KR102639338B1 - Laminate for bonding, method for bonding two adherends, and method for manufacturing bonded structure - Google Patents

Abstract

The present invention has a molecular adhesive layer containing a specific molecular adhesive (M), a first thermoplastic resin layer containing a specific thermoplastic resin, and a second thermoplastic resin layer in this order, and the molecular adhesive layer and the second thermoplastic resin layer. A laminate for bonding in which two thermoplastic resin layers constitute the outermost layer during use, wherein the heat sealable temperature of the first thermoplastic resin layer is T _h1 and the heat sealability of the second thermoplastic resin layer is T h1. When the temperature is T _h2 , a laminate for bonding in which T _h1 > T _h2 , a method of joining two adherends using this laminate for bonding, and a method of manufacturing a bonded structure. By using the laminate for bonding of the present invention, a heat welding process can be performed without adversely affecting the molecular adhesive layer.

Description

Laminate for bonding, method for bonding two adherends, and method for manufacturing bonded structure

The present invention relates to a laminate for bonding having a molecular adhesive layer (refers to a layer formed using a molecular adhesive; the same applies hereinafter), a method for bonding two adherends using this laminate for bonding, and a bonding structure. It is about manufacturing method.

Compounds having two or more types of reactive groups are useful as molecular adhesives because they can form chemical bonds using the characteristics of each reactive group.

For example, in Patent Document 1, as a method of joining base A and base B, a process of forming a molecular adhesive layer on the surface of base A using a specific molecular adhesive, and a process for forming a molecular adhesive layer on the surface of base A, A joining method is described that includes a step of arranging the base B toward the base B and a step of applying force to the base A and the base B to join the base A and the base B.

Patent Document 1 describes a method of forming a molecular adhesive layer on the surface of a base, by preparing a molecular adhesive liquid in which the molecular adhesive is dissolved or dispersed, immersing the base body in this molecular adhesive liquid, and then irradiating it with ultraviolet rays, A method of forming a molecular adhesive layer by forming a chemical bond between a molecular adhesive and the surface of a substrate is described.

WO2012/043631 (US2013/177770 A1)

As described in Patent Document 1, a double-sided adhesive sheet having a molecular adhesive layer on both sides of the base can be efficiently obtained by immersing the base in a molecular adhesive solution. Such a double-sided adhesive sheet is useful as a bonding material for easily and firmly fixing two adherends.

However, when the roll-to-roll method is used to mass-produce such double-sided adhesive sheets, it is difficult to stably form a molecular adhesive layer on both sides of the base by the dipping method.

Therefore, there has been a demand for a method that can firmly bond two adherends using an adhesive sheet having a molecular adhesive layer obtained by employing a roll-to-roll method.

The present inventors studied a method of joining two adherends using a bonding laminate having a molecular adhesive layer on only one surface. As a result, two laminates for bonding having a molecular adhesive layer on a thermoplastic resin layer were prepared, each molecular adhesive layer was bonded to each adherend, and the two thermoplastic resin layers were heat-welded. , it was found that two adherends could be firmly joined.

However, in this joining method, depending on the conditions when heat welding two thermoplastic resin layers, the thermoplastic resin layer may be greatly deformed, and as a result, the molecular adhesive layer may be deformed or the molecular adhesive layer may be damaged. There was a risk that the adhesive strength would decrease.

The present invention was made for the purpose of solving this problem, and is a laminate for bonding having a molecular adhesive layer and a thermoplastic resin layer, which can be subjected to a heat welding process without adversely affecting the molecular adhesive layer. The object is to provide a laminate, a method of joining two adherends using this bonding laminate, and a method of manufacturing a bonded structure.

In order to solve the above problems, the present inventors have intensively studied a method of joining two adherends using a bonding laminate having a molecular adhesive layer and a thermoplastic resin layer.

As a result, it was found that the heat welding process can be performed without adversely affecting the molecular adhesive layer by using a bonding laminate that satisfies the following requirements (a) to (c), and the present invention was completed. reached.

Requirement (a): The thermoplastic resin layer is composed of a first thermoplastic resin layer and a second thermoplastic resin layer.

Requirement (b): A molecular adhesive layer is formed on the first thermoplastic resin layer.

Requirement (c): The second thermoplastic resin layer is a layer that can be heat-welded at a lower temperature than the first thermoplastic resin layer.

In this way, according to the present invention, the laminate for joining of the following (1) to (6), the method of joining two adherends of (7) to (9), and the bonding structure of (10) to (11). Manufacturing methods are provided.

(1) a molecular adhesive layer containing a molecular adhesive (M), a first thermoplastic resin layer having a single-layer structure, and a second thermoplastic resin layer having a single-layer structure or a multi-layer structure in this order, wherein the molecular adhesive layer and a second thermoplastic resin layer each constitute an outermost layer when used, wherein the molecular adhesive (M) contains an amino group, an azide group, a mercapto group, an isocyanate group, a ureido group, and an epoxy group. A compound having at least one type of reactive group (Zα) selected from the group consisting of, a silanol group, and at least one type of reactive group (Zβ) selected from the group consisting of a group that generates a silanol group by a hydrolysis reaction, , the first thermoplastic resin layer has, at least on the surface of the side in contact with the molecular adhesive layer, a reactive partial structure (Zγ) capable of forming a chemical bond with the reactive group (Zα) of the molecular adhesive (M). It contains a thermoplastic resin (P ₁ ), and when the heat sealable temperature of the first thermoplastic resin layer is T _h1 and the heat sealable temperature of the second thermoplastic resin layer is T _h2 , T _h1 > T _h2 phosphorus bonding laminate.

(2) The reactive group (Zα) of the molecular adhesive (M) is at least one selected from the group consisting of an amino group, a mercapto group, an isocyanate group, a ureido group, and an epoxy group, and the thermoplastic resin (P ₁ ) is The reactive partial structure (Zγ) that the molecular adhesive (M) has is at least one selected from the group consisting of a hydroxy group, a carboxyl group, an aldehyde group, and an amino group, or the reactive group (Zα) that the molecular adhesive (M) has is an azide group. and the reactive partial structure (Zγ) of the thermoplastic resin (P ₁ ) is at least one selected from the group consisting of a carbon-carbon single bond, a carbon-carbon double bond, and a carbon-hydrogen single bond, (1) The laminate for joining described in .

(3) The laminate for bonding according to (1) or (2), wherein the molecular adhesive (M) is a compound represented by the following formula (1).

[Formula 1]

(R ¹ is a reactive group (Zα) selected from the group consisting of an amino group, an azide group, a mercapto group, an isocyanate group, a ureido group, and an epoxy group, or a monovalent group having one or more of these reactive groups (however, an amino group, azide group, mercapto group, isocyanate group, ureido group and epoxy group are excluded), G represents a divalent organic group, Y represents a hydrocarbon group having 1 to 20 carbon atoms. a represents an integer of 1 to 3.)

(4) The reactive group (Zα) of the molecular adhesive (M) and the reactive partial structure (Zγ) of the thermoplastic resin (P ₁ ) form a chemical bond according to any one of (1) to (3). Laminate for joining.

(5) The thermoplastic resin (P ₁ ) is at least one selected from the group consisting of olefin resin, cycloolefin resin, acrylic resin, olefin-vinyl acetate resin, olefin ionomer resin, and polyester resin. The laminate for joining according to any one of (1) to (4).

(6) The second thermoplastic resin layer includes, at least on the surface opposite to the molecular adhesive layer, an olefin resin, a cycloolefin resin, an acrylic resin, an olefin-vinyl acetate resin, an olefin ionomer resin, and poly The laminate for bonding according to any one of (1) to (5), which contains at least one member selected from the group consisting of ester resins.

(7) A method of bonding an adherend (I) and an adherend (II) using two bonding laminates, wherein the two bonding laminates each independently have the following properties among (1) to (6): A laminate for bonding according to any one of the above, wherein the first laminate for bonding is a molecular adhesive layer (AM) containing a molecular adhesive ( _MA ), a first thermoplastic resin layer (A-1) having a single-layer structure, and a second thermoplastic resin layer (A-2) having a single-layer structure or a multi-layer structure in this order, represented by a laminate for bonding (A), and the second laminate for bonding comprising a molecular adhesive ( _MB ). For bonding having a molecular adhesive layer (BM), a first thermoplastic resin layer (B-1) having a single-layer structure, and a second thermoplastic resin layer (B-2) having a single-layer structure or a multi-layer structure in this order. When represented as a laminate (B), a process group including the following steps (L1) to (L3), a process group including steps (M1) to (M3), and steps (N1) and (N2) A method for bonding an adherend (I) and an adherend (II), characterized by carrying out a process group selected from the process group containing the following.

Process (L1): Process of bonding the molecular adhesive layer (A-M) of the laminate for bonding (A) and the adherend (I)

Process (L2): Process of bonding the molecular adhesive layer (B-M) of the laminate for bonding (B) and the adherend (II)

Step (L3): Heat welding the second thermoplastic resin layer (A-2) of the laminate obtained in step (L1) and the second thermoplastic resin layer (B-2) of the laminate obtained in step (L2). process

Step (M1): A process of heat welding the second thermoplastic resin layer (A-2) of the laminate for joining (A) and the second thermoplastic resin layer (B-2) of the laminate for joining (B).

Step (M2): A step of bonding the molecular adhesive layer (A-M) of the laminate obtained in step (M1) and the adherend (I).

Step (M3): A step of bonding the molecular adhesive layer (B-M) of the laminate obtained in step (M2) and the adherend (II).

Step (N1): An arrangement in which the second thermoplastic resin layer (A-2) of the laminate for joining (A) and the second thermoplastic resin layer (B-2) of the laminate for joining (B) face each other. , a process of overlapping the adherend (I), the laminate for bonding (A), the laminate for bonding (B), and the adherend (II) in this order.

Step (N2): Heating the product obtained in step (N1), adhesion of the molecular adhesive layer (A-M) and the adherend (I), adhesion of the molecular adhesive layer (B-M) and the adherend (II), and second heat A process of simultaneously performing heat welding of the plastic resin layer (A-2) and the second thermoplastic resin layer (B-2)

(8) A method for bonding an adherend (I) and an adherend (II), carrying out a group of processes including the above steps (L1) to (L3),

In step (L1), the temperature at which the molecular adhesive layer (AM) of the bonding laminate (A) and the adherend (I) are bonded is T _L1 . In the step (L2), the temperature of the bonding laminate (B) is T L1. ) The temperature at which the molecular adhesive layer (BM) and the adherend (II) are bonded is T _L2 , and in step (L3), the second thermoplastic resin layer (A-2) and the second thermoplastic resin layer ( The temperature when heat welding B-2) is T _L3 , the heat sealable temperature of the first thermoplastic resin layer (A-1) of the laminate for joining (A) is T _h1A , and the second thermoplastic resin layer ( The heat sealable temperature of A-2) is T _h2A , the heat sealable temperature of the first thermoplastic resin layer (B-1) of the bonding laminate (B) is T _h1B , and the second thermoplastic resin layer (B) When the heat sealable temperature of -2) is T _h2B , both the following equations (E-1) and (E-2) are satisfied, and at least the following equations (E-3) and (E-4) are satisfied. The method of joining the adherend (I) and the adherend (II) according to (7), which satisfies one of the conditions.

(9) A method of bonding an adherend (I) and an adherend (II), carrying out a group of processes including the above steps (N1) and (N2), wherein the laminate for bonding (A) is subjected to first thermoplasticity. The heat sealable temperature of the resin layer (A-1) is T _h1A , the heat sealable temperature of the second thermoplastic resin layer (A-2) is T _h2A , and the first thermoplastic water of the laminate for bonding (B) is T h2A. The heat sealable temperature of the stratum (B-1) is T _h1B , the heat sealable temperature of the second thermoplastic resin layer (B-2) is T _h2B , and the temperature at the time of heat welding in step (N2) is The method of bonding the adherend (I) and the adherend (II) according to (7), which satisfies at least one of the following formulas (E-5) and (E-6) when T _N2 .

(10) A method for producing a bonded structure having a layer structure of the adherend (I)/laminated body for bonding (A) and the layer/adherent (II) derived from the laminate for bonding (B), comprising: (7) to A method for producing a bonded structure, characterized by bonding the adherend (I) and the adherend (II) using the method according to any one of (9).

(11) The adherend (I) and the adherend (II) each independently contain at least one type selected from the group consisting of metals, inorganic substances, and thermosetting resins on at least the adherend surface, ( 10) The method for manufacturing the bonded structure described in .

In the present invention, a molecular adhesive refers to a compound having two or more types of reactive groups.

The term “containing a molecular adhesive” in “molecular adhesive layer containing a molecular adhesive” means “a molecular adhesive and/or a compound derived from a molecular adhesive (for example, a compound in which the structure of the reactive group has changed through reaction). It means “including.”

“The first thermoplastic resin layer includes a thermoplastic resin having a reactive partial structure (Zγ)” means “a thermoplastic resin having a reactive partial structure (Zγ) and/or a resin derived from this thermoplastic resin (e.g. For example, the structure of the reactive partial structure (Zγ) has changed through reaction).

“The molecular adhesive layer and the second thermoplastic resin layer constitute the outermost layer when each is used” means that when adhering the molecular adhesive layer to an adherend or heat welding the second thermoplastic resin layers to each other, respectively This means that the layer of is the outermost layer. Therefore, from the time the laminate for bonding is manufactured until the time it is used, the laminate for bonding may have a protective sheet or the like as an outermost layer.

The “heat sealable temperature” of the thermoplastic resin layer is the temperature required during heat welding in order to achieve sufficient heat seal strength. Specifically, the heat sealable temperature can be obtained according to the method described in the examples. .

“Temperature when bonding the molecular adhesive layer and the adherend” or “Temperature when heat welding the thermoplastic resin layer and the thermoplastic resin layer” refers to the pressing member of the device when using a heat press machine, etc. refers to the surface temperature of

In addition, in this specification, the unit of temperature is “℃”.

According to the present invention, a bonding laminate has a molecular adhesive layer and a thermoplastic resin layer, and can be subjected to a heat welding process without adversely affecting the molecular adhesive layer. This bonding laminate is used. A method for joining two adherends and a method for manufacturing a bonded structure are provided.

1 is a schematic diagram showing an example of a manufacturing process for a laminate for bonding of the present invention.
Figure 2 is a schematic diagram showing a process group including processes (L1) to (L3).
Figure 3 is a schematic diagram showing a process group including processes (M1) to (M3).
Figure 4 is a schematic diagram showing a process group including processes (N1) and (N2).

Hereinafter, the present invention will be described in detail by dividing it into 1) a laminate for joining, 2) a method of joining two adherends, and 3) a method of manufacturing a bonded structure.

1) Laminate for joining

The laminate for bonding of the present invention includes a molecular adhesive layer containing a molecular adhesive (M), a first thermoplastic resin layer having a single-layer structure, and a second thermoplastic resin layer having a single-layer structure or a multi-layer structure in this order. A laminate for bonding, wherein the molecular adhesive layer and the second thermoplastic resin layer each constitute an outermost layer when used, wherein the molecular adhesive (M) contains an amino group, an azide group, a mercapto group, and an isocyanate. At least one reactive group (Zα) selected from the group consisting of a ureido group and an epoxy group, and at least one reactive group selected from the group consisting of a silanol group and a group that generates a silanol group through a hydrolysis reaction ( It is a compound having Zβ), and the first thermoplastic resin layer has, at least on the surface of the side in contact with the molecular adhesive layer, a reactive moiety capable of forming a chemical bond with the reactive group (Zα) of the molecular adhesive (M). It contains a thermoplastic resin (P ₁ ) having a structure (Zγ), wherein the heat sealable temperature of the first thermoplastic resin layer is T _h1 and the heat sealable temperature of the second thermoplastic resin layer is T _h2 . When T _h1 > T _h2 , it is a laminate for joining.

[Molecular adhesive layer]

The molecular adhesive layer is a layer directly adjacent to the first thermoplastic resin layer.

The molecular adhesive layer is a layer that constitutes one of the outermost layers when using the laminate for bonding.

The molecular adhesive layer is used for adhesion to the adherend.

The molecular adhesive layer is a layer formed using the molecular adhesive (M) and contains the molecular adhesive (M). That is, the molecular adhesive layer in the laminate for bonding contains at least one of the molecular adhesive (M) (where the reactive group remains) and the reaction product of the molecular adhesive (M) (where the structure of the reactive group has changed). will be.

The molecular adhesive (M) contains at least one reactive group (Zα) selected from the group consisting of an amino group, an azide group, a mercapto group, an isocyanate group, a ureido group, and an epoxy group, a silanol group, and a hydrolysis reaction. It is a compound having at least one type of reactive group (Zβ) selected from the group consisting of groups that generate silanol groups. In addition, the “amino group” of the reactive group (Zα) includes an unsubstituted amino group, a mono-substituted amino group, a di-substituted amino group, a primary ammonium group, a secondary ammonium group, a tertiary ammonium group, and a quaternary ammonium group.

The reactive group (Zα) in the molecular adhesive (M) is capable of forming a chemical bond with the reactive partial structure (Zγ) of the thermoplastic resin (P ₁ ) in the first thermoplastic resin layer.

In the laminate for bonding, it is believed that the molecular adhesive (M) is chemically fixed to the surface of the first thermoplastic resin layer by this chemical bond. Chemical bonds at this time include covalent bonds, hydrogen bonds, ionic bonds, and intermolecular forces, but covalent bonds are preferred.

The reactive group (Zβ) in the molecular adhesive (M) is mainly used to form a chemical bond with the adherend when bonding the laminate for bonding to the adherend. Therefore, the laminate for bonding is preferably used for adherends having groups on the surface that are highly reactive with these groups.

Groups that generate silanol groups through hydrolysis reactions include groups having a partial structure represented by Si-X ¹ . X ¹ is an alkoxy group having 1 to 10 carbon atoms, such as a methoxy group, ethoxy group, n-propoxy group, or isopropoxy group; Halogen atoms such as fluorine atom, chlorine atom, and bromine atom; Hydrolyzable groups such as these can be mentioned.

Examples of the molecular adhesive (M) include compounds represented by the following formula (1).

[Formula 2]

(R ¹ represents a reactive group (Zα) or a monovalent group having one or more reactive groups (Zα) (however, the reactive group (Zα) itself is excluded), G represents a divalent organic group, (

Examples of the monovalent group having one or more reactive groups (Zα) for R ¹ include groups represented by the following formulas (2) to (4).

[Formula 3]

In formulas (2) to (4), * represents a bond with G.

R ² represents a divalent hydrocarbon group having 1 to 10 carbon atoms, preferably a divalent hydrocarbon group having 2 to 6 carbon atoms. Examples of the divalent hydrocarbon group for R ² include alkylene groups such as ethylene group, trimethylene group, and propylene group; Arylene groups such as o-phenylene group, m-phenylene group, and p-phenylene group; can be mentioned.

R ³ and R ⁴ each independently represent a hydrogen atom or a hydrocarbon group with 1 to 20 carbon atoms, and a hydrogen atom or a hydrocarbon group with 1 to 10 carbon atoms is preferable.

The hydrocarbon groups of R ³ and R ⁴ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, t-butyl group, n-pentyl group, and n-hexyl group. Alkyl groups such as syl group, n-heptyl group, n-octyl group, n-nonyl group, and n-decyl group; Alkenyl groups such as vinyl group, 1-propenyl group, 2-propenyl group, isopropenyl group, 3-butenyl group, 4-pentenyl group, and 5-hexenyl group; Alkynyl groups such as ethynyl group, propargyl group, and butynyl group; Aryl groups such as phenyl group, 1-naphthyl group, and 2-naphthyl group; etc. can be mentioned.

Z represents a single bond or a divalent group represented by -N(R ⁷ )-. R ⁷ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Examples of the hydrocarbon group for R ⁷ include the same hydrocarbon groups as R ³ and R ⁴ .

R ⁵ and R ⁶ are each independently a reactive group (Zα) or a group represented by the above formula (2) (in this case, in formula (2), * represents the bond with the carbon atom constituting the aromatic ring. indicates).

The divalent organic group of G may have a substituent, or be an unsubstituted alkylene group having 1 to 20 carbon atoms, have a substituent or unsubstituted alkenylene group having 2 to 20 carbon atoms, have a substituent, or be unsubstituted. a substituted alkynylene group having 2 to 20 carbon atoms, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms; etc. can be mentioned.

Examples of the alkylene group having 1 to 20 carbon atoms for G include methylene group, ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, and hexamethylene group.

Examples of the alkenylene group having 2 to 20 carbon atoms for G include vinylene group, propenylene group, butenylene group, and pentenylene group.

Examples of the alkynylene group having 2 to 20 carbon atoms for G include ethynylene group and propynylene group.

Examples of the arylene group having 6 to 20 carbon atoms for G include o-phenylene group, m-phenylene group, p-phenylene group, 2,6-naphthylene group, and 1,5-naphthylene group.

Examples of the alkylene group, alkenylene group, and substituent for the alkynylene group include halogen atoms such as a fluorine atom and a chlorine atom; Alkoxy groups such as methoxy group and ethoxy group; Alkylthio groups such as methylthio groups and ethylthio groups; Alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group; etc. can be mentioned.

Substituents for the arylene group include cyano group; nitro group; Halogen atoms such as fluorine atom, chlorine atom, and bromine atom; Alkyl groups such as methyl group and ethyl group; Alkoxy groups such as methoxy group and ethoxy group; Alkylthio groups such as methylthio groups and ethylthio groups; etc. can be mentioned.

These substituents may be bonded to any position in groups such as alkylene group, alkenylene group, alkynylene group, and arylene group. Additionally, a plurality of substituents, identical or different, may be bonded to a group such as an alkylene group.

Examples of the alkoxy group having 1 to 10 carbon atoms for X include methoxy group, ethoxy group, n-propoxy group, and isopropoxy group.

Halogen atoms for X include fluorine atoms, chlorine atoms, and bromine atoms.

Examples of the hydrocarbon group of Y having 1 to 20 carbon atoms include the same hydrocarbon groups as R ³ and R ⁴ .

Specific examples of the molecular adhesive (M) include, but are not limited to, the following.

3-Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyldiethoxymethylsilane, [3-(N,N-dimethylamino)propyl]tri R such as methoxysilane, [3-(phenylamino)propyl]trimethoxysilane, trimethyl[3-(triethoxysilyl)propyl]ammonium chloride, trimethyl[3-(trimethoxysilyl)propyl]ammonium chloride, etc. ¹ is an amino group; molecular adhesive;

Molecular adhesives in which R ¹ is an azide group, such as (11-azidoundecyl)trimethoxysilane and (11-azidoundecyl)triethoxysilane;

Molecular adhesives in which R ¹ is a mercapto group, such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and 3-mercaptopropyldimethoxymethylsilane;

Molecular adhesives in which R ¹ is an isocyanate group, such as 3-(trimethoxysilyl)propyl isocyanate and 3-(triethoxysilyl)propyl isocyanate;

Molecular adhesives in which R ¹ is a ureido group, such as 3-ureidopropyltrimethoxysilane and 3-ureidopropyltriethoxysilane;

R ¹ is an epoxy group, such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycidoxypropylmethyldiethoxysilane. molecular adhesive;

3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propyltriethoxysilane, 3-(2-aminoethylamino)propyldimethoxymethylsilane, 2-(3, Molecular adhesives in which R ¹ is a monovalent group having one or more reactive groups (Zα), such as 4-epoxycyclohexyl)ethyltrimethoxysilane and compounds represented by formulas (5) to (13) below.

[Formula 4]

Molecular adhesive (M) can be used individually or in combination of two or more types.

Among these compounds, the compound represented by formula (1) is preferably a compound in which R ¹ is a group represented by formula (4), more preferably a compound represented by formulas (5) to (13), and more preferably a compound represented by formula (5) to (13). The compound represented by (10) is more preferable.

These compounds have a triazine ring at R ¹ . The molecular adhesive (M) having a triazine ring tends to be fixed more efficiently on the first thermoplastic resin layer.

As the molecular adhesive (M), a compound known as a silane coupling agent can be used. In addition, compounds in which R ¹ is a group represented by formula (4) can be synthesized according to the methods described in WO2012/046651, WO2012/043631, WO2013/186941, etc.

The molecular adhesive layer may contain components other than the molecular adhesive (M). Components other than the molecular adhesive (M) include catalysts and the like.

The catalyst can be appropriately selected and used depending on the type of reactive group (Zα).

The content of the molecular adhesive (M) in the molecular adhesive layer is preferably 50% by mass or more based on the entire molecular adhesive layer, because if components not involved in adhesion are included, the adhesive strength of the molecular adhesive layer decreases. , it is more preferable that it is 70 mass% or more and 100 mass% or less, it is still more preferable that it is 90 mass% or more and 100 mass% or less, and 100 mass% is especially preferable.

The thickness of the molecular adhesive layer is preferably 200 nm or less, more preferably 150 nm or less, further preferably 100 nm or less, and especially preferably 50 nm or less. Moreover, the thickness of the molecular adhesive layer is preferably 0.5 nm or more, and more preferably 1 nm or more.

[First thermoplastic resin layer]

The first thermoplastic resin layer is a layer adjacent to the molecular adhesive layer and plays a role in fixing the molecular adhesive (M).

The first thermoplastic resin layer has a single-layer structure.

The first thermoplastic resin layer may have a uniform composition, and the composition does not need to be uniform. For example, the first thermoplastic resin layer may contain many specific components near the surface of the layer, and the composition near the surface of the layer may be different from the composition inside the layer.

The first thermoplastic resin layer has, at least on the surface of the side in contact with the molecular adhesive layer, a reactive partial structure (Zγ) capable of forming a chemical bond with the reactive group (Zα) of the molecular adhesive (M). It contains resin (P ₁ ). That is, the first thermoplastic resin layer in the laminate for bonding is a reaction product (reactive partial structure) of the thermoplastic resin (P ₁ ) (where the reactive partial structure (Zγ) remains) and the thermoplastic resin (P ₁ ). It includes at least one of (Zγ) changed).

In addition, “the surface on the side in contact with the molecular adhesive layer contains a thermoplastic resin (P ₁ )” means that in the step before forming the molecular adhesive layer, the surface of the first thermoplastic resin layer contains a thermoplastic resin (P 1 ). ₁ ) This indicates the state of being exposed.

In the step before forming the molecular adhesive layer, the thermoplastic resin (P ₁ ) is exposed to the surface of the first thermoplastic resin layer, so that the reactive partial structure (Zγ) of the thermoplastic resin (P ₁ ) is molecule It can react efficiently with the reactive group (Zα) of the adhesive (M).

Examples of the thermoplastic resin (P ₁ ) include olefin resin, cycloolefin resin, acrylic resin, olefin-vinyl acetate resin, olefin ionomer resin, and polyester resin.

Examples of the olefin resin include low-density polyethylene, linear low-density polyethylene, high-density polyethylene, ethylene-propylene copolymer, polypropylene, propylene-α-olefin copolymer, poly(4-methyl-1-pentene), etc. .

Examples of cycloolefin-based resins include addition polymers of cycloolefins, copolymers of cycloolefins and α-olefins, and ring-opening polymers of norbornene-based monomers.

Examples of cycloolefins include cyclopentene, cyclooctene, and norbornene monomers.

Examples of α-olefins include ethylene and propylene.

Acrylic resins include homopolymers of (meth)acrylic monomers, copolymers of (meth)acrylic monomers, and copolymers of a (meth)acrylic monomer and a monomer copolymerizable therewith.

(meth)acrylic monomers include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, and 2-hydroxyethyl (meth)acrylate. , (meth)acrylic acid esters such as 2-ethylhexyl (meth)acrylate; (meth)acrylic acid; etc. can be mentioned.

Monomers copolymerizable with (meth)acrylic monomers include ethylene; Aromatic vinyl monomers such as styrene, α-methylstyrene, and chlorostyrene; Cyano group-containing ethylenically unsaturated monomers such as acrylonitrile and methacrylonitrile; (meth)acrylamide-based monomers such as (meth)acrylamide, N-methylol (meth)acrylamide, and N-butoxymethyl (meth)acrylamide; etc. can be mentioned.

In this specification, “(meth)acrylic acid” means “acrylic acid or methacrylic acid.” The same applies to similar substrates such as “(meth)acrylic acid ester,” “(meth)acrylic,” and “(meth)acrylate.”

Examples of the olefin-vinyl acetate resin include ethylene-vinyl acetate copolymer.

Examples of the olefinic ionomer resin include a copolymer having a repeating unit derived from an olefinic monomer and a repeating unit derived from a carboxyl group-containing monomer, and a resin having an ionic crosslink connecting the chains of this copolymer.

Examples of olefin-based monomers include ethylene and propylene.

Examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, maleic acid monomethyl ester, and maleic acid monoethyl ester.

The ionic crosslinking of the olefin-based ionomer resin is composed of carboxylate ions and metal ions generated by deprotonation of the carboxyl group of the carboxyl group-containing monomer.

Metal ions include sodium (I) ion, potassium (I) ion, lithium (I) ion, calcium (II) ion, magnesium (II) ion, zinc (II) ion, copper (I) ion, and copper (II) ion. ) ion, cobalt (II) ion, cobalt (III) ion, nickel (II) ion, manganese (II) ion, aluminum (III) ion, etc.

Examples of the polyester resin include those obtained by polycondensation reaction of polyhydric carboxylic acid and polyhydric alcohol.

Polyhydric carboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanoic acid, 1,4-cyclohexanedicarboxylic acid, and 1,4-naphthalene. Dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, trimellitic acid, etc. are mentioned.

Polyhydric alcohols include ethylene glycol, propylene glycol, 1,4-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,9-nonanediol, 1,4-cyclohexanedimethanol, diethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, trimethylolpropane, Glycerin, etc. can be mentioned.

Among polyester resins, amorphous polyester resins are more preferable. An amorphous polyester resin refers to a polyester resin that does not exhibit clear crystallization or crystal melting peaks by DSC (differential scanning calorimetry).

Amorphous polyester resins include glycol-modified polyethylene terephthalate (PETG), glycol-modified poly(1,4-cyclohexanedimethylene terephthalate) (PCTG), and acid-modified poly(1,4-cyclohexanedimethylene terephthalate). ) (PCTA), etc.

Thermoplastic resin (P ₁ ) can be used individually or in combination of two or more types.

The thermoplastic resin (P ₁ ) has a reactive partial structure (Zγ) that can form a chemical bond with the reactive group (Zα) of the molecular adhesive (M).

When the thermoplastic resin (P ₁ ) has a reactive partial structure (Zγ), the molecular adhesive (M) can be efficiently fixed.

The reactive partial structure (Zγ) of the thermoplastic resin (P ₁ ) includes a hydroxy group, a carboxyl group, an aldehyde group, an amino group, a carbon-carbon single bond, a carbon-carbon double bond, and a carbon-hydrogen single bond. As will be described later, these can be appropriately selected according to the reactive group (Zα) in the molecular adhesive (M).

When the thermoplastic resin (P ₁ ) is a thermoplastic resin (P ₁ ') having a functional group such as a hydroxy group, a carboxyl group, an aldehyde group, an amino group, etc. as a reactive partial structure (Zγ), in the thermoplastic resin (P ₁ ') These reactive partial structures (Zγ') can be formed by known methods.

For example, when carrying out a polymerization reaction, a thermoplastic resin (P ₁ ') having a reactive partial structure (Zγ') can be produced by using a monomer having a functional group such as a hydroxy group, carboxyl group, aldehyde group, or amino group. You can. Additionally, a thermoplastic resin (P ₁ ') having a reactive partial structure (Zγ') is produced by performing a polymerization reaction without using these monomers and subjecting the obtained polymer to a modification treatment such as maleic anhydride modification. can do.

By using the thermoplastic resin (P ₁ ') obtained by these methods as a molding material, the first thermoplastic resin layer can be formed efficiently.

Additionally, after forming a thermoplastic resin layer not containing a thermoplastic resin (P ₁ '), the thermoplastic resin layer may be subjected to surface treatment to generate hydroxy groups or carboxyl groups on the surface of the layer. In other words, by performing this surface treatment, this thermoplastic resin layer satisfies the requirements necessary for the first thermoplastic resin layer.

The surface treatment is not particularly limited as long as it generates hydroxy groups or carboxyl groups. Surface treatments include corona treatment, plasma treatment, ultraviolet irradiation treatment, electron beam irradiation treatment, ozone treatment, excimer ultraviolet treatment, acid treatment, and base treatment.

These surface treatments can be performed according to known methods.

The first thermoplastic resin layer may contain components other than the thermoplastic resin (P ₁ ) as long as it does not impair adhesion to the molecular adhesive layer.

Components other than the thermoplastic resin (P ₁ ) include ultraviolet absorbers, light stabilizers, antioxidants, antistatic agents, slip agents, anti-blocking agents, and colorants.

Their content can be determined appropriately according to the purpose.

The content of the thermoplastic resin (P ₁ ) in the first thermoplastic resin layer is usually 50 to 100 mass%, preferably 80 to 100 mass%.

The thickness of the first thermoplastic resin layer is usually 5 to 150 μm, preferably 10 to 120 μm, and more preferably 15 to 80 μm.

When the thickness of the first thermoplastic resin layer is 5 μm or more, it is possible to sufficiently prevent the performance of the molecular adhesive layer from deteriorating due to heating in the thermal welding process. In addition, when the thickness of the first thermoplastic resin layer is 80 μm or less, the joint portion (between adherends) can be thinned.

The heat sealable temperature of the first thermoplastic resin layer is usually 100 to 200°C, preferably 120 to 180°C.

When the heat sealable temperature of the first thermoplastic resin layer is 100°C or higher, it is possible to suppress the shape of the first thermoplastic resin layer from changing during heat welding. In addition, because the heat sealable temperature of the first thermoplastic resin layer is 200°C or lower, the influence on the molecular adhesive layer during heat welding can be suppressed.

The heat sealable temperature of the first thermoplastic resin layer is determined by the type of thermoplastic resin, the molecular weight of the thermoplastic resin, the content of the thermoplastic resin, the type of additive, the content of the additive, the crystallinity of the first thermoplastic resin layer, and the first thermoplastic resin layer. It is a characteristic affected by the density of the thermoplastic resin layer, etc.

Therefore, for example, after determining the thermoplastic resin to be used, the first thermoplastic resin layer having the desired heat sealable temperature can be formed by adjusting the type and amount of additives.

[Second thermoplastic resin layer]

The second thermoplastic resin layer is a layer adjacent to the first thermoplastic resin layer, and is a layer that constitutes one of the outermost layers when the laminate for bonding is used. Additionally, an adhesive layer may exist between the first thermoplastic resin layer and the second thermoplastic resin layer.

As will be described later, the second thermoplastic resin layer is used for heat welding with the second thermoplastic resin layer of another laminate for bonding.

The second thermoplastic resin layer may have a single-layer structure or a multi-layer structure. The second thermoplastic resin layer when the second thermoplastic resin layer has a single-layer structure or each layer when the second thermoplastic resin layer has a multi-layer structure may have a uniform composition or may not have a uniform composition. do. For example, these layers may contain many specific components near the surface of the layer, and the composition near the surface of the layer may be different from the composition at the center of the layer.

The second thermoplastic resin layer is a thermoplastic resin (hereinafter referred to as “thermoplastic resin (P ₂ )) that melts at a relatively low temperature and can solidify in a short time, at least on the surface opposite to the first thermoplastic resin layer. 」 It is desirable to include .

By including a thermoplastic resin (P ₂ ) on the surface opposite to the first thermoplastic resin layer, when heat welding with the thermoplastic resin layer of another laminate for bonding, the process can be carried out efficiently.

“Containing a thermoplastic resin (P ₂ ) on the surface opposite to the first thermoplastic resin layer” means that the thermoplastic resin (P ₂ ) is exposed on the surface opposite to the first thermoplastic resin layer. says

Examples of the thermoplastic resin (P ₂ ) include olefin resin, cycloolefin resin, acrylic resin, olefin-vinyl acetate resin, olefin ionomer resin, and polyester resin.

Specific examples of these thermoplastic resins include the same ones as those shown as thermoplastic resin (P ₁ ).

Thermoplastic resin (P ₂ ) can be used individually or in combination of two or more types.

The second thermoplastic resin layer may contain components other than the thermoplastic resin (P ₂ ) as long as it does not impair thermal weldability.

Components other than the thermoplastic resin (P ₂ ) include ultraviolet absorbers, light stabilizers, antioxidants, antistatic agents, slip agents, anti-blocking agents, and colorants.

Their content can be determined appropriately according to the purpose.

When the second thermoplastic resin layer has a single-layer structure, the second thermoplastic resin layer is a uniform layer containing the thermoplastic resin (P ₂ ), or at least a layer on the opposite side from the first thermoplastic resin layer. An example is a non-uniform layer containing a thermoplastic resin (P ₂ ) on the surface.

The content of the thermoplastic resin (P ₂ ) in the second thermoplastic resin layer having a single-layer structure is usually 50 to 100 mass%, preferably 80 to 100 mass%.

The thickness of the second thermoplastic resin layer having a single-layer structure is usually 5 to 150 μm, preferably 10 to 120 μm, and more preferably 15 to 80 μm.

When the thickness of the second thermoplastic resin layer having a single-layer structure is 5 μm or more, thermal welding can be sufficiently performed. In addition, because the thickness of this second thermoplastic resin layer is 150 μm or less, the joint portion (between adherends) can be thinned.

When the second thermoplastic resin layer has a multilayer structure, the second thermoplastic resin layer includes an outermost layer on the opposite side from the first thermoplastic resin layer (the two outermost layers of the second thermoplastic resin layer having a multilayer structure) Among the outer layers, the outermost layer on the side that is not in contact with the first thermoplastic resin layer) includes a layer with a multi-layer structure, which includes a thermoplastic resin (P ₂ ) on the surface on the opposite side from the first thermoplastic resin layer. there is.

In the second thermoplastic resin layer having a multilayer structure, the content of the thermoplastic resin (P ₂ ) contained in the outermost layer on the opposite side to the first thermoplastic resin layer is usually based on the entire outermost layer. It is 50 to 100 mass%, preferably 80 to 100 mass%.

The thickness of the entire second thermoplastic resin layer having a multilayer structure is usually 3 to 150 μm, preferably 10 to 120 μm, and more preferably 15 to 80 μm.

When the overall thickness of the second thermoplastic resin layer having a multilayer structure is 3 μm or more, thermal welding can be sufficiently performed. In addition, because the thickness of this second thermoplastic resin layer is 150 μm or less, the joint portion (between adherends) can be thinned.

In the second thermoplastic resin layer having a multilayer structure, the number of layers is not particularly limited. The number of layers of the second thermoplastic resin layer having a multilayer structure is usually 2 to 10, and is preferably 2 to 5.

The heat sealable temperature of the second thermoplastic resin layer is usually 50 to 180°C, preferably 70 to 150°C.

When the heat sealable temperature of the second thermoplastic resin layer is 50°C or higher, handleability at room temperature becomes good. In addition, since the heat sealable temperature of the second thermoplastic resin layer is 180° C. or lower, when using the laminate for bonding of the present invention, the layers of the second thermoplastic resin layer can be firmly bonded to each other, 2 Two adherends can be joined more strongly.

The heat-sealable temperature of the second thermoplastic resin layer can be adjusted by the same method as the method of adjusting the heat-sealable temperature of the first thermoplastic resin layer.

In addition, when the second thermoplastic resin layer has a multilayer structure, the heat-sealable temperature of the second thermoplastic resin layer refers to the heat-sealable temperature of the outermost layer on the opposite side to the first thermoplastic resin layer.

[Laminate for joining]

The laminate for bonding is a laminate composed of a first thermoplastic resin layer and a second thermoplastic resin layer (hereinafter sometimes referred to as “laminated body (η)”) on the first thermoplastic resin layer. , can be manufactured directly by forming a molecular adhesive layer.

For example, as shown in FIG. 1, on the first thermoplastic resin layer (1) of the laminate (3) composed of the first thermoplastic resin layer (1) and the second thermoplastic resin layer (2), By directly forming the molecular adhesive layer 4, the laminate for bonding 5 is obtained.

As described above, in the laminate 3, the first thermoplastic resin layer 1 contains a thermoplastic resin (P ₁ ) on the surface 6 on the side in contact with the molecular adhesive layer 4 . In addition, the second thermoplastic resin layer 2 of the laminate 3 preferably includes a thermoplastic resin (P ₂ ) on the surface 7 on the opposite side to the first thermoplastic resin layer 1. .

The manufacturing method of the laminated body (η) is not particularly limited.

For example, a coextruded multilayer film obtained by melting a pellet containing a thermoplastic resin (P ₁ ) and a pellet containing a thermoplastic resin (P ₂ ), respectively, and simultaneously extruding them from a multilayer die, is formed into a laminate ( η) can be used.

Additionally, a multilayer film obtained by bonding a resin film containing a thermoplastic resin (P ₁ ) and a resin film containing a thermoplastic resin (P ₂ ) can be used as a laminate (η).

Additionally, a coating liquid containing the thermoplastic resin (P ₂ ) is applied onto the first thermoplastic resin layer (resin film) containing the thermoplastic resin (P ₁ ), and the obtained coating film is dried to form a second thermoplastic resin. A resin layer is formed, or a coating liquid containing a thermoplastic resin (P ₁ ) is applied onto a second thermoplastic resin layer (resin film) containing a thermoplastic resin (P ₂ ), and the resulting coating film is dried. The multilayer film obtained by forming the first thermoplastic resin layer can be used as a laminate (η).

Among these, it is preferable to use a coextruded multilayer film as the laminate (η) because delamination between the first and second thermoplastic resin layers is less likely to occur.

In addition, in this specification, the resin film in a state in which no other layers have yet been formed may be expressed as “the first thermoplastic resin layer” or “the second thermoplastic resin layer.”

When manufacturing the laminate η, the components of each layer are determined so that the heat-sealable temperature of the first thermoplastic resin layer is higher than the heat-sealable temperature of the second thermoplastic resin layer.

That is, in the laminate for bonding of the present invention, when the heat sealable temperature of the first thermoplastic resin layer is T _h1 and the heat sealable temperature of the second thermoplastic resin layer is T _h2 , T _h1 > T _h2 .

As described later, when two adherends are joined using the bonding laminate of the present invention, the heat sealable temperature of the first thermoplastic resin layer is made higher than the heat sealable temperature of the second thermoplastic resin layer. , the heat welding process can be performed without adversely affecting the molecular adhesive layer.

The molecular adhesive (M) used when forming the molecular adhesive layer takes into account the combination of its reactive group (Zα) and the reactive partial structure (Zγ) of the thermoplastic resin (P ₁ ) in the first thermoplastic resin layer. , can be selected appropriately.

Among these, it is preferable that the reactive group (Zα) and the reactive partial structure (Zγ) satisfy the following requirements (Q1).

Requirements (Q1):

The reactive group (Zα) possessed by the molecular adhesive (M) is at least one selected from the group consisting of an amino group, a mercapto group, an isocyanate group, a ureido group, and an epoxy group, and the reactive moiety possessed by the thermoplastic resin (P ₁ ) The structure (Zγ) is at least one selected from the group consisting of a hydroxy group, a carboxyl group, an aldehyde group, and an amino group, or,

The reactive group (Zα) of the molecular adhesive (M) is an azide group, and the reactive partial structure (Zγ) of the thermoplastic resin (P ₁ ) is a carbon-carbon single bond, a carbon-carbon double bond, and It is at least one type selected from the group consisting of carbon-hydrogen single bonds.

In the laminate for bonding of the present invention, the reactive group (Zα) of the molecular adhesive (M) and the reactive partial structure (Zγ) of the thermoplastic resin (P ₁ ) form a chemical bond, so that the molecular adhesive (M) , it is believed to be fixed to the first thermoplastic resin layer.

It is believed that this chemical bond can be formed efficiently by satisfying the above requirement (Q1).

When the reactive group (Zα) is at least one selected from the group consisting of an amino group, a mercapto group, an isocyanate group, a ureido group, and an epoxy group, a preferred combination of the reactive group (Zα) and the reactive partial structure (Zγ) [reactive group ( [Zα)/reactive partial structure (Zγ)], (amino group/hydroxy group), (amino group/carboxy group), (isocyanate group/hydroxy group), (isocyanate group/carboxy group), (hydroxy group/carboxy group) etc. can be mentioned.

In addition, when the reactive group (Zα) is an azide group, the azide group is activated by irradiation with light as described later. In this case, since nitrene, which is a reaction intermediate, can react with a carbon-carbon single bond, a carbon-carbon double bond, and a carbon-hydrogen single bond, the reactive partial structure (Zγ) of the thermoplastic resin (P ₁ ) is: At least one species selected from the group consisting of a carbon-carbon single bond, a carbon-carbon double bond, and a carbon-hydrogen single bond is preferably used.

If it is a thermoplastic resin, it usually contains at least one of a carbon-carbon single bond, a carbon-carbon double bond, and a carbon-hydrogen single bond. Therefore, when using the molecular adhesive (M) having an azide group, the type of thermoplastic resin (P ₁ ) is not particularly limited.

The method of forming the molecular adhesive layer is not particularly limited. For example, a molecular adhesive solution containing the molecular adhesive (M) is prepared, this solution is applied on the first thermoplastic resin layer, and the obtained coating film is then dried, or the molecular adhesive (M) is applied to the first thermoplastic resin layer. A molecular adhesive layer can be formed by performing a treatment to fix the thermoplastic resin layer.

The solvent used when preparing the molecular adhesive solution is not particularly limited. Examples of the solvent include alcohol-based solvents such as methanol, ethanol, isopropanol, ethylene glycol, and diethylene glycol; Ketone-based solvents such as acetone and methyl ethyl ketone; Ester solvents such as ethyl acetate and butyl acetate; Halogen-containing compound-based solvents such as methylene chloride; Aliphatic hydrocarbon-based solvents such as butane and hexane; Ether-based solvents such as tetrahydrofuran and butyl ether; Aromatic compound-based solvents such as benzene and toluene; Amide-based solvents such as N,N-dimethylformamide and N-methylpyrrolidone; water ; etc. can be mentioned.

These can be used individually or in combination of two or more types.

The concentration of the molecular adhesive (M) in the molecular adhesive solution is not particularly limited. The concentration is preferably 0.005 to 1.000 mol/l, more preferably 0.050 to 0.500 mol/l. By setting the concentration of the molecular adhesive (M) to 0.005 mol/L or more, the molecular adhesive layer can be efficiently formed on the first thermoplastic resin layer. In addition, by setting it to 1.000 mol/l or less, unintended reactions of the molecular adhesive solution can be suppressed, and the stability of the solution is excellent.

The application method of the molecular adhesive solution is not particularly limited, and a known application method can be used. Application methods include, for example, spin coat method, spray coat method, bar coat method, knife coat method, roll knife coat method, roll coat method, blade coat method, dip coat method, curtain coat method, die coat method, Although the gravure coat method etc. can be mentioned, the bar coat method and the gravure coat method are preferable.

After applying the molecular adhesive solution, drying treatment by natural drying or putting it into a drying device is usually necessary to dry the obtained coating film. Among these, it is preferable from the viewpoint of improving productivity to perform drying treatment by putting it into a drying device. The drying equipment includes, for example, a batch-type drying equipment such as an air oven, a heat roll, and a hot-air through mechanism (an open-type drying furnace in which the object to be dried moves and passes through it and is heated and dried while receiving airflow). equipment, etc.) and continuous drying equipment. Additionally, devices that can be used as part of these drying devices, such as heat circulation heaters such as high-frequency heating and oil heaters, and heaters themselves, such as far-infrared heaters, can also be used as drying devices. Among these, a hot air through mechanism is preferable from the viewpoint of improving productivity.

The drying temperature adjusted with the drying device is usually 20 to 250°C, preferably 25 to 200°C, more preferably 30 to 150°C, and particularly preferably 35 to 120°C. The drying time is usually 1 second to 120 minutes, preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes, and particularly preferably 30 seconds to 3 minutes.

When forming a molecular adhesive layer, a treatment (hereinafter sometimes referred to as a fixing treatment) is usually performed to fix the molecular adhesive (M) to the first thermoplastic resin layer. The fixing treatment can be appropriately selected depending on the characteristics of the reactive group (Zα) of the molecular adhesive (M). Usually, chemical bonds are created by applying the molecular adhesive (M) onto the first thermoplastic resin layer, and heating promotes the creation of chemical bonds, so heat treatment is preferable from the viewpoint of improving productivity. do. The heating temperature is usually 40 to 250°C, preferably 60 to 200°C, and more preferably 80 to 120°C. The heating time is usually 1 second to 120 minutes, preferably 1 to 60 minutes, more preferably 1 to 30 minutes.

The heating method is not particularly limited, and the same mechanisms and devices as the drying mechanism described above can be used.

When the reactive group (Zα) has photoreactivity, such as an azide group, light irradiation treatment is performed as the fixing treatment. As the light to be irradiated, ultraviolet rays are usually used. In this case, it is preferable to perform the fixing treatment after the drying treatment from the viewpoint of improving the reactivity of the reactive group (Zα) and the reactive group (Zγ).

Irradiation of ultraviolet rays can be performed using an ultraviolet irradiation device using a light source such as a mercury lamp, metal halide lamp, ultraviolet LED, or electrodeless lamp.

The treatment conditions for the light irradiation treatment are not particularly limited as long as the desired photo reaction can be performed.

When forming the molecular adhesive layer, the application of the molecular adhesive solution, drying treatment, and fixing treatment may be repeated multiple times.

2) How to join two adherends

The method of joining two adherends of the present invention is a method of joining an adherend (I) and an adherend (II) using two bonding laminates, wherein the two bonding laminates are each independent. In this case, it is a laminate for bonding of the present invention, and the first laminate for bonding is a molecular adhesive layer ( _AM ) containing a molecular adhesive (MA), and a first thermoplastic resin layer (A-1) having a single layer structure. , and a second thermoplastic resin layer (A-2) having a single-layer structure or a multi-layer structure in this order is represented by a laminate for bonding (A), and the second laminate for bonding is a molecular adhesive ( _MB ). Bonding having a molecular adhesive layer (BM) comprising, a first thermoplastic resin layer (B-1) having a single-layer structure, and a second thermoplastic resin layer (B-2) having a single-layer structure or a multi-layer structure in this order. When expressed as a laminate (B),

Any process selected from the process group containing the following processes (L1) to (L3), the process group containing processes (M1) to (M3), and the process group containing processes (N1) and (N2). A method for bonding an adherend (I) and an adherend (II), characterized in that the group is carried out.

Process (L1): Process of bonding the molecular adhesive layer (A-M) of the laminate for bonding (A) and the adherend (I)

Process (L2): Process of bonding the molecular adhesive layer (B-M) of the laminate for bonding (B) and the adherend (II)

Step (L3): Heat welding the second thermoplastic resin layer (A-2) of the laminate obtained in step (L1) and the second thermoplastic resin layer (B-2) of the laminate obtained in step (L2). process

Step (M1): A process of heat welding the second thermoplastic resin layer (A-2) of the laminate for joining (A) and the second thermoplastic resin layer (B-2) of the laminate for joining (B).

Step (M2): A step of bonding the molecular adhesive layer (A-M) of the laminate obtained in step (M1) and the adherend (I).

Step (M3): A step of bonding the molecular adhesive layer (B-M) of the laminate obtained in step (M2) and the adherend (II).

Step (N1): An arrangement in which the second thermoplastic resin layer (A-2) of the laminate for joining (A) and the second thermoplastic resin layer (B-2) of the laminate for joining (B) face each other. , a process of overlapping the adherend (I), the laminate for bonding (A), the laminate for bonding (B), and the adherend (II) in this order.

Step (N2): Heating the product obtained in step (N1), adhesion of the molecular adhesive layer (A-M) and the adherend (I), adhesion of the molecular adhesive layer (B-M) and the adherend (II), and second heat A process of simultaneously performing heat welding of the plastic resin layer (A-2) and the second thermoplastic resin layer (B-2)

The laminate for bonding (A) includes a molecular adhesive layer (AM) containing a molecular adhesive ( _MA ), a first thermoplastic resin layer (A-1), and a second thermoplastic resin layer (A-2). This is a laminate for joining in this order.

In the bonding method of the present invention, the laminate for bonding (A) is used for bonding with the adherend (I).

The laminate for bonding (B) includes a molecular adhesive layer (BM) containing a molecular adhesive ( _MB ), a first thermoplastic resin layer (B-1), and a second thermoplastic resin layer (B-2). It is a laminate for joining (B) in this order.

In the bonding method of the present invention, the laminate for bonding (B) is used for bonding with the adherend (II).

The laminate for bonding (A) and the laminate for bonding (B) may be the same or different.

The second thermoplastic resin layer (A-2) of the bonding laminate (A) has a thermoplastic resin (P ₂ ) on the surface opposite to the first thermoplastic resin layer (A-1) (hereinafter, The thermoplastic resin (P ₂ ) contained in the second thermoplastic resin layer (A-2) is sometimes referred to as “thermoplastic resin (P _2A )”), and the laminate for bonding (B) The second thermoplastic resin layer (B-2) has a thermoplastic resin (P ₂ ) on the surface opposite to the first thermoplastic resin layer (B-1) (hereinafter referred to as the second thermoplastic resin layer ( In the case where the thermoplastic resin (P ₂ ) included in B-2) is included (sometimes referred to as “thermoplastic resin (P _2B )”), the thermoplastic resin (P _2A ) (second thermoplastic When the resin layer (A-2) contains two or more types of thermoplastic resin ( _P2A ), the one with the highest content) and the thermoplastic resin ( _P2B ) (the second thermoplastic resin layer (B-2) is 2. When more than one type of thermoplastic resin ( _P2B ) is included, it is preferable that the ones with the highest content are the same. When the thermoplastic resin (P _2A ) and the thermoplastic resin (P _2B ) are the same, the two adherends can be joined more strongly.

Thermoplastic resin (P _2A ) (when the second thermoplastic resin layer (A-2) contains two or more types of thermoplastic resin (P _2A ), the one with the highest content) and thermoplastic resin (P _2B ) (second thermoplastic resin layer (A-2)) 2. When the thermoplastic resin layer (B-2) contains two or more types of thermoplastic resins (P _2B ), when the content (the one with the highest content) is different, and when these thermoplastic resins are crystalline resins, their melting points are It is desirable for the car to be small. By using a combination of a thermoplastic resin (P _2A ) and a thermoplastic resin (P _2B ) with close melting points, thermal welding can be performed more efficiently.

The difference between the melting point of the thermoplastic resin ( _P2A ) and the melting point of the thermoplastic resin ( _P2B ) is preferably 40°C or lower, more preferably 20°C or lower, and particularly preferably 0°C.

Thermoplastic resin (P _2A ) (when the second thermoplastic resin layer (A-2) contains two or more types of thermoplastic resin (P _2A ), the one with the highest content) and thermoplastic resin (P _2B ) (second thermoplastic resin layer (A-2)) 2 When the thermoplastic resin layer (B-2) contains two or more types of thermoplastic resins (P _2B ) and the content (the one with the highest content) is different, it is preferable that the interaction distance Ra of their Hansen solubility parameters is small. . By using a combination of a thermoplastic resin (P _2A ) and a thermoplastic resin (P _2B ) having a close interaction distance Ra of the Hansen solubility parameter, thermal welding can be performed more efficiently.

The interaction distance Ra of the Hansen solubility parameter between the thermoplastic resin ( _P2A ) and the thermoplastic resin ( _P2B ) is preferably 10 or less, more preferably 4.5 or less.

In the present invention, the interaction distance Ra of the Hansen solubility parameter is derived from the following equation.

In the above formula, δD _A is the dispersion component of the Hansen solubility parameter of the thermoplastic resin (P _2A ), δD _B is the dispersion component of the Hansen solubility parameter of the thermoplastic resin (P _2B ), and δP _A is the dispersion component of the Hansen solubility parameter of the thermoplastic resin (P 2B). The polar component of the Hansen solubility parameter of the thermoplastic resin (P _2A ), δP _B is the polar component of the Hansen solubility parameter of the thermoplastic resin (P _2B ), δH _A is the hydrogen bonding component of the Hansen solubility parameter of the thermoplastic resin (P _2A ), δH _B represents the hydrogen bond component of the Hansen solubility parameter of the thermoplastic resin (P _2B ).

In the bonding method of the present invention, the molecular adhesive layer (A-M) of the laminate for bonding (A) is used for adhesion to the adherend (I), and the molecular adhesive layer (B-M) of the laminate for bonding (B) is used for adhesion to the adherend (I). is used for adhesion with the adherend (II).

Adhesion between the molecular adhesive layer (AM) and the adherend (I) or between the molecular adhesive layer (BM) and the adherend (II) is usually a reaction in the molecular adhesive ( _MA ) or (M _B ). This is carried out when the group (Zβ) reacts with a functional group in the compound constituting the adherend (I) or the adherend (II), and a chemical bond is formed.

Therefore, usually, as the adherend (I) or adherend (II), one having a group reactive with the reactive group (Zβ) on its surface is used.

Examples of such an adherend include a member whose surface contains metal, a member whose surface contains an inorganic substance, and a member whose surface contains a silicone resin.

Metals include aluminum, chromium, manganese, iron, cobalt, nickel, copper, zinc, silver, and gold.

Examples of inorganic materials include glass and inorganic oxides (excluding glass).

Surface treatment may be performed on these members. A member in which hydroxy groups, carboxyl groups, etc. have been generated through surface treatment is more preferably used as an adherend.

Additionally, by using surface treatment technology, a member whose surface contains a thermoplastic resin or thermosetting resin can also be used as an adherend.

Surface treatments include corona treatment, plasma treatment, ultraviolet irradiation treatment, electron beam irradiation treatment, ozone treatment, excimer ultraviolet treatment, acid treatment, and base treatment. These surface treatments can be performed according to known methods.

Additionally, a primer layer may be formed on the surface of the adherend as needed.

[Process group including processes (L1) to (L3)]

Each process of the process group including processes (L1) to (L3) is shown in FIG. 2.

In the step (L1), bonding with the molecular adhesive layer (A-M) (8), the first thermoplastic resin layer (A-1) (9), and the second thermoplastic resin layer (A-2) (10) The molecular adhesive layer (A-M) (8) of the laminate (A) (11) and the adherend (I) (12) are bonded to obtain the laminate (13) [FIG. 2(a)].

The process (L1) can be performed using, for example, a heat press machine, an autoclave machine, a vacuum bonding machine, a three-dimensional vacuum heating molding machine (TOM molding machine), a heat laminating machine, etc.

When applying linear pressure in step (L1), the pressure is usually 0.1 to 5 N/mm, preferably 0.2 to 3 N/mm, and more preferably 0.3 to 1 N/mm.

When applying surface pressure in step (L1), the pressure is usually 0.1 to 10 MPa, preferably 0.2 to 5 MPa, more preferably 0.3 to 3 MPa, and still more preferably 0.4 to 1 MPa.

The adhesion temperature in step (L1) is usually 40 to 200°C, preferably 50 to 170°C, and more preferably 60 to 140°C.

The processing time of step (L1) is usually 1 second to 1 hour, preferably 5 seconds to 30 minutes, and more preferably 10 seconds to 10 minutes.

In step (L2), bonding having the molecular adhesive layer (B-M) (14), the first thermoplastic resin layer (B-1) (15), and the second thermoplastic resin layer (B-2) (16) The molecular adhesive layer (B-M) 14 of the laminate (B) 17 and the adherend (II) 18 are bonded to obtain the laminate 19 [FIG. 2(b)].

Step (L2) can be performed by the same method and under the same conditions as step (L1).

In step (L3), the second thermoplastic resin layer (A-2) 10 of the laminate 13 obtained in step (L1) and the second row of the laminate 19 obtained in step (L2) The plastic resin layer (B-2) 16 is heat-welded to obtain the bonded structure 20 [FIG. 2(c)].

The step (L3) can be performed using, for example, a heat press machine, an autoclave machine, a vacuum bonding machine, a three-dimensional vacuum heating molding machine (TOM molding machine), a heat laminating machine, etc.

When applying linear pressure in step (L3), the pressure is usually 0.1 to 5 N/mm, preferably 0.2 to 3 N/mm, and more preferably 0.3 to 1 N/mm.

When applying surface pressure in step (L3), the pressure is usually 0.05 to 10 MPa, preferably 0.1 to 5 MPa, and more preferably 0.2 to 3 MPa.

The thermal welding temperature in step (L3) is usually 50 to 230°C, preferably 60 to 200°C, and more preferably 80 to 170°C.

The processing time of step (L3) is usually 1 second to 1 minute, preferably 3 to 30 seconds.

When carrying out the process group including steps (L1) to (L3), in step (L1), the molecular adhesive layer (AM) of the bonding laminate (A) and the adherend (I) are bonded. The temperature is T _L1 , and in step (L2), the temperature at which the molecular adhesive layer (BM) of the bonding laminate (B) and the adherend (II) are bonded is T _L2 . In step (L3), the temperature is T L2. The temperature when heat welding the second thermoplastic resin layer (A-2) and the second thermoplastic resin layer (B-2) is T _L3 , and the first thermoplastic resin layer (A) of the laminate for joining (A) is The heat sealable temperature of -1) is T _h1A , the heat sealable temperature of the second thermoplastic resin layer (A-2) is T _h2A , and the first thermoplastic resin layer (B-) of the bonding laminate (B) is T h2A. 1) When the heat sealable temperature of the second thermoplastic resin layer (B-2) is T _h1B and the heat sealable temperature of the second thermoplastic resin layer (B-2) is T _h2B , both the following equations (E-1) and (E-2) are satisfied. , it is also preferable to satisfy at least one of the following formulas (E-3) and (E-4).

By satisfying the formula (E-1), deformation of the first thermoplastic resin layer (A-1) of the laminate for bonding (A) in step (L1) is suppressed.

By satisfying the formula (E-2), deformation of the first thermoplastic resin layer (B-1) of the laminate for bonding (B) in step (L2) is suppressed.

By satisfying at least one of the formulas (E-3) and (E-4), the second thermoplastic resin layer (A-2) of the laminate for bonding (A) and the second layer of the laminate for bonding (B) The thermoplastic resin layer (B-2) can be efficiently heat-welded.

Because the second thermoplastic resin layer (A-2) of the bonding laminate (A) and the second thermoplastic resin layer (B-2) of the bonding laminate (B) can be more efficiently heat welded. , it is more preferable to satisfy both equations (E-3) and equations (E-4).

[Process group including processes (M1) to (M3)]

Each process of the process group including processes (M1) to (M3) is shown in FIG. 3.

In step (M1), bonding having a molecular adhesive layer (A-M) (21), a first thermoplastic resin layer (A-1) (22), and a second thermoplastic resin layer (A-2) (23) The second thermoplastic resin layer (A-2) (23), the molecular adhesive layer (B-M) (25), and the first thermoplastic resin layer (B-1) (26) of the laminate (A) (24). , and the second thermoplastic resin layer (B-2) (27) of the laminate for joining (B) (28) having the second thermoplastic resin layer (B-2) (27) is thermally welded to form a laminate. (29) is obtained [Figure 3(a)].

Step (M1) can be performed by the same method and under the same conditions as step (L3).

In step (M2), the molecular adhesive layer (A-M) 21 of the laminate 29 obtained in step (M1) and the adherend (I) 30 are bonded to obtain the laminate 31 [Figure 3(b)].

In step (M3), the molecular adhesive layer (B-M) 25 of the laminate 31 obtained in step (M2) and the adherend (II) 32 are bonded to obtain the bonded structure 33 [Figure 3(c)].

Step (M2) and step (M3) can each be carried out by the same method and under the same conditions as step (L1).

Additionally, step (M2) and step (M3) may be performed simultaneously. For example, the laminate obtained in the adherend (I) and the process (M1) and the adherend (II) are overlapped in this order and subjected to a compression treatment to perform the processes (M2) and (M3) simultaneously. It can be implemented.

[Process group including processes (N1) and (N2)]

Each process of the process group including processes (N1) and (N2) is shown in FIG. 4.

In step (N1), bonding having a molecular adhesive layer (A-M) (34), a first thermoplastic resin layer (A-1) (35), and a second thermoplastic resin layer (A-2) (36) The second thermoplastic resin layer (A-2) (36), the molecular adhesive layer (B-M) (38), and the first thermoplastic resin layer (B-1) (39) of the laminate (A) (37). , and the second thermoplastic resin layer (B-2) 40 of the laminate for joining (B) 41 having the second thermoplastic resin layer (B-2) 40 is arranged to face each other. Complex (I) (42), laminate for bonding (A) (35), laminate for bonding (B) (41), and adherend (II) (43) are overlapped in this order [Figure 4(a)] 〕.

In step (N2), the product (44) obtained in step (N1) is heated to bond the molecular adhesive layer (A-M) to the adherend (I) and to bond the molecular adhesive layer (B-M) to the adherend (II). Adhesion and heat welding of the second thermoplastic resin layer (A-2) and the second thermoplastic resin layer (B-2) are performed simultaneously to obtain the bonded structure 45 [FIG. 4(b)].

The process (N2) can be performed using, for example, a heat press machine, an autoclave machine, a vacuum bonding machine, a three-dimensional vacuum heating molding machine (TOM molding machine), a heat laminating machine, etc.

When applying linear pressure in step (N2), the pressure is usually 0.1 to 5 N/mm, preferably 0.2 to 3 N/mm, and more preferably 0.3 to 1 N/mm.

When applying surface pressure in step (N2), the pressure is usually 0.1 to 10 MPa, preferably 0.2 to 5 MPa, more preferably 0.3 to 3 MPa, and still more preferably 0.4 to 1 MPa.

The thermal welding temperature in step (N2) is usually 50 to 230°C, preferably 60 to 200°C, and more preferably 80 to 170°C.

The processing time of step (N2) is usually 1 second to 1 hour, preferably 5 seconds to 30 minutes, and more preferably 10 seconds to 10 minutes.

When carrying out the process group including steps (N1) and (N2), the heat sealable temperature of the first thermoplastic resin layer (A-1) of the bonding laminate (A) is T _h1A , and the second thermoplastic temperature is T h1A. The heat sealable temperature of the resin layer (A-2) is T _h2A , the heat sealable temperature of the first thermoplastic resin layer (B-1) of the bonding laminate (B) is T _h1B , and the second thermoplastic water. When the heat sealable temperature of the stratum (B-2) is T _h2B and the temperature at the time of heat welding in step (N2) is T _N2 , the following formulas (E-5) and (E-6) It is desirable to satisfy at least one party.

By satisfying at least one of Formula (E-5) and Formula (E-6), the second thermoplastic resin layer (A-2) of the laminate for bonding (A) and the second layer of the laminate for bonding (B) The thermoplastic resin layer (B-2) can be efficiently heat-welded.

Because the second thermoplastic resin layer (A-2) of the bonding laminate (A) and the second thermoplastic resin layer (B-2) of the bonding laminate (B) can be more efficiently heat welded. , it is more preferable to satisfy both Equation (E-5) and Equation (E-6).

When bonding the adherend (I) and the adherend (II), a process group including the above steps (L1) to (L3) or a process group including the above steps (N1) and (N2) are performed. It is desirable.

In the process group including the above steps (L1) to (L3), an adhesion treatment between the molecular adhesive layer and the adherend is performed before the thermal welding treatment. Therefore, since the adhesion treatment between the molecular adhesive layer and the adherend can be performed in a state in which thermal deformation of the thermoplastic resin layer accompanying the heat welding process does not occur, the molecular adhesive layer and the adherend can be more strongly bonded. can do.

In the process group including the above steps (N1) and (N2), the adhesion treatment between the molecular adhesive layer and the adherend and the heat welding treatment between the thermoplastic resin layers are performed simultaneously. Therefore, two adherends can be joined more efficiently.

3) Manufacturing method of bonded structure

The method for producing a bonded structure of the present invention is to manufacture a bonded structure having a layer structure of adherend (I)/laminated body for bonding (A) and layer/adherent (II) derived from the laminate for bonding (B). As a method, the bonding method of the present invention is used to bond the adherend (I) and the adherend (II).

According to the manufacturing method of the present invention, a bonded structure in which the adherend (I) and the adherend (II) are firmly bonded via a bonding laminate is obtained.

As the adherend (I) and the adherend (II), those shown in the invention of the method for joining two adherends can be used.

Among these, it is preferable that the adherend (I) and the adherend (II) each independently contain at least one type selected from the group consisting of metals, inorganic substances, and thermosetting resins, at least on the adherend surface.

When the adherend has a bonded surface formed of a thermoplastic resin, there are cases where the adherends can be joined by direct heat welding even without using the bonding laminate of the present invention.

On the other hand, when metal, inorganic material, or thermosetting resin is present on the adherend surface of the adherend, it is difficult to firmly bond these adherends by this method.

The method for manufacturing the bonded structure of the present invention uses the laminate for bonding of the present invention. Therefore, according to the manufacturing method of the bonded structure of the present invention, even when metal, inorganic material, or thermosetting resin is present on the bonded surface of the adherend, it is possible to obtain a bonded structure in which these adherends are firmly bonded.

Example

Hereinafter, the present invention will be described in more detail through examples. However, the present invention is not limited to the following examples.

Parts and % in each example are based on mass, unless otherwise specified.

[Measurement of heat sealable temperature of each layer of multilayer film]

The heat sealable temperature of each layer of the multilayer films (1) to (5) was determined by the following method.

Two multilayer films (25 mm × 150 mm) were prepared, overlapped so that the layers of the same component faced each other, and these were heat welded at 0.2 MPa for 1 second to obtain a test piece. At this time, the heat welding temperature was changed at 5°C intervals (e.g., 140°C, 145°C, 150°C) to obtain a plurality of test pieces.

Each of the obtained test pieces was tested at 300 mm/min using a tensile tester (manufactured by A&D Co., Ltd., product name “Tensilon Universal Tester”) in an environment of 23°C and 50% humidity (relative humidity). A T-shaped peel test was performed to measure each adhesive strength.

Among the test specimens with an adhesive strength of 5 N/25 mm or more, the thermal welding temperature of the test specimen with the lowest thermal welding temperature was referred to as the “heat sealable temperature.”

[Production Example 1]

Using two types of polypropylene as molding materials, by coextrusion method, “first thermoplastic resin layer [polypropylene (PP) thickness 60 μm]/second thermoplastic resin layer [polypropylene (PP) thickness 50 μm]” A multilayer film (1) with a layer structure of [μm] was obtained. As a result of measuring the heat sealable temperature of each layer of the obtained multilayer film (1), the heat sealable temperature of the first thermoplastic resin layer was 170 ° C., and the heat sealable temperature of the second thermoplastic resin layer was 145 ° C. It was ℃.

[Production Examples 2 and 5]

Multilayer films (2) and (5) were obtained in the same manner as in Production Example 1, except that the molding materials shown in Table 1 were used.

[Production Example 3]

Two types of polyethylene and nylon were used as molding materials, and a coextrusion method was used to form “first thermoplastic resin layer [polyethylene (PE) thickness 25 μm]/second thermoplastic resin layer [nylon (Ny) thickness 30 μm]” A multilayer film (3) with a layer structure of [μm/polyethylene (PE) thickness of 25 μm] was obtained. Regarding the obtained multilayer film 3, the heat sealable temperature of each layer was measured, and the heat sealable temperature of the first thermoplastic resin layer was 140°C, and the heat sealable temperature of the second thermoplastic resin layer (polyethylene layer) was 140°C. The possible temperature was 100°C.

[Production Example 4]

Using a polyester adhesive, a polyethylene film and an ethylene/vinyl acetate copolymer resin film are dry laminated to form “first thermoplastic resin layer [polyethylene (PE) thickness 100 µm]/second thermoplastic resin layer [ethylene/acetic acid]. A multilayer film (4) having a layer structure of “vinyl copolymer resin (EVA) with a thickness of 50 μm” was obtained. Regarding the obtained multilayer film 4, the heat-sealable temperature of each layer was measured, and the heat-sealable temperature of the first thermoplastic resin layer was 140°C, and the heat-sealable temperature of the second thermoplastic resin layer was 110°C. It was ℃.

Details of the multilayer films (1) to (5) are shown in Table 1.

In addition, in Table 1, the resin component names are abbreviated as follows.

Polypropylene: PP

Polyethylene: PE

Nylon: Ny

Ethylene-vinyl acetate copolymer resin: EVA

[Production Example 6]

According to the method described in WO2012/046651, 6-(3-triethoxysilylpropyl)amino-1,3,5-triazine-2,4-diazide (compound represented by formula (10) above, 2 A molecular adhesive solution containing (described as “PTES” in the table) (solvent: ethanol, concentration 0.1 g/l) was obtained.

[Production Example 1]

The laminate for bonding (1) was manufactured using the multilayer film (1) by the following method.

For the first thermoplastic resin layer of the multilayer film (1), a corona processor (manufactured by Shinko Electric Measurement Co., Ltd., product name “Corona Scanner ASA-4”, output voltage: 9 kV (surface voltage), oscillation frequency: 20 kHz) A coronavirus survey was conducted. Next, the molecular adhesive solution obtained in Production Example 6 was applied to the surface subjected to corona irradiation using a Meyer bar (No. 12), and the obtained coating film was dried at 80°C for 60 seconds.

Next, using an ultraviolet irradiation device (manufactured by Heraeus Co., Ltd., product name "Light Hammer 10 MARK II", light source: mercury lamp), a fixing treatment is performed by irradiating ultraviolet rays to this coating film, thereby forming a molecular adhesive layer and a first heat A laminate for bonding (1) consisting of a plastic resin layer and a second thermoplastic resin layer (multilayer film (1)) was obtained.

In addition, the ultraviolet irradiation conditions were set at an illuminance of 84 mW/cm2 and a light quantity of 29 mJ/cm2, and the illuminance and light quantity were measured in the UVC range using an illuminance/photometer (manufactured by EIT, product name “UV Power Puck II”). Illuminance and light quantity were measured.

[Manufacturing Examples 2 to 4, Manufacturing Comparative Example 1]

A laminate for bonding was prepared in the same manner as in Production Example 1, except that instead of the multilayer film (1), the multilayer films (2) to (5) shown in Table 2 were used, respectively. 2) ~ (5) were obtained.

Details of the laminates (1) to (5) for bonding obtained in Production Examples 1 to 4 and Production Comparative Example 1 are shown in Table 2.

[Example 1]

Two sheets of laminate for bonding (1) (10 mm × 10 mm) obtained in Production Example 1 and two sheets of adherend [plasma-treated glass plate (30 mm × 70 mm × 2 mm)] were prepared.

The bonding laminate (1) and the adherend (glass plate) are overlapped so that the molecular adhesive layer of the bonding laminate (1) faces the plasma-treated surface of the glass plate, and this is applied for 5 hours under the conditions of 100°C and 0.5 MPa (surface pressure). By thermocompression bonding for a minute, a laminate consisting of the adherend/molecular adhesive layer/first thermoplastic resin layer/second thermoplastic resin layer was obtained.

Separately from this operation, the same operation was performed using the remaining laminate for bonding (1) and the adherend to obtain another laminate.

Next, the second thermoplastic resin layers of the two obtained laminates were thermocompressed for 10 seconds at 145°C and 0.5 MPa (surface pressure) to obtain a bonded structure.

[Example 2]

Two sheets of laminate for bonding (2) (10 mm × 10 mm) obtained in Production Example 2 and two sheets of adherend [plasma-treated glass plate (30 mm × 70 mm × 2 mm)] were prepared.

An adherend such that each molecular adhesive layer of the two bonding laminates 2 faces the plasma treated surface of the glass plate, and the second thermoplastic resin layers of the two bonding laminates 2 face each other. The laminate for bonding (2), the laminate for bonding (2), and the adherend were stacked in this order, and this was thermocompressed for 5 minutes under conditions of 145°C and 0.5 MPa (surface pressure) to obtain a bonded structure.

[Examples 3, 4, Comparative Example 1]

A bonded structure was obtained in the same manner as in Example 2, except that the bonding laminate and manufacturing conditions shown in Table 3 were used.

[Comparative Example 2]

Two sheets of multilayer film (1) (10 mm × 10 mm) obtained in Production Example 1 and two sheets of adherend [plasma-treated glass plate (30 mm × 70 mm × 2 mm)] were prepared.

A layer having a heat sealable temperature of 170° C. of the two multilayer films 1 is positioned so as to face the plasma treated surface of the glass plate, respectively, and a layer of the two multilayer films 1 having a heat sealable temperature of 145° C. The adherend, the multilayer film 1, the multilayer film 1, and the adherend were stacked in this order so as to face each other, and this was thermocompressed for 5 minutes under conditions of 145°C and 0.5 MPa (surface pressure) to obtain a bonded structure.

[Measurement of adhesive strength]

The bonded structures obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were used as test pieces, and the adhesive strength was measured with a universal tensile tester (Instron 5581, manufactured by Instron) under the condition of a tensile speed of 50 mm/min. . Additionally, the condition of the test piece was observed after the test was completed. The results are shown in Table 3.

Additionally, in Comparative Example 2, the adherend and the multilayer film were not sufficiently adhered, so the adhesive strength could not be measured.

[Evaluation of shape change]

The bonded structures obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were used as test pieces, and the leaching of the bonded laminate after heat compression was visually confirmed and evaluated based on the following criteria.

A: Leaching at the ends due to deformation of the laminate for joining could not be visually confirmed.

F: Leaching at the ends due to deformation of the laminate for joining could be visually confirmed.

From Table 3, the following can be seen.

In Examples 1 to 4, no destruction occurred within the layer derived from the laminate for bonding or at the interface between the layer derived from the laminate for bonding and the adherend in the test piece after measuring the adhesive strength. Therefore, in Examples 1 to 4, it can be seen that the two adherends are firmly joined.

On the other hand, in the laminate for bonding used in Comparative Example 1, the heat-sealable temperature of the first thermoplastic resin layer and the heat-sealable temperature of the second thermoplastic resin layer are the same. For this reason, deformation occurred during heat compression.

Additionally, in Comparative Example 2, the adherend and the multilayer film were not sufficiently adhered. Therefore, it is difficult to join glass plates with this method.

1: First thermoplastic resin layer
2: Second thermoplastic resin layer
3: Laminate composed of a first thermoplastic resin layer and a second thermoplastic resin layer
4: Molecular adhesive layer
5: Laminate for joining
6: Surface on the side in contact with the molecular adhesive layer
7: Surface opposite to the first thermoplastic resin layer
8. 21. 34: Molecular adhesive layer (AM)
9. 22. 35: First thermoplastic resin layer (A-1)
10. 23. 36: Second thermoplastic resin layer (A-2)
11. 24. 37: Laminate for joining (A)
12. 30. 42: Adhere (I)
13: Laminate resulting from process (L1)
14. 25. 38: Molecular adhesive layer (BM)
15. 26. 39: First thermoplastic resin layer (B-1)
16. 27. 40: Second thermoplastic resin layer (B-2)
17. 28. 41: Laminate for joining (B)
18. 32. 43: Adsorbent (II)
19: Laminate resulting from process (L2)
20. 33. 45: Junction structure
29: Laminate resulting from process (M1)
31: Laminate resulting from process (M2)
44: Obtained in process (N1)

Claims (11)

It has a molecular adhesive layer containing a molecular adhesive (M), a first thermoplastic resin layer having a single-layer structure, and a second thermoplastic resin layer having a single-layer structure or a multi-layer structure in this order, wherein the molecular adhesive layer and the second thermoplastic resin layer have a single-layer structure. A laminate for joining wherein the thermoplastic resin layer constitutes the outermost layer when each is used,
The molecular adhesive (M) contains at least one reactive group (Zα) selected from the group consisting of an amino group, an azide group, a mercapto group, an isocyanate group, a ureido group, and an epoxy group, a silanol group, and a hydrolysis reaction. It is a compound having at least one type of reactive group (Zβ) selected from the group consisting of a group that generates a silanol group by,
The first thermoplastic resin layer has, at least on the surface of the side in contact with the molecular adhesive layer, a reactive partial structure (Zγ) capable of forming a chemical bond with the reactive group (Zα) of the molecular adhesive (M). It contains a plastic resin (P ₁ ),
When the heat-sealable temperature of the first thermoplastic resin layer is T _h1 and the heat-sealable temperature of the second thermoplastic resin layer is T _h2 , T _h1 > T _h2 . According to claim 1,
The reactive group (Zα) possessed by the molecular adhesive (M) is at least one selected from the group consisting of an amino group, a mercapto group, an isocyanate group, a ureido group, and an epoxy group, and the reactive moiety possessed by the thermoplastic resin (P ₁ ) The structure (Zγ) is at least one selected from the group consisting of a hydroxy group, a carboxyl group, an aldehyde group, and an amino group, or,
The reactive group (Zα) of the molecular adhesive (M) is an azide group, and the reactive partial structure (Zγ) of the thermoplastic resin (P ₁ ) is a carbon-carbon single bond, a carbon-carbon double bond, and A laminate for joining, which is at least one member selected from the group consisting of carbon-hydrogen single bonds. According to claim 1,
A laminate for bonding, wherein the molecular adhesive (M) is a compound represented by the following formula (1).

(R ¹ is a reactive group (Zα) selected from the group consisting of an amino group, an azide group, a mercapto group, an isocyanate group, a ureido group, and an epoxy group, or a monovalent group having one or more of these reactive groups (however, an amino group, azide group, mercapto group, isocyanate group, ureido group and epoxy group are excluded), G represents a divalent organic group, Y represents a hydrocarbon group having 1 to 20 carbon atoms. a represents an integer of 1 to 3.) According to claim 1,
A laminate for joining in which the reactive group (Zα) of the molecular adhesive (M) and the reactive partial structure (Zγ) of the thermoplastic resin (P ₁ ) form a chemical bond. According to claim 1,
Bonding, wherein the thermoplastic resin (P ₁ ) is at least one selected from the group consisting of olefin resin, cycloolefin resin, acrylic resin, olefin-vinyl acetate resin, olefin ionomer resin, and polyester resin. For laminate. According to claim 1,
The second thermoplastic resin layer is composed of olefin resin, cycloolefin resin, acrylic resin, olefin-vinyl acetate resin, olefin ionomer resin, and polyester resin, at least on the surface opposite to the molecular adhesive layer. A laminate for joining, comprising at least one member selected from the group consisting of: A method of joining an adherend (I) and an adherend (II) using two bonding laminates, comprising:
The two bonding laminates are each independently the bonding laminate according to any one of claims 1 to 6,
The first laminate for bonding is comprised of a molecular adhesive layer (AM) containing a molecular adhesive ( _MA ), a first thermoplastic resin layer (A-1) having a single-layer structure, and a second layer having a single-layer structure or a multi-layer structure. The thermoplastic resin layer (A-2) is represented as a laminate for bonding (A) having this order, and the second laminate for bonding is a molecular adhesive layer (BM) containing a molecular adhesive ( _MB ), single layer structure. When represented as a laminate for bonding (B) having a first thermoplastic resin layer (B-1) having a single layer structure or a second thermoplastic resin layer (B-2) having a single-layer structure or a multi-layer structure in this order,
A process group including the following steps (L1) to (L3), a process group including steps (M1) to (M3), and a process group including steps (N1) and (N2). A method for bonding an adherend (I) and an adherend (II), characterized by carrying out a group of processes.
Process (L1): Process of bonding the molecular adhesive layer (AM) of the laminate for bonding (A) and the adherend (I)
Process (L2): Process of bonding the molecular adhesive layer (BM) of the laminate for bonding (B) and the adherend (II)
Step (L3): Heat welding the second thermoplastic resin layer (A-2) of the laminate obtained in step (L1) and the second thermoplastic resin layer (B-2) of the laminate obtained in step (L2). process
Step (M1): A process of heat welding the second thermoplastic resin layer (A-2) of the laminate for joining (A) and the second thermoplastic resin layer (B-2) of the laminate for joining (B).
Step (M2): A step of bonding the molecular adhesive layer (AM) of the laminate obtained in step (M1) and the adherend (I).
Step (M3): A step of bonding the molecular adhesive layer (BM) of the laminate obtained in step (M2) and the adherend (II).
Step (N1): An arrangement in which the second thermoplastic resin layer (A-2) of the laminate for joining (A) and the second thermoplastic resin layer (B-2) of the laminate for joining (B) face each other. , a process of overlapping the adherend (I), the laminate for bonding (A), the laminate for bonding (B), and the adherend (II) in this order.
Step (N2): Heating the product obtained in step (N1), adhesion of the molecular adhesive layer (AM) and the adherend (I), adhesion of the molecular adhesive layer (BM) and the adherend (II), and second heat A process of simultaneously heat welding the plastic resin layer (A-2) and the second thermoplastic resin layer (B-2) According to claim 7,
A method for bonding an adherend (I) and an adherend (II), comprising carrying out a group of processes including the above steps (L1) to (L3),
In the step (L1), the temperature when bonding the molecular adhesive layer (AM) of the bonding laminate (A) and the adherend (I) is T _L1 ,
In the step (L2), the temperature when bonding the molecular adhesive layer (BM) of the bonding laminate (B) and the adherend (II) is T _L2 ,
In step (L3), the temperature when heat welding the second thermoplastic resin layer (A-2) and the second thermoplastic resin layer (B-2) is T _L3 ,
The heat sealable temperature of the first thermoplastic resin layer (A-1) of the bonding laminate (A) is T _h1A , the heat sealable temperature of the second thermoplastic resin layer (A-2) is T _h2A ,
When the heat sealable temperature of the first thermoplastic resin layer (B-1) of the bonding laminate (B) is T _h1B and the heat sealable temperature of the second thermoplastic resin layer (B-2) is T _h2B ,
An adherend (I) and an adherend ( II) How to join.

According to claim 7,
A method for bonding an adherend (I) and an adherend (II), comprising carrying out a group of processes including the above steps (N1) and (N2),
The heat sealable temperature of the first thermoplastic resin layer (A-1) of the bonding laminate (A) is T _h1A , the heat sealable temperature of the second thermoplastic resin layer (A-2) is T _h2A ,
The heat sealable temperature of the first thermoplastic resin layer (B-1) of the bonding laminate (B) is T _h1B , the heat sealable temperature of the second thermoplastic resin layer (B-2) is T _h2B ,
In step (N2), when the temperature during heat welding is T _N2 ,
A method of bonding an adherend (I) and an adherend (II) that satisfies at least one of the following formulas (E-5) and (E-6).

A method for producing a bonded structure having a layer structure of the adherend (I)/laminated body for bonding (A) and the layer/adherent (II) derived from the laminate for bonding (B), comprising the method according to claim 7. A method for producing a bonded structure, characterized in that the adherend (I) and the adherend (II) are bonded using the method. According to claim 10,
A method for producing a bonded structure, wherein the adherend (I) and the adherend (II) each independently contain a metal, an inorganic substance, or a thermosetting resin at least on the adherend surface.

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