional group of component (B) is a group having a carbon-carbon double bond, for example, light as a radical generator for promoting film formation of the composition (X). A radical generator can be used, and a thermal radical generator can be used as component (C). And a component (A) and a component (B) may be superposed | polymerized by light irradiation, a composition (X) may be made into a film, and a laminated body may be formed using the obtained adhesive composition film | membrane. Here, examples of the reactive functional group having a carbon-carbon double bond include an acryloyl group, a methacryloyl group, an allyl group, a vinyl group, an allyloxy group, a vinyloxy group, and a norbornenyl group.

  The composition (X) containing a radical generator for promoting film formation of the composition (X) may further contain a catalyst for polymerizing the component (A) and the component (B) at room temperature. Good. However, the composition (X) containing a radical generator for promoting the film formation of the composition (X) is formed into a film even if the catalyst or the like is not included. Therefore, the composition (X) contains a radical generator for promoting film formation of the composition (X) and does not contain the catalyst. Both the storage stability of X) and the film strength of the adhesive layer in the laminate obtained by applying energy to the laminate are obtained.

  The form in which the component (C) and the other radical generator are used in combination is not limited to the above form. For example, the radical generation in which the composition (X) is formed into a film by using a photoradical generator as the component (C). A form using a thermal radical generator as the agent may be used. Moreover, the form which uses a component (C) and another radical generator together uses two types of photo radical generators activated by the light of a different wavelength, and after film-forming composition (X) by light irradiation The laminated body may be obtained by irradiating the superposed body with light having a wavelength different from that of the light used for forming the composition (X) into a film.

<< Arbitrary ingredient >>
The composition (X) may further contain an optional component. Optional components include catalysts, surface conditioners, solvents, binders, fillers, pigment dispersants, conductivity imparting agents, UV absorbers, antioxidants, anti-drying agents, penetrants, pH adjusters, metal sequestering agents, anti-blocking agents. Examples include fungicides, surfactants, plasticizers, waxes, leveling agents and the like.

(Catalyst (D))
The composition (X) may use a catalyst that promotes the reaction between the component (A) and the component (B) (hereinafter also referred to as “catalyst (D)”).
For example, when the component (B) contains an isocyanate group as a reactive functional group, any thiourethanization catalyst can be used as the catalyst (D).
Examples of the thiourethanization catalyst include ditintin dilaurate, dibutyltin diacetate, dibutyltin thiocarboxylate, dibutyltin dimaleate, dioctyltin thiocarboxylate, tin octenoate, monobutyltin oxide, and the like; stannous chloride Inorganic tin 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; inorganics such as sulfuric acid, phosphoric acid and perchloric acid Acid; sodium alcoholate, hydroxylated Lithium, aluminum alcoholate, bases such as sodium hydroxide; tetrabutyl titanate, tetraethyl titanate, titanium compounds such as tetraisopropyl titanate; bismuth compounds; quaternary ammonium salts, and the like.
Among these, as the thiourethanization catalyst, the above amines are preferable, and triethylenediamine (TEDA) is more preferable. These catalysts may be used alone or in combination of two or more.

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

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

(Surface conditioner (E))
The composition (X) may contain a surface conditioner (hereinafter also referred to as “surface conditioner (E)”) as necessary. Any surface conditioning agent can be used as the surface conditioning agent (E). Examples of the surface conditioner include acrylic, vinyl, silicone, fluorine, and silicone acrylate. Among these, from the viewpoint of compatibility and surface tension reducing ability, a silicone acrylate type is preferable as the surface conditioner (E).

(solvent)
The composition (X) may contain a solvent as necessary. 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. Examples of the aliphatic solvent include hexane, butyl acetate, MEK (methyl ethyl ketone), and the like.

<< Amount of each component >>
The ratio (FG / SH) of the total number of moles of reactive functional groups (FG) contained in the compound (B) to the total number of moles (SH) of thiol groups contained in the polythiol compound (A) is 0.15. It is 0.25 or less.
When the ratio (FG / SH) is 0.15 or more, the film strength of the adhesive layer in the laminated body obtained by applying energy to the superposed body is higher than when the ratio is smaller than 0.15. Further, when the ratio (FG / SH) is 0.25 or less, the ratio of the thiol group in the component (A) to the reactive functional group in the component (B) is larger than that in the case where it is larger than 0.25. The amount of thiol groups remaining without reacting with the reactive functional group increases. Therefore, thiol-ene reaction is sufficiently performed between the thiol group and the carbon-carbon double bond on the surface of the first layer by applying energy to the superposed body, and the first layer and the adhesive layer High interfacial adhesive strength at the interface is easily obtained.
In particular, in the superposed body, since the first layer contains unvulcanized rubber, the ratio (FG / SH) is compared with the case where the first layer does not contain unvulcanized rubber and is only vulcanized rubber. ) Is smaller (that is, the proportion of thiol groups is larger), it is easier to obtain high adhesive strength.
Note that the ratio (FG / SH) is preferably 0.17 or more, more preferably 0.20 or more. The ratio (FG / SH) is preferably 0.22 or less, and more preferably 0.20 or less.

Here, the “total number of thiol groups contained in polythiol compound (A) (SH)” is obtained by multiplying the number of moles of polythiol compound (A) by the number of thiol groups possessed by one molecule of polythiol compound (A). Can be calculated. That is, “the total number of moles of thiol groups (SH) contained in the polythiol compound (A)” refers to the total amount of thiol groups in the total amount of the polythiol compound (A) contained in the composition (X). It does not indicate the number of thiol groups in one molecule of the polythiol compound.
Further, “the total number of reactive functional groups (FG) contained in the compound (B)” is obtained by dividing the blending amount by the theoretical molecular weight and multiplying by the number of reactive functional groups possessed by one molecule of the compound (B). Can be obtained. That is, “total number of reactive functional groups contained in compound (B) (FG)” is the total amount of reactive functional groups in the total amount of compound (B) contained in the composition (X). It does not indicate the number of reactive functional groups in one molecule of the compound (B).

In addition, when all the reactive functional groups of a component (B) are isocyanate groups, you may measure by JISK1603-1 B method and may obtain | require the total mole number of the isocyanate group contained in a compound (B).
Moreover, when a compound (B) is an epoxy resin, the epoxy equivalent (mass of resin containing 1 equivalent of epoxy groups) of an epoxy resin is measured by the method based on JISK7236: 2001, and the number average of an epoxy resin The total number of moles of epoxy groups contained in the compound (B) may be calculated by dividing the molecular weight by the obtained epoxy equivalent.

  In addition, after preparing composition (X) or after an adhesive composition film or an adhesive layer is formed, the total number of moles (SH) of the thiol groups and the total number of moles (FG) of the reactive functional groups are determined. In this case, for example, the component (A) and the component (B) contained in the composition (X) (the composition before becoming an adhesive composition film or an adhesive layer) using a known measurement technique such as NMR measurement or IR measurement. ), The (SH) value and (FG) value may be determined by the above method.

  The ratio (radical generator (C) / thiol group) of the total number of moles of the radical generator (C) to be blended with respect to the total number of moles of thiol groups contained in the polythiol compound (A) is 0.025 or more. It is preferable. Thereby, sufficient adhesive force (especially interface adhesive force) can be exhibited. From the same viewpoint, the ratio (radical generator (C) / thiol group) is preferably 0.03 or more, more preferably 0.035 or more, and particularly preferably 0.04 or more. Further, from the viewpoint of improving the adhesive force, the ratio (radical generator (C) / thiol group) is preferably 0.80 or less, more preferably 0.70 or less, and particularly preferably 0.60. It is as follows.

  Moreover, when using a photoradical generator as another radical generator which makes composition (X) into a film, the sum total of the photoradical generator mix | blended with respect to the total mole number of the thiol group contained in a polythiol compound (A). The molar ratio (photo radical generator / thiol group) is preferably 0.0001 or more, more preferably 0.0005 or more, and particularly preferably 0.000 or more from the viewpoint of obtaining high film strength of the adhesive layer. 001 or more. From the viewpoint of improving the adhesive layer strength, the ratio (photo radical generator / thiol group) is preferably 0.05 or less, more preferably 0.02 or less, and particularly preferably 0.01 or less. is there.

  When component (B) contains an isocyanate group as a reactive functional group, as described above, a thiourethanization catalyst may be included in composition (X) as component (D). The content of the thiourethanization catalyst in the composition (X) is an isocyanate group from the viewpoint of sufficiently accelerating the thiourethanization reaction between the component (A) and the component (B) and increasing the film strength of the adhesive layer. It is preferable that it is 0.00001 mass part-5 mass parts with respect to 100 mass parts of component (B) to contain, 0.0001 mass part-0.5 mass part is still more preferable, 0.001 mass part-0.00. 1 part by mass is particularly preferred.

  When the component (B) contains at least one of acryloyl group and methacryloyl group as the reactive functional group, as described above, a Michael addition catalyst may be included in the composition (X) as the component (D). The content of the Michael addition catalyst in the composition (X) is at least one of an acryloyl group and a methacryloyl group from the viewpoint of promoting the Michael addition reaction between the component (A) and the component (B) to increase the film strength of the adhesive layer. It is preferable that it is 0.00001 mass part-5 mass parts with respect to 100 mass parts of component (B) containing 1 type, 0.0001 mass part-0.5 mass part is still more preferable, 0.001 mass part -0.1 mass part is especially preferable.

  When the component (B) includes an epoxy group as a reactive functional group, as described above, an anionic polymerization catalyst may be included as the component (D). The content of the anionic polymerization catalyst in the composition (X) is the component (B) containing an epoxy group from the viewpoint of enhancing the film strength of the adhesive layer by promoting anionic polymerization of the component (A) and the component (B). It is preferably 0.00001 parts by mass to 5 parts by mass with respect to 100 parts by mass, more preferably 0.0001 parts by mass to 0.5 parts by mass, and particularly preferably 0.001 parts by mass to 0.1 parts by mass. preferable.

As described above, the composition (X) contains components (A) to (C) and optional component (D), as well as other optional components (for example, a surface conditioner (E) and a solvent). You may contain. However, from the viewpoint of strongly adhering rubber (particularly unvulcanized rubber), the total content of components (A) to (D) with respect to the entire component (ie, solid content) excluding the solvent from the composition (X) is The content is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and particularly preferably 98% by mass or more.
From the same viewpoint, the total content of the components (A) to (E) with respect to the total components excluding the solvent from the composition (X) is preferably 90% by mass or more, more preferably 95% by mass or more, and still more preferably. It is 99 mass% or more, Most preferably, it is 100 mass%.

In addition, the amount of the solvent contained in the composition (X) is not particularly limited, but it is 50% by mass with respect to the entire composition (X) from the viewpoint of reducing the work load such as a drying step during the production of the laminate. The following is preferable, and 30% by mass or less is more preferable.
Since the composition (X) has the above composition, the amount of the solvent can be reduced as compared with a conventional adhesive (for example, an azine thiol adhesive). By using the composition (X) in which the amount of the solvent is in the above range, the time required for the drying step of the composition (X) can be suppressed, and the swelling with respect to the unvulcanized rubber with which the composition (X) is in contact is suppressed. can do.

<First Embodiment>
In the first embodiment, the third layer is a layer containing unvulcanized rubber.
The third layer containing the unvulcanized rubber is desirably provided so that the unvulcanized rubber contained in the third layer is in direct contact with the second layer. That is, a first layer containing unvulcanized rubber, a second layer that is in contact with the first layer and formed using the composition (X), and a second layer that is in contact with the second layer and contains unvulcanized rubber. A stacked body having three layers in this order is preferable.
Since the superposed body has the above-described configuration, the second layer is given the same energy as that of the interface between the first layer and the second layer by applying energy for activating the component (C) to the second layer. Chemical bonding also occurs at the interface between this layer and the third layer. Therefore, high film strength of the adhesive layer due to the polymerization of the component (A) and the component (B) in the composition (X) in the second layer, the second layer is the first layer and the third layer High interfacial adhesion due to chemical bonding with both layers is obtained. As a result, a laminate in which the first layer and the third layer are bonded with high adhesive force through the adhesive layer is obtained.

The unvulcanized rubber contained in the first layer and the unvulcanized rubber contained in the third layer may be the same type or different types.
In the present embodiment, as described above, the first layer and the third layer are bonded via the layer formed using the composition (X). Therefore, even if the unvulcanized rubber contained in the first layer and the unvulcanized rubber contained in the third layer are difficult to directly adhere to each other, each unvulcanized rubber is not bonded to the second layer. It is chemically bonded at the interface and bonded with high adhesive strength.
Hereinafter, the manufacturing method of each layer and a laminated body is demonstrated.

<< first layer and third layer >>
The unvulcanized rubber contained in the first layer and the third layer is not particularly limited, and is independently, for example, natural rubber (NR); polyisoprene synthetic rubber (IR), polybutadiene rubber (BR), styrene-butadiene. Conjugated diene synthetic rubbers such as copolymer rubber (SBR), acrylonitrile butadiene rubber (NBR), chloroprene rubber (CR), butyl rubber (IIR); ethylene-propylene copolymer rubber (EPM); ethylene-propylene-diene copolymer Polymer rubber (EPDM); polysiloxane rubber, and the like. These rubber layer materials may be used singly or in combination of two or more. Among these, natural rubber (NR) and a mixture of natural rubber and styrene-butadiene copolymer rubber (SBR / NR) are preferable.

The first layer and the third layer may contain unvulcanized rubber at least on the surface in contact with the second layer. For example, the first layer and the third layer may be uncoated on the surface opposite to the surface in contact with the second layer. Materials (vulcanized rubber, resin, metal, etc.) other than vulcanized rubber may be included.
Specifically, for example, an unvulcanized rubber film formed on the surface of a member made of a material other than unvulcanized rubber may be used for at least one of the first layer and the third layer. Good. Then, by applying energy to the obtained superposed body and changing the second layer into an adhesive layer, the unvulcanized rubber film is vulcanized, so that the unvulcanized material is added to the second layer. A rubber film may also serve as an adhesive. In this manner, adhesion to a member made of a material other than the unvulcanized rubber may be performed.

<< Second layer >>
As described above, as the second layer, for example, a coating layer obtained by applying the composition (X) to at least one surface of the first layer and the third layer, and the composition (X) Examples thereof include a layer of an adhesive composition film in which the component (A) and the component (B) therein are polymerized to form a film.
And as above-mentioned, when a 2nd layer is a layer of a coating film, the said film formation is performed in an energy provision process, and when a 2nd layer is a layer of an adhesive composition film | membrane, before an energy provision process The film is formed.
The composition (X) used for forming the second layer is as described above.

<< Manufacturing method of superposed body >>
Hereinafter, the manufacturing method of a laminated body is divided and demonstrated to the case where a 2nd layer is a layer of a coating film, and the case where a 2nd layer is a layer of an adhesive composition film | membrane.

-When the second layer is a coating layer-
When the second layer is a coating layer, first, the composition (X) is applied to at least one surface of the first layer and the third layer (the surface in contact with the second layer).
That is, when the composition (X) is applied only to the surface of the first layer to form a coating film, an overlapped body is obtained by laminating the third layer on the coating film, and the coating is applied. The film becomes the second layer. Similarly, when the composition (X) is applied only to the surface of the third layer, an overlapping body is obtained by laminating the first layer on the coating film, and the coating film is the second layer. It becomes.
Also, for example, by applying the composition (X) to the surfaces of both the first layer and the third layer, a first coating film is formed on the first layer, and on the third layer. A second coating film may be formed. In that case, a laminated body is obtained by bonding the first coating film and the second coating film so that they are in contact with each other, and the coating film is composed of the first coating film and the second coating film. The entire layer becomes the second layer.

Examples of the coating method for applying the composition (X) to the surface of at least one of the first layer and the third layer include a spray coating method, a dip coating method, and a spin coating method. It is not something.
Moreover, what is necessary is just to set the thickness of a coating film, a shape, a magnitude | size, etc. suitably according to the objective.

In addition, after apply | coating composition (X) to the surface of at least one of a 1st layer and a 3rd layer, before forming a laminated body, by leaving as it is for a predetermined time as needed, it is The viscosity may be increased. For example, when the component (A) and the component (B) in the composition start polymerization at room temperature as in the case where the catalyst (D) is contained in the composition, a polymerization reaction occurs due to the standing, and the coating film May increase in viscosity. In addition, when the composition contains a solvent that volatilizes at room temperature, the solvent may volatilize due to the above-mentioned standing, and the viscosity of the coating film may increase. And by increasing the viscosity of the coating film and forming the overlapped body, even if energy is applied while applying pressure to the stacked body, the coated film is unlikely to protrude from the stacked body, May be improved.
For the same reason, the viscosity of the second layer may be increased by leaving it for a predetermined time as necessary even after forming the superposed body and before applying energy to the superposed body.
The standing time varies depending on the composition of the composition, but for example, a range of 0 to 30 minutes is exemplified, and preferably 1 to 15 minutes.

-When the second layer is a layer of an adhesive composition film-
As described above, the adhesive composition film is a film formed by polymerizing the component (A) and the component (B) in the composition.
When the second layer is a layer of an adhesive composition film, for example, the composition (on the surface of at least one of the first layer and the third layer as in the case where the second layer is a coating film) X) may be applied to form a coating film, and then the coating film may be formed into a film to form an adhesive composition film.
Specifically, for example, when a coating film is formed on the first layer, and the adhesive composition is formed by forming the coating film into a film, the third layer is formed on the surface of the adhesive composition film that is not in contact with the first layer. The laminated body is obtained by laminating so as to be in contact with each other, and the adhesive composition film becomes the second layer. The same applies when a coating film is formed on the third layer.
In addition, after obtaining the laminated body whose 2nd layer mentioned above is a layer of a coating film, the said coating film is made into a film and it is good also as a laminated body whose 2nd layer is a layer of an adhesive composition film | membrane.

  Further, for example, the composition (X) is applied on a support other than the first layer and the third layer to form a coating film, and an adhesive composition film is formed by film formation, and then on the support. The second layer may be formed by applying the adhesive composition film on the first layer or the third layer. In that case, for example, after bonding the first layer or the third layer to the surface opposite to the support in the obtained adhesive composition film, the support may be peeled off, or the adhesive is peeled off in advance. The first layer and the third layer may be bonded to the composition film.

  The support for forming the adhesive composition film is not particularly limited, and examples thereof include a sheet-like support such as a release sheet, and a pedestal. The thickness and shape of the support can be appropriately set according to the shape of the adhesive composition film to be formed.

Examples of materials that can be used for the sheet-like support include paper, resin, resin-coated paper, metal, and the like.
For example, the material of the resin release sheet includes polyester resins such as polyethylene terephthalate, polycyclohexylene terephthalate, polyethylene naphthalate, polyamide resins such as nylon 46, modified nylon 6T, nylon MXD6, polyphthalamide, and polyphenylene sulfide. And ketone resins such as polythioether sulfone and sulfone resins such as polysulfone and polyether sulfone. In addition, as the release sheet, a transparent resin substrate mainly composed of an organic resin such as polyether nitrile, polyarylate, polyether imide, polyamide imide, polycarbonate, polymethyl methacrylate, triacetyl cellulose, polystyrene, and polyvinyl chloride is suitably used. Can be used.

The method for forming the coating film of the composition (X) into a film is appropriately selected according to the composition and properties of the composition (X).
When the composition (X) in which the component (A) and the component (B) are polymerized in a room temperature environment is used, for example, by leaving the coating film at room temperature for a predetermined time, the coating film becomes a film, and the adhesive composition film Is obtained. As a composition in which the component (A) and the component (B) are polymerized in a room temperature environment, for example, the component (B) is at least one of an isocyanate group, an acryloyl group, a methacryloyl group, and an epoxy group as a reactive functional group. And a composition (X) containing a catalyst (D).

  In addition, even if it is a case where the composition (X) superposed | polymerized under room temperature environment is used, as long as the component (C) in composition (X) does not activate, you may heat. From this point of view, the temperature of the coating film during standing is preferably 0 ° C. or higher and 60 ° C. or lower, more preferably 15 ° C. or higher and 40 ° C. or lower. The standing time is preferably 1 minute or longer, more preferably 3 minutes or longer, from the viewpoint of maintaining the shape of the adhesive composition film so as to maintain the shape.

  Moreover, when the composition (X) in which the component (A) and the component (B) are polymerized by light irradiation is used, the coating film is irradiated with light to form a film to obtain an adhesive composition film. As the composition (X) in which the component (A) and the component (B) are polymerized by light irradiation, for example, as described above, the reactive functional group of the component (B) has a carbon-carbon double bond. And the composition (X) containing a photoradical generator as another radical generator is mentioned. In the composition (X), the thiol group of the component (A) in the coating film becomes a thiyl radical by the photoradical polymerization agent activated with light, and the carbon-carbon dioxygen contained in the reactive functional group of the component (B). Polymerizes by causing a heavy bond and a thiol-ene reaction.

  The wavelength of the light irradiation means and the light to be irradiated is not particularly limited as long as it activates a photo radical generator that contributes to film formation of the coating film. Specific examples of the light irradiation means include ultra high pressure, high pressure, medium pressure, and low pressure mercury lamps, xenon lamps, metal halide lamps, fluorescent lamps, semiconductor lasers, and light emitting diodes (LEDs). Moreover, as a wavelength of the light to irradiate, the range of 300 nm or more and 420 nm or less is mentioned, for example, 350 nm or more and 400 nm or less are mentioned more suitably.

As the intensity of the irradiated light, although depending on the light irradiating means used, for example, when using the LED, 100 mW / cm ² or more 2000 mW / cm ² or less in the range of preferably mentioned from the viewpoint of curability. Also, the light irradiation integrated light amount depends on the light irradiation means to be used and the intensity of light, but when light irradiation is performed with an intensity in the above range using, for example, an LED, the shape retention property and high adhesive strength of the adhesive composition film From the viewpoint of obtaining the above, 150 mJ / cm ² or more and 1800 mJ / cm ² or less are preferable.

The thickness of the adhesive composition film can be appropriately selected according to the objects to be bonded (the first layer and the third layer), the required adhesive force, and the like, and is, for example, 20 to 1000 μm, preferably Is 30 to 300 μm, more preferably 30 to 200 μm.
The magnitude | size of an adhesive composition film | membrane can be suitably selected according to the object (1st layer and 3rd layer) to adhere | attach, the adhesive force requested | required, etc.

Second Embodiment
In the second embodiment, the third layer is a layer containing at least one of a resin and a metal (such as a resin).
When the third layer is a layer containing a resin or the like, a fourth layer formed between the second layer and the third layer by using an adhesive having an adhesive force to the resin or the like It is desirable to have That is, the first layer, the second layer in contact with the first layer, the fourth layer in contact with the second layer, and the third layer in contact with the fourth layer in this order. The superposition body which has is preferable.

In the superposed body, by applying energy for activating the component (C) to the second layer, chemical bonding occurs at the interface between the first layer and the second layer, and the second layer The layer becomes an adhesive layer. Since the fourth layer has an adhesive force to the resin or the like, the adhesive layer and the third layer are strongly bonded through the fourth layer.
That is, when the superposed body having the above-described structure is used, the adhesive layer has high film strength, high interfacial adhesive force due to chemical bonding at the interface between the first layer and the second layer, and adhesion to a resin or the like. A high adhesive force between the adhesive layer and the third layer by the adhesive having strength is obtained. As a result, a laminate in which the first layer and the third layer are bonded with high adhesive force through the adhesive layer and the fourth layer is obtained.
Hereinafter, although the manufacturing method of each layer and a laminated body is demonstrated, description may be abbreviate | omitted about the content similar to the said embodiment.

<< Fourth Layer >>
The “adhesive having an adhesive force to resin or the like” used for the fourth layer refers to an adhesive that satisfies the following conditions.
Specifically, first, a laminate in which “resins etc.” included in the third layer are bonded to each other via an adhesive is prepared, and the “resins etc.” at the ends of the laminate are drawn at a tensile rate of 50 mm / The peel strength at 25 ° C. (N / 25 mm) is measured by pulling in the direction of 180 ° under the condition of minutes. Then, an adhesive having a peel strength of 100 (N / 25 mm) or more obtained by measurement is referred to as an “adhesive having an adhesive force to a resin or the like”. Specific examples of the “adhesive having an adhesive force with respect to a resin or the like” will be described later.

The adhesive having an adhesive force with respect to the resin or the like is not particularly limited as long as it satisfies the above conditions, but from the viewpoint of the adhesive force with respect to the adhesive layer formed using the composition (X) and the third layer. For example, a solvent-diluted halogenated rubber-based adhesive can be used. Among solvent-diluted halogenated rubber-based adhesives, Chemlock 2000, Metallok PH56, and the like are preferably used from the viewpoint of adhesive strength with respect to the adhesive layer and the third layer.
Note that the thickness of the fourth layer can be selected as appropriate according to the type of adhesive used.

<< Third layer >>
There is no particular limitation on at least one of the resin and metal used for the third layer.
In addition, when the third layer is a resin or the like, it is preferable to perform a primer treatment or a surface treatment in advance on the surface that comes into contact with the fourth layer, whereby the interface between the fourth layer and the third layer is more preferable. High adhesion can be obtained.

<< Manufacturing method of superposed body >>
When the second layer is a layer of a coating film, the third layer may be bonded to the first layer after the second layer and the fourth layer are sequentially formed on the first layer, and the fourth layer is added to the third layer. After the first layer and the second layer are sequentially formed, the first layer may be bonded. Alternatively, after the second layer is formed on the first layer and the fourth layer is formed on the third layer, the second layer and the fourth layer may be bonded to each other.

  When the second layer is a layer of an adhesive composition film, another film is formed after forming the coating film of the composition (X) formed on the first layer or the fourth layer, or Bonding may be performed, and the coating film may be formed into a film after obtaining a laminated body in which the second layer is a coating film layer.

Moreover, a laminated body may be manufactured using the adhesive composition film obtained by providing composition (X) on another support body, forming a coating film, and film-forming a coating film.
Specifically, for example, the support may be peeled off after bonding the first layer to the adhesive composition film on the support, or the third layer in which the fourth layer is formed is bonded. The support may be peeled later, or the support may be peeled after the fourth layer is formed and the third layer is bonded. Moreover, you may manufacture a laminated body using the adhesive composition film previously peeled from the support body.
Other matters (for example, a method for forming a coating film and a support to be used) are the same as those in the above embodiment.

<Third Embodiment>
In the third embodiment, the third layer is a layer containing vulcanized rubber.
When the third layer is a layer containing vulcanized rubber, it may have a fifth layer formed by using a composition (Y) described later between the second layer and the third layer. desirable. That is, the first layer, the second layer in contact with the first layer, the fifth layer in contact with the second layer, and the third layer in contact with the fifth layer in this order. The superposition body which has is preferable.

Here, the composition (Y) is a polythiol compound (hereinafter, the polythiol compound used in the composition (Y) is also referred to as “polythiol compound (A ′)”), a compound having a functional group that reacts with a thiol group (hereinafter referred to as “polythiol compound (A ′)”). A compound having a functional group that reacts with a thiol group used in the composition (Y) is also referred to as “compound (B ′)” or “compound (B ′)” having a functional group that reacts with a thiol group), and radical generation Agent (hereinafter, the radical generator used in the composition (Y) is also referred to as “radical generator (C ′)”) with respect to the total number of moles (SH ′) of thiol groups contained in the polythiol compound (A ′). It is a composition comprising a ratio (FG ′ / SH ′) of a total number of moles (FG ′) of functional groups that react with the thiol group contained in the compound (B ′) in a range from 0.25 to 1.20. .
Hereinafter, a polythiol compound (A ′), a compound (B ′) having a functional group that reacts with a thiol group, and a radical generator (C ′), respectively, component (A ′), component (B ′), and component (C ').

The composition (Y) has high affinity with the composition (X) and adheres to the vulcanized rubber with high adhesive force.
Specifically, as in the case of the composition (X), a part of the thiol groups of the component (A ′) contained in the composition (Y) reacts with the reactive functional group of the component (B ′). Thus, polymerization of the component (A ′) and the component (B ′) occurs. On the other hand, the component (C ′) is activated by the application of energy and acts on other thiol groups in the component (A ′) to generate thiyl radicals. The generated thiyl radical causes a carbon-carbon double bond and a thiol-ene reaction (Thiol-Ene Reactions) contained in the vulcanized rubber of the third layer (the vulcanized rubber in contact with the fifth layer). Chemical bonding occurs at the interface between the fifth layer and the third layer. Even if the vulcanized rubber does not contain a carbon-carbon double bond, the thiyl radical may extract hydrogen from the carbon-carbon bond main chain in the vulcanized rubber and chemically bond it. Since the ratio (FG ′ / SH ′) in the composition (Y) is in the above range, the film strength by polymerization of the component (A ′) and the component (B ′), the composition (Y), It is presumed that the balance between the interfacial adhesive force due to chemical bonding at the interface with the vulcanized rubber is good.

  Therefore, when the energy for activating component (C) and the energy for activating component (C ′) are applied to the second layer and the fifth layer, the second layer and the fifth layer become adhesive layers, In addition to the interface between the first layer and the adhesive layer, chemical bonding also occurs at the interface between the adhesive layer and the third layer. And high film strength of the adhesive layer, high interfacial adhesive force at the interface between the first layer and the adhesive layer, and high interfacial adhesive force at the interface between the third layer and the adhesive layer can be obtained in a well-balanced manner. A laminated body in which the first layer and the third layer are bonded with high adhesive force through the adhesive layer is obtained.

In the above-described superposed body, the second layer and the fifth layer may each independently be a coating layer or an adhesive composition film layer.
Moreover, in the said laminated body, it is preferable that the 2nd layer and the 5th layer contacted before at least one of a 2nd layer and a 5th layer was formed into a film. Specifically, as the form in which the second layer and the fifth layer come into contact before being formed into a film, for example, the second layer and the fifth layer are respectively a coating layer of the composition (X) and In addition to the form that is a layer of a coating film of composition (Y), an adhesive composition film in which each coating film is formed in a state where the coating film of composition (X) and the coating film of composition (Y) are in contact with each other The form which is is mentioned.
Hereinafter, although the manufacturing method of each layer and a laminated body is demonstrated, description may be abbreviate | omitted about the content similar to the said embodiment.

<< 5th layer >>
As described above, the composition (Y) used for the fifth layer includes the component (A ′), the component (B ′), and the component (C ′), and the ratio (FG ′ / SH ′) is 0.00. It is greater than 25 and less than or equal to 1.20. As said component (A '), component (B'), and component (C '), the thing similar to the component (A), component (B), and component (C) in a composition (X) is respectively used. It is done.
Moreover, the composition (Y) may contain the said component (D) as a catalyst which accelerates | stimulates reaction with a component (A ') and a component (B') as needed like the composition (X). The component (E), the solvent, and other components may be included.

  In addition, the combination of the composition (X) used for the second layer and the composition (Y) used for the fifth layer is such that each composition has the above-described conditions (that is, the ratio (FG / SH) and the ratio). There is no particular limitation as long as (FG ′ / SH ′)) is satisfied. That is, the composition (X) and the composition (Y) may have the same components and compositions except that the ratio (FG / SH) and the ratio (FG ′ / SH ′) are different, or different types. It may be composed of these components.

<< Third layer >>
The vulcanized rubber used for the third layer is not particularly limited, and for example, a vulcanized rubber obtained by vulcanizing a rubber similar to the unvulcanized rubber contained in the first layer described above. Can be mentioned.
However, the unvulcanized rubber used for the first layer and the vulcanized rubber used for the third layer may be of the same type or different types.

As described above, by applying energy to the stacked body, chemical bonding occurs at the interface between the fifth layer and the third layer. Therefore, the laminate bonded with a sufficiently high adhesive force can be obtained without performing roughening treatment such as polishing or other surface treatment on the bonding surface of the third layer (the surface in contact with the fifth layer). can get. Then, by omitting the surface treatment on the bonding surface of the third layer, it is possible to simplify and increase the efficiency of the bonding process.
However, when the coating film of the composition (Y) is directly formed on the third layer, the anchor effect can be utilized by performing a roughening treatment on the bonding surface of the third layer. Polymerization of the component (A ′) and the component (B ′) after the coating film of the composition (Y) is in contact with the roughened adhesion surface of the third layer and the composition (Y) enters the unevenness As a result, higher interfacial adhesion can be obtained.

<< Manufacturing method of superposed body >>
When the second layer and the fifth layer are coating layers, the third layer may be bonded to the first layer after the second layer and the fifth layer are sequentially formed on the first layer. After the fifth layer and the second layer are sequentially formed on this layer, the first layer may be bonded. Alternatively, the second layer may be formed on the first layer and the fifth layer may be formed on the third layer, and then bonded so that the second layer and the fifth layer are in contact with each other.

  When the second layer and the fifth layer are layers of the adhesive composition film, the coating film of the composition (X) and the coating of the composition (Y) are applied to either the first layer or the third layer. Both of the films may be sequentially formed and formed into a film to form a layer of the adhesive composition film, and then other layers may be bonded together. Moreover, after obtaining the laminated body in which the second layer and the fifth layer are both coating layers, the coating film may be formed into a film.

Further, on the support other than the first layer and the third layer, at least one of the coating film of the composition (X) and the coating film of the composition (Y) is formed, and the coating film of the composition (X) In addition, an adhesive composition film in which the coating film of the composition (Y) is integrally formed may be formed.
Specifically, for example, a coating film of the composition (X) is formed on the first support, a coating film of the composition (Y) is formed on the second support, and the coating of the composition (X) is performed. There is a method in which the film and the coating film of the composition (Y) are brought into contact with each other to form a film, and an adhesive composition film having each support on both sides is obtained. In this case, for example, the second support may be peeled after the first support is peeled off and the first layer and the adhesive composition film are bonded together, or the second support is peeled off. The first support may be peeled off after the third layer and the adhesive composition film are bonded together. Moreover, after peeling both the 1st support body and the 2nd support body, you may bond together with a 1st layer and a 3rd layer, respectively.
Moreover, you may obtain an adhesive composition film | membrane by forming the coating film of composition (X) and the coating film of composition (Y) in order on one support body, and forming it into a film.

The thickness of the adhesive composition film can be appropriately selected according to the object to be bonded, the required adhesive strength, etc., but for example, the thickness of the second layer and the thickness of the fifth layer As a total, the range of 20-1000 micrometers is mentioned, Preferably it is 30-300 micrometers, More preferably, it is 30-200 micrometers.
Other matters (for example, a method for forming a coating film and a support to be used) are the same as those in the above embodiment.

[Manufacturing method of laminate]
The manufacturing method of the laminated body in one embodiment of the present invention includes a superposed body forming step for forming the superposed body, and the radical generator (C) contained in the second layer with respect to the superposed body. And an energy applying step for applying energy for activating the above.

For example, when the superposed body of the first embodiment is used as a superposed body, the second layer becomes an adhesive layer by applying energy in the energy applying step, and the layer derived from the first layer, the adhesive layer, A laminate having the layers derived from the three layers in this order is obtained.
The “layer derived from the first layer” constituting the laminate means a layer that was the “first layer containing unvulcanized rubber” before the energy application step, and the production process of the laminate In the concept, the first layer is changed. Specifically, the layer derived from the first layer may be, for example, one obtained by vulcanizing an unvulcanized rubber contained in the first layer constituting the superposed body by an energy application step. Even after passing, it may remain unvulcanized rubber. The same applies to the “layer derived from the third layer”.

In addition, when the stacked body of the second embodiment is used, the second layer becomes an adhesive layer by applying energy, and the layer derived from the first layer, the adhesive layer, and the layer derived from the fourth layer, A laminate having the layers derived from the third layer in this order is obtained.
The layer derived from the first layer, the layer derived from the fourth layer, and the layer derived from the third layer are the same as described above. For example, when the third layer is a photocurable resin and the applied energy is light, examples of the layer derived from the third layer include a layer obtained by photocuring a photocurable resin.

  In addition, when the stacked body of the third embodiment is used, the second layer and the fifth layer become adhesive layers by applying energy, and the layers derived from the first layer, the adhesive layer, and the third layer A layered product having layers derived from the above in this order is obtained. The layer derived from the first layer and the layer derived from the third layer are the same as described above.

  Even in the case of using the laminated body in any of the embodiments, according to the method for manufacturing a laminate, at least the first layer and the second layer are bonded with high adhesive force by applying energy. And the laminated body by which the layer derived from the 1st layer and the layer derived from the 3rd layer were adhere | attached with high adhesive force through the contact bonding layer is obtained.

<Energy application process>
After obtaining an overlapped body by the above method, energy is applied to the overlapped body.
As described above, when using the superposed body of the first embodiment and when using the superposed body of the second embodiment, the energy for activating the component (C) contained in the composition (X) is used. Give.
Moreover, when using the superposition body of 3rd Embodiment, the energy which activates the component (C ') contained in a composition (Y) and the component (C') contained in a composition (Y) Is applied to each layer. The energy for activating component (C) and the energy for activating component (C ′) may be the same type of energy or different types of energy. Further, the energy for activating the component (C) and the energy for activating the component (C ′) may be applied simultaneously or separately.
Hereinafter, the energy for activating the component (C) when using the superposed body of the first embodiment will be described. However, the superposed body of the second embodiment and the superposed body of the third embodiment are used. The same applies to the case. The same applies to the energy for activating the component (C ′) when using the superposed body of the third embodiment.

The type of energy applied to the superposed body is determined by the type of component (C) contained in the composition (X).
When the composition (X) contains a thermal radical generator as the component (C), thermal energy is imparted to the superposed body in the energy imparting step. As the heating temperature, a temperature at which the thermal radical generator efficiently generates radicals can be appropriately selected, but it is preferably about 1 minute half-life temperature of ± 30 ° C. of the thermal radical generator.

  Moreover, when the composition (X) contains a photoradical generator as the component (C), light energy is imparted to the superposed body in the energy imparting step. 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.

  In the case where the composition (X) contains a plurality of types of radical generators, in the energy application step, at least the energy for activating the radical generator (C) contained as the component (C) may be applied to the superposed body. In addition, the radical imparting agent may be activated together with the activation of the component (C) by the energy imparted to the superposed body in the energy imparting step. Specifically, for example, when the composition (X) includes a thermal radical generator as the component (C) and a photo radical generator as the other radical generator, at least the thermal energy is applied in the energy application step. Well, both thermal energy and light energy may be applied. In addition, for example, when both component (C) and other radical generators are photoradical generators, in the energy application step, light having a wavelength that activates only component (C) may be irradiated. You may irradiate the light which a radical generator activates.

In the energy application step, energy may be applied while applying a press pressure in the thickness direction to the stacked body as necessary.
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 0.4 to 4.0 MPa, and particularly preferably. 0.5 to 3.0 MPa. The pressing time is preferably 5 to 120 minutes, more preferably 10 to 60 minutes, and particularly preferably 15 to 45 minutes.

  In the manufacturing method of the said laminated body, you may further have other processes, such as a drying process, as needed.

[Laminate]
The laminated body which concerns on one Embodiment of this invention is a laminated body obtained by the manufacturing method of the said laminated body.
For example, when the stacked body of the first embodiment is used, the stacked body includes a layer derived from the first layer and an adhesive layer (derived from the second layer) in which the second layer is changed by the energy application step. Adhesive layer) and a layer derived from the third layer are laminated in this order. That is, the laminate includes a rubber layer derived from a layer containing unvulcanized rubber, an adhesive layer derived from the composition (X), and a rubber layer derived from a layer containing unvulcanized rubber in this order. It is the laminated body which has.

  In addition, when the stacked body of the second embodiment is used, the stacked body includes a layer derived from the first layer, an adhesive layer derived from the second layer, and an adhesive layer derived from the fourth layer. And a layer derived from the third layer are laminated in this order. That is, the laminate includes a rubber layer derived from a layer containing unvulcanized rubber, an adhesive layer derived from the composition (X), a layer derived from an adhesive having an adhesive force with respect to a resin, and the like. And a layer derived from the above in this order.

  When the stacked body according to the third embodiment is used, the stacked body includes a layer derived from the first layer, an adhesive layer derived from the second layer and the fifth layer, and a third layer. And the layers derived from are laminated in this order. That is, the laminate includes a rubber layer derived from a layer containing unvulcanized rubber, an adhesive layer derived from the composition (X) and the composition (Y), and a layer containing vulcanized rubber in this order. It is the laminated body which has.

In addition, the above-mentioned “adhesive layer derived from the composition (X)” is “the layer of the coating film coated with the composition (X) or the coating film of the composition (X) formed into a film before applying the energy”. The layer of the adhesive composition film (that is, the second layer) is meant. Similarly, the “adhesive layer derived from the composition (X) and the composition (Y)” means those which were the second layer and the fifth layer before the application of energy.
The “adhesive layer derived from the composition (X)” and the “adhesive layer derived from the composition (X) and the composition (Y)” are those in which the second layer is not yet present in the first layer by applying energy. It is chemically bonded to vulcanized rubber. In the first embodiment, the second layer is also chemically bonded to the third layer. In the second embodiment, the second layer is bonded to the third layer via the fourth layer. In the third embodiment, the fifth layer is chemically bonded to the third layer.

That is, the laminate is obtained by bonding at least a layer derived from the first layer to the adhesive layer with a high adhesive force. In each of the above embodiments, the layer derived from the first layer is bonded to the layer derived from the third layer with a high adhesive force via the adhesive layer.
In addition, as for the layer derived from the said 1st layer and the layer derived from the said 3rd layer adhere | attached by an adhesive layer, the whole adhesive surface may be adhere | attached through the adhesive layer, and in each layer Only a part of the surface may be bonded via an adhesive layer.
The dimensions and the number of layers derived from the first layer, the adhesive layer, and the third layer can be appropriately selected according to the purpose.

  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.

(Example A)
[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. (primary thiol)
Pentaerythritol tetrakis (thioglycolate) (PETG): manufactured by Sakai Chemical Co., Ltd. (primary thiol)

<Compound (B) having a reactive functional group (component (B))>
-Compound (Z-Iso) represented by the structural formula (1) (reactive functional group: isocyanate group)
-Compound (D-MAc) represented by the following structural formula (16) (reactive functional group: methacryloyl group)

<Radical generator (C) (component (C))>
Thermal radical generator: t-butyl-2-ethylperoxyhexanoate: NOF Corporation, trade name "Perbutyl O"
<Other radical generators>
Photoradical generator: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (TPO): BASF, trade name “LUCIRIN TPO”

<Catalyst (D) (Component (D))>
Triethylenediamine (TEDA): manufactured by Air Products, trade name “DABCO 33LY catalyst”

<Surface Conditioner (E) (Component (E))>
・ Silicone acrylate surface conditioner: Toyo Chemicals Co., Ltd., trade name “SIU2400”

[Measurement of the total number of moles of thiol groups (SH)]
The “total number of thiol groups contained in polythiol compound (A) (SH)” is calculated by dividing the blending amount by the theoretical molecular weight and multiplying by the number of thiol groups possessed by one molecule of the polythiol compound (A). Asked.

[Measurement of total moles (FG) of reactive functional groups]
When the reactive functional group was an isocyanate group, it was measured by JIS K1603-1 B method, and the total number of moles of isocyanate groups contained in the component (B) was determined.
When the reactive functional group was a methacryloyl group, it was calculated by dividing the blending amount by the theoretical molecular weight and multiplying by the number of methacryloyl groups possessed by one molecule of component (B).

[First layer]
According to the composition shown in Table 1 below, unvulcanized rubber (length 100 mm × 25 width mm × thickness 3 mm) was produced. Specifically, the following components were mixed in the formulation shown in Table 1 below, molded to the above dimensions, and used as the first layer without vulcanization.

The details of each component in Table 1 are as follows.
Natural rubber (NR): RSS # 3
Styrene-butadiene copolymer rubber (SBR): Product name “JSR 1500” manufactured by JSR Corporation
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)”

[Third layer]
As the third layer, the same unvulcanized rubber (length 100 mm × 25 width mm × thickness 3 mm) as the first layer was used.

[Examples and Comparative Examples]
<Comparative Example A-1>
A composition in which a solvent (methyl ethyl ketone) is added to each of the above components (A) to (E) as necessary according to the following Table 2 (the numerical value of each component indicates the content (% by mass) of nonvolatile content). Product (X) was obtained. In addition, the quantity of the solvent in obtained composition (X) was 19 mass% with respect to the whole composition (X).

The obtained composition (X) was applied to the surface of the first layer to form a coating film, and left at room temperature (25 ° C.) for 180 minutes to obtain an adhesive composition film having a thickness of 100 μm. .
By bringing the third layer into contact with the surface of the adhesive composition film that is not in contact with the first layer, the second layer and the third layer, which are layers of the adhesive composition film, are brought into contact with each other. A superposed body having this order was obtained.
The obtained layered product was held for 30 minutes while applying a pressurization pressure of 2.5 MPa at a temperature of 150 ° C., so that a rubber layer and a composition (X ) And a rubber layer obtained by vulcanizing the third layer of the unvulcanized rubber was obtained in this order.
In addition, the thickness of the adhesive layer in the obtained laminate was 100 μm.

<Comparative Example A-2>
A laminate was obtained in the same manner as in Comparative Example A-1, except that the types and amounts of the components (A) to (E) used for preparing the composition (X) were as shown in Table 2 below.

<Comparative Example A-3>
A composition in which a solvent (methyl ethyl ketone) is added to each of the above components (A) to (E) as necessary according to the following Table 2 (the numerical value of each component indicates the content (% by mass) of nonvolatile content). Product (X) was obtained.

The obtained composition (X) was applied to the surface of the first layer to form a coating film. The integrated light amount becomes 800 mJ / cm ² by a light emitting diode (UV-LED, LED-UV irradiation head (water-cooled) manufactured by Sentec Co., Ltd., light intensity 1200 mW / cm ² ) that emits light of 365 nm on the obtained coating film. As described above, an adhesive composition film was obtained by irradiating light. The thickness of the obtained adhesive composition film was 100 μm.
By bringing the third layer into contact with the surface of the adhesive composition film that is not in contact with the first layer, the second layer and the third layer, which are layers of the adhesive composition film, are brought into contact with each other. A superposed body having this order was obtained.
The obtained layered product was held for 30 minutes while applying a pressurization pressure of 2.5 MPa at a temperature of 150 ° C., so that a rubber layer and a composition (X ) And a rubber layer obtained by vulcanizing the third layer of the unvulcanized rubber was obtained in this order.
In addition, the thickness of the adhesive layer in the obtained laminate was 100 μm.

<Example A-1 and Example A-2>
A laminate was obtained in the same manner as in Comparative Example A-1, except that the types and amounts of the components (A) to (E) used for preparing the composition (X) were as shown in Table 2 below.

<Example A-3>
A laminate was obtained in the same manner as in Comparative Example A-3 except that the types and amounts of the components (A) to (E) used for the preparation of the composition (X) were as shown in Table 2 below.

<Example A-4>
A laminate was obtained in the same manner as in Comparative Example A-1, except that the types and amounts of the components (A) to (E) used for preparing the composition (X) were as shown in Table 2 below.

<Example A-5>
After coating the obtained composition (X) on the surface of the first layer to form a coating film, the third layer is brought into contact without passing through a step of leaving at room temperature (25 ° C.) for 180 minutes, A laminated body was obtained in the same manner as in Example A-2, except that a superposed body having the first layer and the second layer as the coating layer and the third layer in this order was obtained.
In addition, the thickness of the adhesive layer in the obtained laminate was 100 μm.

  About the laminated body obtained by the said Example and comparative example, the adhesive force about an adhesive layer was measured as follows. The results are shown in Table 2.

[Measurement method of adhesive strength of adhesive layer (T peel test)]
A T peel test is performed by pulling the rubber layer derived from the first layer and the rubber layer derived from the third layer at the end of the laminate in the direction of 180 ° under the condition of a tensile speed of 50 mm / min. The peel strength (N / 25 mm) was measured and used as an index of adhesive strength. In addition, Table 2 shows the failure modes.
As the value of “adhesive strength” in the evaluation results, if the peel strength is 100 N / 25 mm or more, the adhesive strength is sufficient to destroy the rubber substrate before peeling occurs. Preferably it is 300 N / 25 mm or more. On the other hand, when the value of “adhesive strength” (peel strength) is less than 100 N / 25 mm, the interface between the rubber layer and the adhesive layer derived from the first layer and the rubber layer and the adhesive layer derived from the third layer The chemical bond at the interface is not sufficient and peeling occurs at the interface, or the cohesive force of the adhesive layer is not sufficient and the adhesive layer itself cohesively breaks down, so that the adhesive force is not sufficient.

[Evaluation]
As shown in the above-mentioned table, in the examples, the reactive functional groups contained in component (B) with respect to the total number of moles of thiol groups contained in components (A) to (C) and contained in component (A). Since the second layer was formed using the composition (X) having a total molar ratio (FG / SH) of 0.15 or more and 0.25 or less, the adhesive strength was high.
On the other hand, in the comparative example, since the ratio (FG / SH) was outside the above range, the adhesive force was low.

(Example B)
[Raw materials]
Component (A), component (B), component (C), component (D), component (E), and other radical generators are the same as in Example A above.
Moreover, the following were used as other raw materials.

<Adhesive having adhesion to at least one of resin and metal>
・ Chemlock 2000 (CH2000): Solvent-diluted halogenated rubber adhesive, manufactured by Lord, trade name “Chemlock 2000”

[First layer]
The same unvulcanized rubber (length 100 mm × 25 width mm × thickness 3 mm) as the first layer used in Example A was used as the first layer.

[Third layer]
The following resin and metal were prepared as the third layer. In addition, all cut | disconnected and used for the magnitude | size of "length 100mm x 25 width mm x thickness 3mm".

<Resin>
XPA9055 (resin type: nylon elastomer, manufacturer: Ube Industries, product name: XPA9055)
Pebax 5533: (resin type: nylon elastomer, manufacturer: manufactured by Artema, product name: XPA9055)

<Metal>
・ Steel (Product number: SPCC, manufactured by Test Piece Co., Ltd.)
Note that when the third layer was a metal, the surface of the metal in contact with the fourth layer was subjected to the following surface treatment to be used as the third layer. Specifically, surface cleaning and roughness were imparted by blasting.

[Examples and Comparative Examples]
<Example B-1>
A composition in which a solvent (methyl ethyl ketone) is added to each of the components (A) to (E) as necessary in accordance with the following Table 3 (the numerical value of each component indicates the content (% by mass) of the nonvolatile content). Product (X) was obtained.

Chemlock 2000 was spray coated on the release sheet to form a 10 μm thick layer (fourth layer).
Then, the obtained composition (X) was apply | coated on the layer of Chemlock 2000, and the coating film was formed. The integrated light amount becomes 800 mJ / cm ² by a light emitting diode (UV-LED, LED-UV irradiation head (water-cooled) manufactured by Sentec Co., Ltd., light intensity 1200 mW / cm ² ) that emits light of 365 nm on the obtained coating film. As described above, an adhesive composition film was obtained by irradiating light. The thickness of the obtained adhesive composition film was 100 μm.

The surface of the first layer was brought into contact with the surface of the adhesive composition film that was not in contact with the release sheet, and the release sheet was peeled off.
Thereafter, the third layer shown in Table 3 is bonded onto the layer of Chemlock 2000 (the surface from which the release sheet is peeled), whereby the first layer and the second layer which is a layer of the adhesive composition film An overlapped body having a fourth layer and a third layer which are layers of Chemlock 2000 in this order was obtained.

The obtained layered product was held for 30 minutes while applying a pressurization pressure of 2.5 MPa at a temperature of 150 ° C., so that a rubber layer and a composition (X The laminated body which has the adhesion layer originating in (4), the layer originating in the 4th layer, and the 3rd layer in this order was obtained.
In addition, the thickness of the adhesive layer in the obtained laminate was 100 μm.

<Example B-2, Example B-3>
A laminate in the same manner as in Example B-1, except that the types and amounts of the components (A) to (E) used for the preparation of the composition (X) and the third layer are as shown in Table 3 below. Got.

<Comparative Example B-1>
Chemlock 2000 was sprayed directly onto the third layer to form a 10 μm thick layer (fourth layer).
Thereafter, the first layer was bonded to the surface of the Chemlock 2000 layer not in contact with the third layer, and an overlapped body having the first layer, the fourth layer, and the third layer in this order was obtained. .
The obtained layered product is held at a temperature of 150 ° C. for 30 minutes while applying a press pressure of 2.5 MPa, whereby the first layer of the unvulcanized rubber and the fourth layer are vulcanized. The laminated body which has the layer and 3rd layer originating in this order was obtained.

  About the laminated body obtained by the said Example and comparative example, the adhesive force of the rubber layer originating in a 1st layer and a 3rd layer was measured as follows. The results are shown in Table 3.

[Measurement method of adhesive strength (180 degree peel test)]
A 180 degree peel test was conducted by pulling the rubber layer derived from the first layer at the end of the laminate and the third layer in the direction of 180 ° under the condition of a tensile speed of 50 mm / min, and the peel strength (N / 25 mm) was measured and used as an index of adhesive strength. In addition, Table 3 shows the failure modes.
As the value of “adhesive strength” in the evaluation results, if the peel strength is 100 N / 25 mm or more, the adhesive strength is sufficient to destroy the rubber substrate before peeling occurs. Preferably it is 300 N / 25 mm or more. On the other hand, when the value of “adhesive strength” (peel strength) is less than 100 N / 25 mm, the adhesion between the rubber layer derived from the first layer and the third layer is not sufficient, and is it peeled off at each interface? Or, the adhesive layer itself cohesively breaks, and it cannot be said that the adhesive force is sufficient.

[Evaluation]
As shown in the above-mentioned table, in the examples, the reactive functional groups contained in component (B) with respect to the total number of moles of thiol groups contained in components (A) to (C) and contained in component (A). Since the second layer was formed using the composition (X) having a total molar ratio (FG / SH) of 0.15 or more and 0.25 or less, the adhesive strength was high.
On the other hand, since the second layer was not used in the comparative example, the adhesive force was low.

(Example C)
[Raw materials]
Component (A), component (B), component (C), component (D), component (E), and other radical generators are the same as in Example A above.
In addition, as the component (A ′), the component (B ′), and the component (C ′), those similar to the component (A), the component (B), and the component (C) were used, respectively.

[First layer]
The same unvulcanized rubber (length 100 mm × 25 width mm × thickness 3 mm) as the first layer used in Example A was used as the first layer.

[Third layer]
The same unvulcanized rubber as the first layer used in Example A was vulcanized at 165 ° C. for 30 minutes to produce a vulcanized rubber (length 100 mm × 25 width mm × thickness 3 mm). Used as 3 layers.

[Examples and Comparative Examples]
<Example C-1>
A composition (X) was obtained in the same manner as in Example A-2.
According to the following Table 4 (the numerical value of each component indicates the content (% by mass) of non-volatile content), if necessary, each of the above components (A ′) to (C ′) and (D) to (E) is a solvent. (Methyl ethyl ketone) was added to obtain a blended composition (Y).

The obtained composition (X) was applied to the surface of the first layer to form a coating film of the composition (X). On the other hand, the obtained composition (Y) was applied to the surface of the release sheet to form a coating film of the composition (Y).
The composition (X) and the composition (Y) are in contact with each other while the coating film of the composition (X) and the coating film of the composition (Y) are in liquid form (within 5 minutes after the coating film is formed). Thus, the 1st layer in which the coating film of composition (X) was formed, and the peeling sheet in which the coating film of composition (Y) was formed were bonded together. Then, by leaving it at room temperature (25 ° C.) for 180 minutes, a 200 μm thick adhesive composition film (the second layer and the coating film of the composition (X) and the coating film of the composition (Y) formed into a film) A fifth layer) was obtained.

  By peeling the release sheet and bonding the third layer to the surface of the adhesive composition film that is not in contact with the first layer (the surface from which the release sheet is peeled), the first layer and the adhesive composition film Thus, an overlapped body having the second layer, the fifth layer, and the third layer in this order was obtained.

The obtained layered product was held for 30 minutes while applying a pressurization pressure of 2.5 MPa at a temperature of 150 ° C., so that a rubber layer and a composition (X ) And an adhesive layer derived from the composition (Y) and a third layer in this order were obtained.
In addition, the thickness of the adhesive layer in the obtained laminate was 100 μm.

[Measurement method of adhesive strength of adhesive layer (T peel test)]
A T peel test was performed by pulling the rubber layer derived from the first layer at the end of the laminate and the third layer in the direction of 180 ° under the condition of a tensile speed of 50 mm / min, and the peel strength (N / 25 mm) was measured and used as an index of adhesive strength.
As a result, in Example C-1, the peel strength value (adhesive force) was 195 (N / 25 mm), and the failure mode was rubber failure.
As described above, the value of “adhesive strength” in the evaluation result is sufficient adhesive strength at which the rubber substrate is destroyed before peeling occurs when the peel strength is 100 N / 25 mm or more.

[Evaluation]
As shown in the above-mentioned table, in the examples, the composition (X) containing the components (A) to (C) and having a ratio (FG / SH) of 0.15 or more and 0.25 or less is used. A fifth layer is formed using the composition (Y) that forms a layer and includes the components (A ′) to (C ′) and the ratio (FG ′ / SH ′) is greater than 0.25 and equal to or less than 1.20. Because of this layer, the adhesive strength was high.
The disclosure of Japanese Patent Application No. 2014-136126 filed on July 1, 2014 is incorporated herein by reference in its entirety.
All documents, patent applications, and technical standards mentioned in this specification are to the same extent as if each individual document, patent application, and technical standard were specifically and individually described to be incorporated by reference, Incorporated herein by reference.

  In the superposed body in one embodiment of the present invention, the layer containing the unvulcanized rubber and the layer formed using the composition (X) are bonded with high adhesion by applying energy. In addition to mutual bonding, it can be used for bonding unvulcanized rubber and other members (vulcanized rubber, resin, and metal).

Claims (15)

A first layer comprising unvulcanized rubber;
A polythiol compound, a compound having a functional group that reacts with a thiol group, and a radical generator are included in the compound having a functional group that reacts with the thiol group with respect to the total number of moles (SH) of the thiol group contained in the polythiol compound. The first layer is formed by using the composition (X) containing a ratio (FG / SH) of the total number of moles (FG) of the functional groups that react with the thiol group to be 0.15 or more and 0.25 or less. A second layer in contact with,
I have a,
The polythiol compound has a primary thiol group as the thiol group,
The compound having a functional group that reacts with the thiol group is a laminate including at least one selected from an isocyanate group, an acryloyl group, and a methacryloyl group as the functional group that reacts with the thiol group .   The superposition body according to claim 1, wherein the polythiol compound has 3 to 6 thiol groups in one molecule.   The layered product according to claim 1 or 2, wherein the polythiol compound is a mercapto fatty acid esterified product.   The compound having a functional group that reacts with the thiol group includes at least one selected from an isocyanate group and a methacryloyl group as the functional group that reacts with the thiol group. The superimposed body described. The superimposed body according to any one of claims 1 to 4 , wherein the compound having a functional group that reacts with the thiol group has three or more functional groups that react with the thiol group in one molecule. The layered product according to any one of claims 1 to 5 , wherein the compound having a functional group that reacts with the thiol group has a cyclic structure. The first layer, the second layer, and a third layer including at least one selected from unvulcanized rubber, vulcanized rubber, resin, and metal in this order. The superposed body according to any one of claims 6 to 7 . The laminated body according to claim 7 , wherein the third layer includes unvulcanized rubber and contacts the second layer. The third layer includes at least one of a resin and a metal;
8. The method according to claim 7 , further comprising a fourth layer formed between the second layer and the third layer by using an adhesive having an adhesive force with respect to at least one of the resin and the metal. The superimposed body described. The third layer comprises vulcanized rubber;
Between the second layer and the third layer, a polythiol compound, a compound having a functional group that reacts with a thiol group, and a radical generator containing a total number of moles of thiol groups contained in the polythiol compound (SH ′ ) The ratio (FG ′ / SH ′) of the total number of moles (FG ′) of the functional groups reacting with the thiol group contained in the compound having the functional group reacting with the thiol group is greater than 0.25 and 1.20. have a fifth layer formed by using the composition comprising the following (Y),
The polythiol compound contained in the composition (Y) has a primary thiol group as the thiol group,
The compound having a functional group that reacts with the thiol group contained in the composition (Y) includes at least one selected from an isocyanate group, an acryloyl group, and a methacryloyl group as the functional group that reacts with the thiol group. The superimposed body according to claim 7 . Said 2nd layer and said 5th layer are the said in the coating film of said composition (X) in the state which the coating film of said composition (X) and the coating film of said composition (Y) contacted. The composition by polymerization of a polythiol compound and a compound having a functional group that reacts with the thiol group, and polymerization of the polythiol compound and a compound having a functional group that reacts with the thiol group in the coating film of the composition (Y) The layered product according to claim 10 , which is an adhesive composition film in which the coating film of (X) and the coating film of the composition (Y) are formed into a film. The second layer is an adhesive composition film in which the polythiol compound and a compound having a functional group that reacts with the thiol group are polymerized to form a coating film of the composition (X). The superposed body according to any one of claims 1 to 9 . An overlapping body forming step of forming the overlapping body according to any one of claims 1 to 9 and claim 12 ,
By applying energy for activating the radical generator contained in the second layer of the superposed body to the superposed body, and making the second layer an adhesive layer, the first layer Obtaining a laminate having the adhesive layer on the layer, an energy application step;
The manufacturing method of the laminated body containing this. An overlapping body forming step for forming the overlapping body according to claim 10 or 11 ,
Energy for activating the radical generator included in the second layer of the stack and energy for activating the radical generator included in the fifth layer are applied to the stack. An energy application step of obtaining a laminate having the first layer, the adhesive layer, and the third layer in this order by using the second layer and the fifth layer as an adhesive layer;
The manufacturing method of the laminated body containing this. The polythiol compound, a compound having a functional group that reacts with a thiol group, and a compound having a functional group that reacts with the thiol group with respect to the total number of moles (SH) of thiol groups contained in the polythiol compound are included in the polythiol compound. Reacts with the coating film of the composition (X) containing the ratio (FG / SH) of the total number of moles (FG) of the functional groups that react with the thiol group (FG / SH) between 0.15 and 0.25, the polythiol compound, and the thiol group. A functional group that reacts with the thiol group contained in the compound having a functional group and a compound that has a functional group that reacts with the thiol group relative to the total number of moles (SH ′) of thiol groups contained in the polythiol compound. A coating film of the composition (Y) containing a ratio (FG ′ / SH ′) of the total number of moles (FG ′) of greater than 0.25 and not greater than 1.20; In contact,
Polymerization of the polythiol compound and a compound having a functional group that reacts with the thiol group in the coating film of the composition (X) and a function of reacting with the polythiol compound and the thiol group in the coating film of the composition (Y). An adhesive composition film in which the coating film of the composition (X) and the coating film of the composition (Y) are formed into a film by polymerization with a compound having a group ;
The polythiol compound contained in the composition (X) and the polythiol compound contained in the composition (Y) have a primary thiol group as the thiol group,
The compound having a functional group that reacts with the thiol group contained in the composition (X) and the compound having a functional group that reacts with the thiol group contained in the composition (Y) are functionally reactive with the thiol group. An adhesive composition film comprising at least one selected from an isocyanate group, an acryloyl group, and a methacryloyl group as a group .