WO2019189667A1 - Layered product for bonding, method for bonding two adherends, and method for producing bonded structure - Google Patents

Abstract

The present invention relates to: a layered product for bonding which comprises, in the following order, a molecular-adhesive layer comprising a specific molecular adhesive (M), a first thermoplastic resin layer, which comprises a specific thermoplastic resin, and a second thermoplastic resin layer, the molecular-adhesive layer and the second thermoplastic resin layer serving as the outermost layers at the time of use, wherein, when the heat-sealable temperature of the first thermoplastic resin layer is expressed by Th1 and that of the second thermoplastic resin layer is expressed by Th2, then Th1>Th2; a method for bonding two adherends with this layered product for bonding; and a method for producing a bonded structure. Use of the layered product for bonding of the present invention makes it possible to conduct a thermal fusion-bonding step without adversely affecting the molecular-adhesive layer.

Description

Laminated body for joining, method for joining two adherends, and method for producing joined structure

The present invention relates to a bonding laminate having a molecular adhesive layer (a layer formed using a molecular adhesive; hereinafter the same), a method of bonding two adherends using the bonding laminate, And it is related with the manufacturing method of a joining structure.

A compound having two or more types of reactive groups is useful as a molecular adhesive because it can form a chemical bond utilizing the characteristics of each reactive group.
For example, Patent Document 1 discloses a method of bonding a base A and a base B, a step of forming a molecular adhesive layer on the surface of the base A using a specific molecular adhesive, and the surface of the base A A bonding method is described which includes a step of disposing the base B so as to face the molecular adhesive, and a step of bonding the base A and the base B by applying a force to the base A and the base B.

In Patent Document 1, as a method for forming a molecular adhesive layer on the surface of a substrate, a molecular adhesive solution in which a molecular adhesive is dissolved or dispersed is prepared, and after the substrate is immersed in the molecular adhesive solution, A method is described in which a chemical bond is formed between a molecular adhesive and the surface of a substrate by irradiating the object with ultraviolet rays, thereby forming a molecular adhesive layer.

WO2012 / 043631 (US2013 / 177770 A1)

As described in Patent Document 1, a double-sided adhesive sheet having molecular adhesive layers on both sides of a substrate can be efficiently obtained by immersing the substrate in a molecular adhesive solution. Such a double-sided adhesive sheet is useful as a bonding material when two adherends are easily and firmly fixed.
However, when a roll-to-roll method is employed to mass-produce such a double-sided adhesive sheet, it has been difficult to stably form molecular adhesive layers on both sides of the substrate by an immersion method.
Therefore, there has been a demand for a method capable of firmly joining two adherends using an adhesive sheet having a molecular adhesive layer obtained by employing a roll-to-roll method.

The present inventors examined a method of joining two adherends using a joining laminate having a molecular adhesive layer only on one surface. As a result, two laminates for bonding having a molecular adhesive layer on the thermoplastic resin layer were prepared, each molecular adhesive layer was bonded to each adherend, and two thermoplastic resin layers were further bonded. It has been found that two adherends can be bonded firmly by heat welding.

However, in this joining method, the thermoplastic resin layer may be greatly deformed depending on the conditions at which the two thermoplastic resin layers are thermally welded. As a result, the molecular adhesive layer may be deformed or the molecular adhesive may be deformed. There was a possibility that the adhesive strength of the layer might be reduced.

The present invention was made for the purpose of solving this problem, and is a bonding laminate having a molecular adhesive layer and a thermoplastic resin layer, without adversely affecting the molecular adhesive layer. It is an object of the present invention to provide a laminate for bonding capable of performing a heat welding step, a method for bonding two adherends using the laminate for bonding, and a method for manufacturing a bonded structure.

In order to solve the above-mentioned problems, the present inventors diligently studied a method of joining two adherends using a joining laminate having a molecular adhesive layer and a thermoplastic resin layer.
As a result, it has been found that by using a laminate for bonding that satisfies the following requirements (a) to (c), a thermal welding process can be performed without adversely affecting the molecular adhesive layer, and the present invention is completed. It came to.
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 thermally welded at a lower temperature than the first thermoplastic resin layer.

Thus, according to the present invention, the following laminates for bonding (1) to (6), the method of bonding the two adherends of (7) to (9), and the bonding structure of (10) to (11) A method of manufacturing a body is 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 multilayer structure are provided in this order. The molecular adhesive layer and the second thermoplastic resin layer are each a laminate for bonding that constitutes the outermost layer in use, and the molecular adhesive (M) is an amino group, an azide group, a mercapto At least one selected from the group consisting of at least one reactive group (Zα) selected from the group consisting of a group, an isocyanate group, a ureido group, and an epoxy group, a silanol group, and a group that generates a silanol group by a hydrolysis reaction. A compound having a reactive group (Zβ) of the species, and the first thermoplastic resin layer has at least a reactive group (M) of the molecular adhesive (M) on the surface in contact with the molecular adhesive layer. Zα) and chemical bond A thermoplastic resin having formed may reactive moiety structure (Zγ) are those containing a (P _1), heat-sealable temperature of the first thermoplastic resin layer is T _h1, the second thermoplastic resin layer When the heat-sealable temperature of _Th2 is _Th2 , the laminated body for joining which is _Th1 > _Th2 .
(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 a thermoplastic resin ( The reactive partial structure (Zγ) of P ₁ ) is at least one selected from the group consisting of a hydroxy group, a carboxy group, an aldehyde group, and an amino group, or the reaction that the molecular adhesive (M) has The reactive group (Zγ) of the thermoplastic resin (P ₁ ) is a carbon-carbon single bond, a carbon-carbon double bond, and a carbon-hydrogen single bond. The laminate for bonding according to (1), which is at least one selected from the group consisting of:
(3) The bonding laminate according to (1) or (2), 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, an azide group, a mercapto group, an isocyanate group, a ureido group and an epoxy group are excluded.) G represents a divalent organic group, X represents a hydroxy group, an alkoxy having 1 to 10 carbon atoms. And Y represents a hydrocarbon group having 1 to 20 carbon atoms, and 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, (1) to (3) The laminated body for bonding in any one.
(5) The thermoplastic resin (P ₁ ) is at least one selected from the group consisting of olefin resins, cycloolefin resins, acrylic resins, olefin-vinyl acetate resins, olefin ionomer resins, and polyester resins. The bonding laminate according to any one of (1) to (4), wherein
(6) The second thermoplastic resin layer has an olefin resin, a cycloolefin resin, an acrylic resin, an olefin-vinyl acetate resin, an olefin ionomer resin on at least the surface opposite to the molecular adhesive layer. And a laminate for bonding according to any one of (1) to (5), comprising at least one selected from the group consisting of polyester resins.
(7) A method of bonding an adherend (I) and an adherend (II) using two bonding laminates, wherein the two bonding laminates are independently The bonding laminate according to any one of (1) to (6), wherein the first bonding laminate comprises a molecular adhesive layer (AM) containing a molecular adhesive (M _A ), a single layer A bonding laminate (A) having a first thermoplastic resin layer (A-1) having a structure and a second thermoplastic resin layer (A-2) having a single layer structure or a multilayer structure in this order; A second bonding laminate, a molecular adhesive layer (BM) containing a molecular adhesive (M _B ), a first thermoplastic resin layer (B-1) having a single-layer structure, and a single When the second thermoplastic resin layer (B-2) having a layer structure or a multilayer structure is expressed as a bonding laminate (B) having this order, the following steps (L1) to (L3) ), A process group including processes (M1) to (M3), and a process group including processes (N1) and (N2). A method for joining the adherend (I) and the adherend (II).
Step (L1): Step of bonding the molecular adhesive layer (AM) of the bonding laminate (A) and the adherend (I) Step (L2): Molecular adhesive of the bonding laminate (B) Step (L3) for bonding the layer (BM) and the adherend (II): the second thermoplastic resin layer (A-2) of the laminate obtained in the step (L1), and a step ( Step (M1) of heat-welding the second thermoplastic resin layer (B-2) of the laminate obtained in L2): the second thermoplastic resin layer (A- 2) and step (M2) of thermally welding the second thermoplastic resin layer (B-2) of the laminate for bonding (B): molecular adhesive layer of the laminate obtained in step (M1) Step (M3) for bonding (AM) and adherend (I): molecular adhesive layer (BM) and adherend (II) of the laminate obtained in step (M2) Process process ( 1) An arrangement in which the second thermoplastic resin layer (A-2) of the laminate for bonding (A) and the second thermoplastic resin layer (B-2) of the laminate for bonding (B) face each other. , Adherend (I), bonding laminate (A), bonding laminate (B), and adherend (II) are stacked in this order (step (N2): obtained in step (N1) Are heated, the adhesion between the molecular adhesive layer (AM) and the adherend (I), the adhesion between the molecular adhesive layer (BM) and the adherend (II), the second (8) performing the thermal welding of the thermoplastic resin layer (A-2) and the second thermoplastic resin layer (B-2) at the same time (8) performing the process group including the steps (L1) to (L3); A method of joining the adherend (I) and the adherend (II),
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 , and in the step (L2), the bonding laminate The temperature at which the molecular adhesive layer (BM) of the body (B) and the adherend (II) are bonded is T _L2 , and in the step (L3), the second thermoplastic resin layer (A-2) The temperature at which the second thermoplastic resin layer (B-2) is thermally welded is T _L3 , and the heat-sealable temperature of the first thermoplastic resin layer (A-1) of the laminate for joining (A) T _h1A , the heat-sealable temperature of the second thermoplastic resin layer (A-2) is _{Th 2A} , and the heat seal of the first thermoplastic resin layer (B-1) of the laminate for bonding (B) possible temperature _{T h1b,} when the heat-sealable temperature of the second thermoplastic resin layer (B-2) is a _{T H2B,} the following formula (E The adherend (I) according to (7), wherein both 1) and formula (E-2) are satisfied, and at least one of the following formulas (E-3) and (E-4) is satisfied: A method of joining the adherend (II).

(9) A method of joining the adherend (I) and the adherend (II), wherein the process group including the steps (N1) and (N2) is performed, and the joining laminate (A) The heat-sealable temperature of the thermoplastic resin layer (A-1) No. 1 is _Th1A , the heat-sealable temperature of the second thermoplastic resin layer (A-2) is _Th2A , and the laminate for bonding (B) In the step (N2), the heat-sealable temperature of the first thermoplastic resin layer (B-1) is T _h1B , and the heat-sealable temperature of the second thermoplastic resin layer (B-2) is _Th2B . When the temperature at the time of heat welding is _TN2 , at least one of the following formulas (E-5) and (E-6) is satisfied: A method of joining the body (II).

(10) A method for producing a bonded structure having a layer structure of an adherend (I) / bonded laminate (A) and a layer derived from the bonded laminate (B) / adhered body (II). A method for producing a bonded structure comprising bonding the adherend (I) and the adherend (II) using the method according to any one of (7) to (9).
(11) The adherend (I) and the adherend (II) each independently include at least one selected from the group consisting of metals, inorganic substances, and thermosetting resins on the adherend surface. (10) The manufacturing method of the junction structure according to (10).

In the present invention, the molecular adhesive refers to a compound having two or more reactive groups.
“Molecular adhesive containing” in the “molecular adhesive layer containing molecular adhesive” means “molecular adhesive and / or a compound derived from a molecular adhesive (for example, the structure of a reactive group has changed through a reaction). Compound) ”.
“The first thermoplastic resin layer contains a thermoplastic resin having a reactive partial structure (Zγ)” means “a thermoplastic resin having a reactive partial structure (Zγ) and / or derived from this thermoplastic resin. It includes a resin (for example, a resin that has undergone a reaction to change the structure of the reactive partial structure (Zγ)).
“The molecular adhesive layer and the second thermoplastic resin layer each constitute the outermost layer in use” means that the molecular adhesive layer is adhered to the adherend or the second thermoplastic resin layers are bonded to each other. Each layer is the outermost layer when thermally welded. Therefore, the laminate for bonding may have a protective sheet or the like as the outermost layer after the laminate for manufacturing is used until it is used.
The “heat sealable temperature” of the thermoplastic resin layer is a temperature necessary for heat welding in order to achieve a sufficient heat seal strength. Specifically, according to the method described in the examples, heat seal Possible temperature can be determined.
"Temperature when adhering the molecular adhesive layer and adherend" and "Temperature when thermally welding the thermoplastic resin layer and the thermoplastic resin layer" are used when a heating press or the like is used. The surface temperature of the crimping member of the device.
In this specification, the unit of temperature is “° C.”.

According to the present invention, a bonding laminate having a molecular adhesive layer and a thermoplastic resin layer, the bonding laminate capable of performing a heat welding step without adversely affecting the molecular adhesive layer, A method for bonding two adherends using the bonding laminate and a method for manufacturing a bonded structure are provided.

It is a schematic diagram showing an example of the manufacturing process of the laminated body for joining of this invention. FIG. 5 is a schematic diagram showing a process group including processes (L1) to (L3). FIG. 5 is a schematic diagram showing a process group including processes (M1) to (M3). It is a schematic diagram showing the process group containing process (N1) and (N2).

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

1) Bonding Laminate The bonding laminate of the present invention has a molecular adhesive layer containing a molecular adhesive (M), a first thermoplastic resin layer having a single layer structure, and a single layer structure or a multilayer structure. The molecular adhesive layer has a second thermoplastic resin layer in this order, and each of the molecular adhesive layer and the second thermoplastic resin layer constitutes an outermost layer at the time of use. (M) is at least one reactive group (Zα) selected from the group consisting of an amino group, an azido group, a mercapto group, an isocyanate group, a ureido group and an epoxy group, a silanol group, and a silanol group by hydrolysis reaction. Is a compound having at least one reactive group (Zβ) selected from the group consisting of groups that form a group, and the first thermoplastic resin layer is at least on the surface in contact with the molecular adhesive layer, Molecular adhesion Those containing a thermoplastic resin (P ₁₎ having a reactive group (M) reactive moieties capable of forming (Zα) and the chemical bond (Zγ), heat-sealing of the first thermoplastic resin layer When the possible temperature is T _h1 and the heat-sealable temperature of the second thermoplastic resin layer is T _h2 , the laminated body for joining _satisfying T _h1 > T _h2 .

[Molecular adhesive layer]
The molecular adhesive layer is a layer directly adjacent on the first thermoplastic resin layer.
The molecular adhesive layer is a layer constituting one of the outermost layers when the bonding laminate is used.
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 includes the molecular adhesive (M). That is, the molecular adhesive layer in the bonding laminate is a reaction product of the molecular adhesive (M) (reactive group remaining) and the molecular adhesive (M) (reactive group structure changes). At least one of the above).

The molecular adhesive (M) includes 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. Is a compound having at least one reactive group (Zβ) selected from the group consisting of groups that generate silanol groups. 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. Is included.

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 laminated body for joining, it is considered that the molecular adhesive (M) is chemically fixed to the surface of the first thermoplastic resin layer by this chemical bond. Examples of the chemical bond at this time include a covalent bond, a hydrogen bond, an ionic bond, and an intermolecular force, and a covalent bond is preferable.

The reactive group (Zβ) in the molecular adhesive (M) is mainly used for forming a chemical bond with the adherend when the bonding laminate is bonded to the adherend. . Therefore, the laminate for bonding is preferably used for an adherend having a group having high reactivity with these groups on the surface.

Examples of the group that generates a silanol group by a hydrolysis reaction include a group having a partial structure represented by Si—X ¹ . X ¹ is a hydrolyzable group such as an alkoxy group having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group, an n-propoxy group or an isopropoxy group; a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom; Can be mentioned.

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

(R ¹ represents a reactive group (Zα) or a monovalent group having one or more reactive groups (Zα) (excluding the reactive group (Zα) itself), and G is a divalent group. Represents an organic group, X represents a hydroxy group, an alkoxy group having 1 to 10 carbon atoms or a halogen atom, Y represents a hydrocarbon group having 1 to 20 carbon atoms, a represents an integer of 1 to 3 .)

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).

In the 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; and arylene groups such as o-phenylene group, m-phenylene group and p-phenylene group.

R ³ and R ⁴ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, preferably a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.
Examples of the hydrocarbon group for 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, n Alkyl groups such as -hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group; vinyl group, 1-propenyl group, 2-propenyl group, isopropenyl group, 3-butenyl group, Alkenyl groups such as 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;

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 as those shown as the hydrocarbon groups for 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), * is a bond with a carbon atom constituting an aromatic ring. Represents a hand.)

The divalent organic group for G has a substituent or an unsubstituted alkylene group having 1 to 20 carbon atoms, a substituent, or an unsubstituted alkenylene group having 2 to 20 carbon atoms, or a substituent. Or an unsubstituted alkynylene group having 2 to 20 carbon atoms, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, and the like.

Examples of the alkylene group having 1 to 20 carbon atoms of G include a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group.
Examples of the alkenylene group having 2 to 20 carbon atoms of G include vinylene group, propenylene group, butenylene group, pentenylene group and the like.
Examples of the alkynylene group having 2 to 20 carbon atoms of G include an ethynylene group and a propynylene group.
Examples of the arylene group having 6 to 20 carbon atoms of G include o-phenylene group, m-phenylene group, p-phenylene group, 2,6-naphthylene group, 1,5-naphthylene group and the like.

Examples of the substituent for the alkylene group, alkenylene group, and alkynylene group include a halogen atom such as a fluorine atom and a chlorine atom; an alkoxy group such as a methoxy group and an ethoxy group; an alkylthio group such as a methylthio group and an ethylthio group; a methoxycarbonyl group; An alkoxycarbonyl group such as an ethoxycarbonyl group; and the like.

Examples of the substituent for the arylene group include: a cyano group; a nitro group; a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom; an alkyl group such as a methyl group and an ethyl group; an alkoxy group such as a methoxy group and an ethoxy group; And alkylthio groups such as ethylthio group; and the like.
These substituents may be bonded to any position in a group such as an alkylene group, an alkenylene group, an alkynylene group and an arylene group. A plurality of substituents may be bonded to a group such as an alkylene group, which are the same or different.

Examples of the alkoxy group having 1 to 10 carbon atoms of X include a methoxy group, an ethoxy group, an n-propoxy group, and an isopropoxy group.
Examples of the halogen atom for X include a fluorine atom, a chlorine atom, and a bromine atom.
Examples of the hydrocarbon group having 1 to 20 carbon atoms for Y include the same as those shown as the hydrocarbon groups for 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] trimethoxysilane, Molecules in which R ¹ is an amino group such as [3- (phenylamino) propyl] trimethoxysilane, trimethyl [3- (triethoxysilyl) propyl] ammonium chloride, trimethyl [3- (trimethoxysilyl) propyl] ammonium chloride adhesive;

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

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

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

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

Molecules in which R ¹ is an epoxy group such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane adhesive;

3- (2-aminoethylamino) propyltrimethoxysilane, 3- (2-aminoethylamino) propyltriethoxysilane, 3- (2-aminoethylamino) propyldimethoxymethylsilane, 2- (3,4-epoxy A molecular adhesive in which R ¹ is a monovalent group having one or more reactive groups (Zα) such as (cyclohexyl) ethyltrimethoxysilane, compounds represented by the following formulas (5) to (13);

A molecular adhesive (M) can be used individually by 1 type or in combination of 2 or more types.
Among these compounds, the compound represented by the formula (1) is preferably a compound in which R ¹ is a group represented by the formula (4), more preferably the compounds represented by the formulas (5) to (13). Compounds represented by formulas (5) to (10) are more preferable.
These compounds have a triazine ring at R ¹ . The molecular adhesive (M) having a triazine ring tends to be more efficiently fixed on the first thermoplastic resin layer.

As the molecular adhesive (M), a compound known as a silane coupling agent can be used. Further, compounds wherein ^{R 1} is a group represented by the formula (4) is No. WO2012 / 046651, No. WO2012 / 043631, can be synthesized according to the method described in such as JP WO2013 / 186941.

The molecular adhesive layer may contain components other than the molecular adhesive (M). Examples of components other than the molecular adhesive (M) include a catalyst.
The catalyst can be appropriately selected and used depending on the type of the reactive group (Zα).

The content of the molecular adhesive (M) in the molecular adhesive layer is 50% on the basis of the whole molecular adhesive layer because the adhesive force of the molecular adhesive layer is reduced when a component not involved in adhesion is included. It is preferably at least mass%, more preferably at least 70 mass% and at most 100 mass%, further preferably at least 90 mass% and at most 100 mass%, particularly preferably at least 100 mass%.

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 particularly preferably 50 nm or less. Further, 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 of 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 or a non-uniform composition. For example, the first thermoplastic resin layer may contain a lot of 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 a reactive partial structure (Zγ) capable of forming a chemical bond with the reactive group (Zα) of the molecular adhesive (M) on the surface in contact with the molecular adhesive layer. A thermoplastic resin (P ₁ ) having That is, the first thermoplastic resin layer in the bonding laminate is a reaction product of the thermoplastic resin (P ₁ ) (reactive partial structure (Zγ) remains) and the thermoplastic resin (P ₁ ). And at least one of the products (reactive partial structures (Zγ) changed).
Note that “the surface on the side in contact with the molecular adhesive layer contains a thermoplastic resin (P ₁ )” means that the surface of the first thermoplastic resin layer is thermoplastic before the molecular adhesive layer is formed. This represents a state in which the resin (P ₁ ) is exposed.
In the stage before forming the molecular adhesive layer, by a thermoplastic resin (P ₁₎ is exposed on the surface of the first thermoplastic resin layer, the reactive moiety of the thermoplastic resin (P ₁₎ ( Zγ) can efficiently react with the reactive group (Zα) of the molecular adhesive (M).

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

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. Is mentioned.

Examples of cycloolefin resins include cycloolefin addition polymers, copolymers of cycloolefins and α-olefins, and ring-opening polymers of norbornene monomers.
Examples of the cycloolefin include cyclopentene, cyclooctene, and norbornene monomers.
Examples of the α-olefin include ethylene and propylene.

As acrylic resins, homopolymers of (meth) acrylic monomers, copolymers of (meth) acrylic monomers, (meth) acrylic monomers, and single quantities copolymerizable therewith And a copolymer with the body.
(Meth) acrylic monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2- (Meth) acrylic acid esters such as ethylhexyl (meth) acrylate; (meth) acrylic acid; and the like.
Monomers copolymerizable with (meth) acrylic monomers include ethylene; aromatic vinyl monomers such as styrene, α-methylstyrene and chlorostyrene; cyano group-containing ethylene such as acrylonitrile and methacrylonitrile. Unsaturated monomers; (meth) acrylamide monomers such as (meth) acrylamide, N-methylol (meth) acrylamide, and N-butoxymethyl (meth) acrylamide;
In the present specification, “(meth) acrylic acid” means “acrylic acid or methacrylic acid”. The same applies to the same description of “(meth) acrylic acid ester”, “(meth) acrylic”, “(meth) acrylate”, and the like.

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

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 carboxy group-containing monomer, and a resin having an ionic cross-linking that links the copolymer chains. It is done.
Examples of the olefin monomer include ethylene and propylene.
Examples of the carboxy 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 ionomer resin is composed of a carboxylate ion generated by deprotonation of the carboxy group of the carboxy group-containing monomer and a metal ion.
Metal ions include sodium (I) ion, potassium (I) ion, lithium (I) ion, calcium (II) ion, magnesium (II) ion, zinc (II) ion, copper (I) ion, copper (II) ) Ion, cobalt (II) ion, cobalt (III) ion, nickel (II) ion, manganese (II) ion, aluminum (III) ion and the like.

Examples of the polyester resin include those obtained by a polycondensation reaction of a polyvalent carboxylic acid and a polyhydric alcohol.
Examples of the polyvalent carboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanoic acid, 1,4-cyclohexanedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, Examples include 2,6-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, trimellitic acid, and the like.
Examples of polyhydric alcohols include ethylene glycol, propylene glycol, 1,4-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 3-methyl-1,5-pentane. Diol, 1,2-hexanediol, 1,6-hexanediol, 1,9-nonanediol, 1,4-cyclohexanedimethanol, diethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, trimethylolpropane, glycerin, etc. Is mentioned.

Among the polyester resins, an amorphous polyester resin is more preferable. An amorphous polyester resin refers to a polyester resin that does not show a clear crystallization or crystal melting peak by DSC (differential scanning calorimetry).
Amorphous polyester resins include glycol-modified polyethylene terephthalate (PETG), glycol-modified poly (1,4-cyclohexanedimethylene terephthalate) (PCTG), acid-modified poly (1,4-cyclohexanedimethylene terephthalate) (PCTA), etc. Is mentioned.

The thermoplastic resin (P ₁₎ can be used in combination singly or two or more.

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

Examples of the reactive partial structure (Zγ) of the thermoplastic resin (P ₁ ) include a hydroxy group, a carboxy group, an aldehyde group, an amino group, a carbon-carbon single bond, a carbon-carbon double bond, and a carbon-hydrogen single bond. Is mentioned. As 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 carboxy group, an aldehyde group, and an amino group as a reactive partial structure (Zγ), These reactive partial structures (Zγ ′) in P ₁ ′) can be formed by a known method.

For example, when performing a polymerization reaction, a thermoplastic resin (P ₁ ) having a reactive partial structure (Zγ ′) is obtained by using a monomer having a functional group such as a hydroxy group, a carboxy group, an aldehyde group, or an amino group. ') Can be manufactured. In addition, the polymer obtained by carrying out the polymerization reaction without using these monomers may be subjected to a modification treatment such as maleic anhydride modification to cause heat having a reactive partial structure (Zγ ′). A plastic resin (P ₁ ′) can be produced.
By using the thermoplastic resin (P ₁ ′) obtained by these methods as a molding material, the first thermoplastic resin layer can be efficiently formed.

In addition, after forming a thermoplastic resin layer that does not contain the thermoplastic resin (P ₁ ′), surface treatment is performed on the thermoplastic resin layer, thereby generating hydroxy groups or carboxy groups on the surface of the layer. May be. That is, by performing this surface treatment, the 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 a hydroxy group or a carboxy group. Examples of the surface treatment 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 the adhesion with the molecular adhesive layer is not inhibited.
Examples of components other than the thermoplastic resin (P ₁ ) include ultraviolet absorbers, light stabilizers, antioxidants, antistatic agents, slip agents, antiblocking agents, and colorants.
These contents can be appropriately determined according to the purpose.

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

The thickness of the first thermoplastic resin layer is usually 5 to 150 μm, preferably 10 to 120 μm, more preferably 15 to 80 μm.
It can fully suppress that the performance of a molecular adhesive layer falls by the heating in a heat welding process because the thickness of a 1st thermoplastic resin layer is 5 micrometers or more. Moreover, a junction part (between adherends) can be made thin because the thickness of a 1st thermoplastic resin layer is 80 micrometers or less.

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 a change in the shape of the first thermoplastic resin layer when performing heat welding. Moreover, since the heat-sealable temperature of the first thermoplastic resin layer is 200 ° C. or less, the influence on the molecular adhesive layer during heat welding can be suppressed.
The heat-sealable temperature of the first thermoplastic resin layer is 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 additive, the first thermoplastic resin The characteristics are influenced by the crystallinity of the layer, the density of the first thermoplastic resin layer, and the like.
Therefore, for example, after determining the thermoplastic resin to be used, the first thermoplastic resin layer having the target heat-sealable temperature can be formed by adjusting the type and amount of the additive.

[Second thermoplastic resin layer]
The second thermoplastic resin layer is a layer adjacent to the first thermoplastic resin layer, and constitutes one of the outermost layers when the bonding laminate is used. Note that 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 thermal welding with the second thermoplastic resin layer of the other laminate for bonding.

The second thermoplastic resin layer may have a single layer structure or a multilayer structure. Even if the composition of the second thermoplastic resin layer when the second thermoplastic resin layer has a single-layer structure and each layer when the second thermoplastic resin layer has a multilayer structure are uniform, The composition may not be uniform. 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”) that can be melted at a relatively low temperature and solidified in a short time on at least the surface opposite to the first thermoplastic resin layer. (It may be referred to as (P ₂ ) ”).
By including the thermoplastic resin (P ₂ ) on the surface opposite to the first thermoplastic resin layer, the process is efficiently performed when thermally bonding with the thermoplastic resin layer of the other laminate for bonding. be able to.
“The thermoplastic resin (P ₂ ) is included on the surface opposite to the first thermoplastic resin layer” means that the thermoplastic resin (P ₂ ) is on the surface opposite to the first thermoplastic resin layer. It means being exposed.

Examples of the thermoplastic resin (P ₂ ) include olefin resins, cycloolefin resins, acrylic resins, olefin-vinyl acetate resins, olefin ionomer resins, and polyester resins.
Specific examples of these thermoplastic resins include the same as those shown as the thermoplastic resin (P ₁ ).
Thermoplastic resin (P ₂₎ can be used in combination singly or two or more.

The second thermoplastic resin layer may contain components other than the thermoplastic resin (P ₂ ) as long as it does not hinder the heat weldability.
Examples of components other than the thermoplastic resin (P ₂ ) include ultraviolet absorbers, light stabilizers, antioxidants, antistatic agents, slip agents, antiblocking agents, and colorants.
These contents can be appropriately determined according to the purpose.

When the second thermoplastic resin layer has a single layer structure, the second thermoplastic resin layer may be a uniform layer containing a thermoplastic resin (P ₂ ) or at least the first thermoplastic resin. A non-uniform layer containing a thermoplastic resin (P ₂ ) on the surface opposite to the resin layer can be mentioned.
The content of the thermoplastic resin (P ₂ ) in the _second thermoplastic resin layer having a single layer structure is usually 50 to 100% by mass, preferably 80 to 100% by 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, 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. Moreover, a junction part (between adherends) can be made thin because the thickness of this 2nd thermoplastic resin layer is 150 micrometers or less.

When the second thermoplastic resin layer has a multilayer structure, the second thermoplastic resin layer is the outermost layer on the side opposite to the first thermoplastic resin layer (second heat having a multilayer structure). Among the two outermost layers of the thermoplastic resin layer, the outermost layer that is not in contact with the first thermoplastic resin layer) has a thermoplastic resin (P ₂ ) on the surface opposite to the first thermoplastic resin layer. And a layer having a multilayer structure.
In the second thermoplastic resin layer having a multilayer structure, the content of the thermoplastic resin (P ₂ ) contained in the outermost layer opposite to the first thermoplastic resin layer is based on the entire outermost layer. The amount is usually 50 to 100% by mass, preferably 80 to 100% by mass.
The total thickness of the 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 thickness of the entire second thermoplastic resin layer having a multilayer structure is 3 μm or more, thermal welding can be sufficiently performed. Moreover, a junction part (between adherends) can be made thin because the thickness of this 2nd thermoplastic resin layer is 150 micrometers or less.
In the second thermoplastic resin layer having a multilayer structure, the number of layers is not particularly limited. The number of the second thermoplastic resin layers having a multilayer structure is usually 2 to 10, and 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, the handleability at normal temperature is improved. Moreover, when the heat-sealable temperature of the second thermoplastic resin layer is 180 ° C. or less, when the laminate for bonding of the present invention is used, the interlayer between the second thermoplastic resin layers is firmly bonded. It is possible to bond the two adherends more firmly.
The heat-sealable temperature of the second thermoplastic resin layer can be adjusted by the same method as the method for adjusting the heat-sealable temperature of the first thermoplastic resin layer.
When the second thermoplastic resin layer has a multilayer structure, the heat-sealable temperature of the second thermoplastic resin layer is the heat of the outermost layer on the side opposite to the first thermoplastic resin layer. The temperature that can be sealed.

[Laminate for bonding]
The bonding laminate is a first heat of a laminate composed of a first thermoplastic resin layer and a second thermoplastic resin layer (hereinafter sometimes referred to as “laminate (η)”). It can be produced by forming a molecular adhesive layer directly on the plastic resin layer.

For example, as shown in FIG. 1, the 1st thermoplastic resin layer (1) of the laminated body (3) comprised by the 1st thermoplastic resin layer (1) and the 2nd thermoplastic resin layer (2). A laminated body (5) for bonding is obtained by directly forming a molecular adhesive layer (4) thereon.
As described above, in the laminate (3), the first thermoplastic resin layer (1) includes the thermoplastic resin (P ₁ ) on the surface (6) in contact with the molecular adhesive layer (4). . Furthermore, the second thermoplastic resin layer (2) of the laminate (3) contains a thermoplastic resin (P ₂ ) on the surface (7) opposite to the first thermoplastic resin layer (1). Is preferred.

The manufacturing method of a laminated body ((eta)) is not specifically 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 ) and extruding them simultaneously from a multilayer die is used as a laminate. It can be used as (η).
Further, a resin film containing a thermoplastic resin (P _1), the multi-layer film obtained by pasting a resin film containing a thermoplastic resin (P _2), can be used as a laminate (eta) .

Also, on the first thermoplastic resin layer containing a thermoplastic resin (P ₁₎ (resin film), a coating solution containing a thermoplastic resin (P ₂₎ was applied, and drying the resulting coating film Forming a second thermoplastic resin layer, or applying a coating solution containing the thermoplastic resin (P ₁ ) on the second thermoplastic resin layer (resin film) containing the thermoplastic resin (P ₂ ). A multilayer film obtained by coating and drying the obtained coating film to form the first thermoplastic resin layer can be used as the laminate (η).

Among these, it is preferable to use a coextruded multilayer film as the laminate (η) because delamination between the first thermoplastic resin layer and the second thermoplastic resin layer hardly occurs.

In the present specification, a resin film in which other layers are not yet formed may be expressed as “first thermoplastic resin layer” or “second thermoplastic resin layer”.

When producing the laminate (η), the components of each layer are adjusted 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. decide.
That is, when the heat-sealable temperature of the first thermoplastic resin layer is _Th1 and the heat-sealable temperature of the second thermoplastic resin layer is _Th2 in the bonding laminate of the present invention, _Th1 > T _h2 .
As will be described later, when two adherends are bonded using the bonding laminate of the present invention, the heat-sealable temperature of the first thermoplastic resin layer is set to the heat-sealable temperature of the second thermoplastic resin layer. By making it higher than this, the heat welding step can be performed without adversely affecting the molecular adhesive layer.

The molecular adhesive (M) used when forming the molecular adhesive layer is composed of the reactive group (Zα) and the reactive partial structure (Zγ) of the thermoplastic resin (P ₁ ) in the _first thermoplastic resin layer. ) Can be selected as appropriate.
Of these, the reactive group (Zα) and the reactive partial structure (Zγ) preferably satisfy the following requirement (Q1).
Requirement (Q1):
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 ). The reactive partial structure (Zγ) of is at least one selected from the group consisting of a hydroxy group, a carboxy 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, carbon-carbon two At least one selected from the group consisting of a heavy bond and a carbon-hydrogen single bond.

In the bonding laminate 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, It is considered that the adhesive (M) is fixed to the first thermoplastic resin layer.
It is considered that this chemical bond can be efficiently formed 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, the reactive group (Zα) and the reactive partial structure (Zγ) Preferred combinations [reactive group (Zα) / reactive partial structure (Zγ)] include (amino group / hydroxy group), (amino group / carboxy group), (isocyanate group / hydroxy group), and (isocyanate group / carboxy group). Group), (hydroxy group / carboxy group) and the like.

When the reactive group (Zα) is an azide group, the azide group is activated by irradiation with light as described later. In this case, nitrene as a reaction intermediate can react with a carbon-carbon single bond, a carbon-carbon double bond, and a carbon-hydrogen single bond, so that the reactive partial structure (Zγ) of the thermoplastic resin (P ₁ ). Is preferably 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.
A thermoplastic resin usually contains at least one of a carbon-carbon single bond, a carbon-carbon double bond, and a carbon-hydrogen single bond. Therefore, when the molecular adhesive (M) having an azide group is used, the type of the thermoplastic resin (P ₁ ) is not particularly limited.

The method for 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 onto the first thermoplastic resin layer, and then the obtained coating film is subjected to a drying treatment or molecular adhesive ( A molecular adhesive layer can be formed by performing a process of fixing M) to the first thermoplastic resin layer.

The solvent used when preparing the molecular adhesive solution is not particularly limited. Examples of the solvent include alcohol solvents such as methanol, ethanol, isopropanol, ethylene glycol, and diethylene glycol; ketone solvents such as acetone and methyl ethyl ketone; ester solvents such as ethyl acetate and butyl acetate; halogen-containing compound solvents such as methylene chloride; Aliphatic hydrocarbon solvents such as butane and hexane; Ether solvents such as tetrahydrofuran and butyl ether; Aromatic solvents such as benzene and toluene; Amides solvents such as N, N-dimethylformamide and N-methylpyrrolidone; Water And the like.
These can be used alone or in combination of two or more.

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. Moreover, the reaction which the molecular adhesive solution does not intend can be suppressed by setting it as 1.000 mol / L or less, and it is excellent in stability of a solution.

The application method of the molecular adhesive solution is not particularly limited, and a known application method can be used. Examples of the coating method include spin coating, spray coating, bar coating, knife coating, roll knife coating, roll coating, blade coating, dip coating, curtain coating, die coating, and gravure coating. The bar coating method and the gravure coating method are preferable.

After applying the molecular adhesive solution, normally, in order to dry the obtained coating film, it is necessary to carry out a natural drying or a drying process by putting it into a drying mechanism. Among these, it is preferable from the viewpoint of improvement in productivity to perform a drying process by charging into a drying mechanism. As the drying mechanism, for example, a batch-type drying mechanism such as an air oven, a heat roll, a hot air through mechanism (a drying target moves and passes through an open drying furnace, and is heated and dried while receiving air. A continuous drying mechanism, etc.). An apparatus that can also be used as a part of these drying mechanisms, for example, a heating medium circulating heater such as high-frequency heating or an oil heater, and a heater such as a far-infrared heater itself can be used as the drying mechanism. Among these, a hot air through mechanism is preferable from the viewpoint of improving productivity.
The drying temperature adjusted by the drying mechanism 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 the molecular adhesive layer, a process of fixing the molecular adhesive (M) to the first thermoplastic resin layer (hereinafter sometimes referred to as a fixing process) is usually performed. The fixing treatment can be appropriately selected according to the characteristics of the reactive group (Zα) of the molecular adhesive (M). Usually, a chemical bond is generated by applying the molecular adhesive (M) onto the first thermoplastic resin layer, and the generation of the chemical bond is promoted by heating. It is preferable from the viewpoint of improvement. The heating temperature is usually 40 to 250 ° C, preferably 60 to 200 ° C, 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.
It does not specifically limit as a heating method, The mechanism and apparatus similar to the above-mentioned drying mechanism can be used.

When the reactive group (Zα) has photoreactivity, such as an azide group, a light irradiation process is performed as the fixing process. As the irradiation light, 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 between the reactive group (Zα) and the reactive group (Zγ).
Ultraviolet irradiation can be performed using an ultraviolet irradiation device using a light source such as a mercury lamp, a metal halide lamp, an ultraviolet LED, or an electrodeless lamp.
The treatment conditions for the light irradiation treatment are not particularly limited as long as the target photoreaction can be performed.

When forming the molecular adhesive layer, the application of the molecular adhesive solution, the drying process, and the fixing process may be repeated a plurality of times.

2) Method of joining two adherends The method of joining two adherends of the present invention uses two laminates for joining, and uses adherend (I) and adherend (II). The two laminates for bonding are each independently the laminate for bonding of the present invention, and the first laminate for bonding contains a molecular adhesive (M _A ). A molecular adhesive layer (AM), 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 multilayer structure. This is expressed as a bonding laminate (A) having this order, and the second bonding laminate is composed of a molecular adhesive layer (BM) containing a molecular adhesive (M _B ), a first layer having a single layer structure. A bonding laminate (B) having a thermoplastic resin layer (B-1) and a second thermoplastic resin layer (B-2) having a single layer structure or a multilayer structure in this order; When you,
Any one selected from a process group including the following processes (L1) to (L3), a process group including the processes (M1) to (M3), and a process group including the processes (N1) and (N2). It is a method for joining the adherend (I) and the adherend (II), characterized by performing a process group.
Step (L1): Step of bonding the molecular adhesive layer (AM) of the bonding laminate (A) and the adherend (I) Step (L2): Molecular adhesive of the bonding laminate (B) Step (L3) for bonding the layer (BM) and the adherend (II): the second thermoplastic resin layer (A-2) of the laminate obtained in the step (L1), and a step ( Step (M1) of heat-welding the second thermoplastic resin layer (B-2) of the laminate obtained in L2): the second thermoplastic resin layer (A- 2) and step (M2) of thermally welding the second thermoplastic resin layer (B-2) of the laminate for bonding (B): molecular adhesive layer of the laminate obtained in step (M1) Step (M3) for bonding (AM) and adherend (I): molecular adhesive layer (BM) and adherend (II) of the laminate obtained in step (M2) Process process ( 1) An arrangement in which the second thermoplastic resin layer (A-2) of the laminate for bonding (A) and the second thermoplastic resin layer (B-2) of the laminate for bonding (B) face each other. , Adherend (I), bonding laminate (A), bonding laminate (B), and adherend (II) are stacked in this order (step (N2): obtained in step (N1) Are heated, the adhesion between the molecular adhesive layer (AM) and the adherend (I), the adhesion between the molecular adhesive layer (BM) and the adherend (II), the second A step of simultaneously performing thermal welding between the thermoplastic resin layer (A-2) and the second thermoplastic resin layer (B-2).

The bonding laminate (A) includes a molecular adhesive layer (AM) containing a molecular adhesive (M _A ), a first thermoplastic resin layer (A-1), and a second thermoplastic resin layer ( A laminated body for bonding having A-2) in this order.
In the bonding method of the present invention, the bonding laminate (A) is used for adhesion to the adherend (I).

The bonding laminate (B) includes a molecular adhesive layer (BM) containing a molecular adhesive (M _B ), a first thermoplastic resin layer (B-1), and a second thermoplastic resin layer ( It is a laminated body (B) having B-2) in this order.
In the bonding method of the present invention, the bonding laminate (B) is used for adhesion to the adherend (II).

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

The second thermoplastic resin layer (A-2) of the laminate for bonding (A) has a thermoplastic resin (P ₂ ) (hereinafter referred to as “the first thermoplastic resin layer (A-1)” on the surface opposite to the first thermoplastic resin layer (A-1). 2), the thermoplastic resin (P ₂ ) contained in the second thermoplastic resin layer (A-2) may be represented as “thermoplastic resin (P _2A )”. The second thermoplastic resin layer (B-2) of the laminate (B) has a thermoplastic resin (P ₂ ) (in the following, on the surface opposite to the first thermoplastic resin layer (B-1)). When the thermoplastic resin (P ₂ ) contained in the second thermoplastic resin layer (B-2) includes a “thermoplastic resin (P _2B )”), the thermoplastic resin (P _2A ) (when the second thermoplastic resin layer (A-2) contains two or more thermoplastic resins (P _2A ), the content is the highest) and The thermoplastic resin (P _2B ) (the one with the highest content when the second thermoplastic resin layer (B-2) contains two or more thermoplastic resins (P _2B )) must be the same Is preferred. Since the thermoplastic resin (P _2A ) and the thermoplastic resin (P _2B ) are the same, the two adherends can be bonded more firmly.

Thermoplastic resin (P _2A ) (when the second thermoplastic resin layer (A-2) contains two or more kinds of thermoplastic resins (P _2A ), the content is the highest) and thermoplastic resin (P _2B ) (when the second thermoplastic resin layer (B-2) contains two or more thermoplastic resins (P _2B ), the content is the highest), these thermoplastic resins are crystalline. In the case of a functional resin, it is preferable that the difference between these melting points is small. By using a combination of a thermoplastic resin (P _2A ) and a thermoplastic resin (P _2B ) having close melting points, thermal welding can be performed more efficiently.
The difference between the melting point of the thermoplastic resin (P _2A ) and the melting point of the thermoplastic resin (P _2B ) is preferably 40 ° C. or less, more preferably 20 ° C. or less, and particularly preferably 0 ° C.

Thermoplastic resin (P _2A ) (when the second thermoplastic resin layer (A-2) contains two or more kinds of thermoplastic resins (P _2A ), the content is the highest) and thermoplastic resin (P _2B ) (if the second thermoplastic resin layer (B-2) contains two or more thermoplastic resins (P _2B ), the content is the highest), these Hansen solubility parameters It is preferable that the working distance Ra 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 between the Hansen solubility parameters of the thermoplastic resin (P _2A ) and the thermoplastic resin (P _2B ) 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 a dispersive component of the Hansen solubility parameter of the thermoplastic resin (P _2A ), δD _B is a dispersive component of the Hansen solubility parameter of the thermoplastic resin (P _2B ), and δP _A is a thermoplastic resin ( The polar component of the Hansen solubility parameter of 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 a hydrogen bonding component of the Hansen solubility parameter of the thermoplastic resin (P _2B ).

In the bonding method of the present invention, the molecular adhesive layer (AM) of the bonding laminate (A) is used for bonding to the adherend (I), and the molecular bonding of the bonding laminate (B). The agent layer (BM) is used for adhesion to the adherend (II).

The adhesion between the molecular adhesive layer (AM) and the adherend (I) and the adhesion between the molecular adhesive layer (BM) and the adherend (II) are usually molecular adhesion. The reactive group (Zβ) in the agent (M _A ) or (M _B ) reacts with the functional group in the compound constituting the adherend (I) or the adherend (II) to form a chemical bond. Is done.
Therefore, usually, as the adherend (I) or the adherend (II), one having a group having reactivity with the reactive group (Zβ) on its surface is used.

Examples of such an adherend include a member containing a metal on the surface, a member containing an inorganic substance on the surface, and a member containing a silicone resin on the surface.
Examples of the metal include aluminum, chromium, manganese, iron, cobalt, nickel, copper, zinc, silver, and gold.
Examples of inorganic substances include glass and inorganic oxides (excluding glass).
These members may be subjected to surface treatment. A member in which a hydroxy group, a carboxy group or the like is generated by the surface treatment is more preferably used as an adherend.
Moreover, the member which contains a thermoplastic resin and a thermosetting resin on the surface can also be utilized as a to-be-adhered body by utilizing a surface treatment technique.
Examples of the surface treatment 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.
A primer layer may be provided on the surface of the adherend as necessary.

[Process group including processes (L1) to (L3)]
FIG. 2 shows each step of the step group including steps (L1) to (L3).
In the step (L1), the molecular adhesive layer (AM) (8), the first thermoplastic resin layer (A-1) (9), and the second thermoplastic resin layer (A-2) ( 10) Adhering the molecular adhesive layer (AM) (8) of the laminate (A) (11) for bonding and the adherend (I) (12) to obtain the laminate (13) [FIG. 2 (a)].

Process (L1) can be performed using, for example, a heating press machine, an autoclave apparatus, a vacuum bonding machine, a three-dimensional vacuum heating molding machine (TOM molding machine), a heating laminating apparatus, or the like.

When a linear pressure is applied in the step (L1), the pressure is usually 0.1 to 5 N / mm, preferably 0.2 to 3 N / mm, more preferably 0.3 to 1 N / mm.
When the surface pressure is applied in the 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 further preferably 0.4 to 1 MPa.

The adhesion temperature in the step (L1) is usually 40 to 200 ° C., preferably 50 to 170 ° C., more preferably 60 to 140 ° C.
The treatment time in the step (L1) is usually 1 second to 1 hour, preferably 5 seconds to 30 minutes, more preferably 10 seconds to 10 minutes.

In the step (L2), the molecular adhesive layer (BM) (14), the first thermoplastic resin layer (B-1) (15), and the second thermoplastic resin layer (B-2) ( 16) Adhering the molecular adhesive layer (BM) (14) and the adherend (II) (18) of the bonding laminate (B) (17) having the laminate 16) to obtain the laminate (19) [FIG. 2 (b)].
Step (L2) can be performed according to a method and conditions similar to those of step (L1).

In the step (L3), the second thermoplastic resin layer (A-2) (10) of the laminate (13) obtained in the step (L1) and the laminate (19) obtained in the step (L2) are used. ) And the second thermoplastic resin layer (B-2) (16) are thermally welded to obtain a bonded structure (20) [FIG. 2 (c)].

The step (L3) can be performed using, for example, a heating press machine, an autoclave apparatus, a vacuum bonding machine, a three-dimensional vacuum heating molding machine (TOM molding machine), a heating laminating apparatus, or the like.
When a linear pressure is applied in the step (L3), the pressure is usually 0.1 to 5 N / mm, preferably 0.2 to 3 N / mm, more preferably 0.3 to 1 N / mm.
When the surface pressure is applied in the step (L3), the pressure is usually 0.05 to 10 MPa, preferably 0.1 to 5 MPa, more preferably 0.2 to 3 MPa.

The heat welding temperature in the step (L3) is usually 50 to 230 ° C., preferably 60 to 200 ° C., more preferably 80 to 170 ° C.
The treatment time in the step (L3) is usually 1 second to 1 minute, preferably 3 to 30 seconds.

When performing the process group including the processes (L1) to (L3), the molecular adhesive layer (AM) of the bonding laminate (A) and the adherend (I) are bonded in the process (L1). temperature _{T L1} of time, in step (L2), the temperature _{T L2} when the molecular adhesive layer (B-M) for adhering the adherend (II) of the bonded laminate for (B), step ( L3), the temperature at which the second thermoplastic resin layer (A-2) and the second thermoplastic resin layer (B-2) are thermally welded is T _L3 , and the joining laminate (A) The heat-sealable temperature of the first thermoplastic resin layer (A-1) is T _h1A , and the heat-sealable temperature of the second thermoplastic resin layer (A-2) is _Th2A. The heat-sealable temperature of the first thermoplastic resin layer (B-1) of B) is _Th1B , and the heat of the second thermoplastic resin layer (B-2) is When the tossable temperature is _{Th 2B} , _both of the following formulas (E-1) and (E-2) are satisfied, and at least one of the following formulas (E-3) and (E-4) is satisfied It is preferable to satisfy.

By satisfying the formula (E-1), deformation of the first thermoplastic resin layer (A-1) of the laminate for bonding (A) in the step (L1) is suppressed.
By satisfying the formula (E-2), the deformation of the first thermoplastic resin layer (B-1) of the bonding laminate (B) in the step (L2) is suppressed.

By satisfying at least one of formula (E-3) and formula (E-4), the second thermoplastic resin layer (A-2) of the joining laminate (A) and the joining laminate (B) The second thermoplastic resin layer (B-2) can be efficiently heat-welded.
More efficiently heat-welding 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). Therefore, it is more preferable that both the formula (E-3) and the formula (E-4) are satisfied.

[Process group including processes (M1) to (M3)]
FIG. 3 shows each step in the step group including steps (M1) to (M3).
In the step (M1), the molecular adhesive layer (AM) (21), the first thermoplastic resin layer (A-1) (22), and the second thermoplastic resin layer (A-2) ( 23) the second thermoplastic resin layer (A-2) (23) of the laminate (A) (24) for bonding, the molecular adhesive layer (BM) (25), the first thermoplastic layer The second thermoplastic resin layer (B-) of the laminate for bonding (B) (28) having the resin layer (B-1) (26) and the second thermoplastic resin layer (B-2) (27). 2) (27) is thermally welded to obtain a laminate (29) [FIG. 3 (a)].
Step (M1) can be performed according to a method and conditions similar to those of step (L3).

In the step (M2), the molecular adhesive layer (AM) (21) and the adherend (I) (30) of the laminate (29) obtained in the step (M1) are adhered, and the laminate (31) is obtained [FIG. 3 (b)].
In the step (M3), the molecular adhesive layer (BM) (25) and the adherend (II) (32) of the laminate (31) obtained in the step (M2) are bonded to each other to form a bonded structure. A body (33) is obtained [FIG. 3 (c)].

Step (M2) and step (M3) can be performed in the same manner and under the same conditions as in step (L1), respectively.
In addition, you may perform a process (M2) and a process (M3) simultaneously. For example, by stacking the adherend (I), the laminate obtained in the step (M1) and the adherend (II) in this order, and performing a pressure-bonding treatment on this, the step (M2) and The step (M3) can be performed simultaneously.

[Process group including processes (N1) and (N2)]
Each process of the process group containing process (N1) and (N2) is shown in FIG.
In the step (N1), the molecular adhesive layer (AM) (34), the first thermoplastic resin layer (A-1) (35), and the second thermoplastic resin layer (A-2) ( 36) the second thermoplastic resin layer (A-2) (36) of the bonding laminate (A) (37), the molecular adhesive layer (BM) (38), the first thermoplasticity The second thermoplastic resin layer (B--) of the laminate (B) (41) having the resin layer (B-1) (39) and the second thermoplastic resin layer (B-2) (40). 2) In an arrangement in which (40) face each other, the adherend (I) (42), the bonding laminate (A) (35), the bonding laminate (B) (41), the adherend (II) ( 43) are overlapped in this order [FIG. 4 (a)].

In the step (N2), the product (44) obtained in the step (N1) is heated to bond the molecular adhesive layer (AM) and the adherend (I), and the molecular adhesive layer ( BM) and adherend (II) are bonded together, and the second thermoplastic resin layer (A-2) and second thermoplastic resin layer (B-2) are simultaneously welded together. A structure (45) is obtained [FIG. 4 (b)].

Step (N2) can be performed using, for example, a heating press machine, an autoclave apparatus, a vacuum bonding machine, a three-dimensional vacuum heating molding machine (TOM molding machine), a heating laminating apparatus, or the like.

When a linear pressure is applied in the step (N2), the pressure is usually 0.1 to 5 N / mm, preferably 0.2 to 3 N / mm, more preferably 0.3 to 1 N / mm.
When the surface pressure is applied in the 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 further preferably 0.4 to 1 MPa.

The heat welding temperature in the step (N2) is usually 50 to 230 ° C., preferably 60 to 200 ° C., more preferably 80 to 170 ° C.
The treatment time in the step (N2) is usually 1 second to 1 hour, preferably 5 seconds to 30 minutes, more preferably 10 seconds to 10 minutes.

When the process group including the processes (N1) and (N2) is performed, the heat-sealable temperature of the first thermoplastic resin layer (A-1) of the bonding laminate (A) is _Th1A , the second thermoplasticity. The heat-sealable temperature of the resin layer (A-2) is _Th2A , and the heat-sealable temperature of the first thermoplastic resin layer (B-1) of the bonding laminate (B) is _Th1B , second heat-sealable temperature of the thermoplastic resin layer (B-2) is a _{T H2B,} in step (N2), when the temperature at the time of heat welding is _{T N2,} the following equation (E-5) formula ( It is preferable to satisfy at least one of E-6).

By satisfying at least one of the formula (E-5) and the formula (E-6), the second thermoplastic resin layer (A-2) of the bonding laminate (A) and the bonding laminate (B) The second thermoplastic resin layer (B-2) can be efficiently heat-welded.
More efficiently heat-welding 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). Therefore, it is more preferable that both the formula (E-5) and the formula (E-6) are satisfied.

When bonding the adherend (I) and the adherend (II), a process group including the steps (L1) to (L3) or a process group including the steps (N1) and (N2) is included. Preferably it is done.
In the process group including the processes (L1) to (L3), the adhesion process between the molecular adhesive layer and the adherend is performed before the heat welding process. Therefore, since the adhesion treatment between the molecular adhesive layer and the adherend can be performed in a state where the thermoplastic resin layer is not thermally deformed due to the thermal welding treatment, the molecular adhesive layer and the adherend are It is possible to bond more firmly.

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

3) Method for Producing Bonded Structure The method for producing a bonded structure according to the present invention comprises an adherend (I) / laminate for joining (A) and a layer / adherent (II) derived from the laminate for joining (B). ), A bonded structure having a layer structure, wherein the adherend (I) and the adherend (II) are bonded using the bonding method of the present invention.

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

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, the adherend (I) and the adherend (II) are each independently at least one selected from the group consisting of metals, inorganic substances, and thermosetting resins on at least the adherend surface. The inclusion is preferred.

When the adherends have an adherend surface formed of a thermoplastic resin, the adherends can be directly heat welded and joined without using the bonding laminate of the present invention. There is.
On the other hand, when a metal, an inorganic substance, or a thermosetting resin exists on the adherend surface of the adherend, it is difficult to firmly bond the adherends by this method.

The method for manufacturing a bonded structure according to the present invention uses the bonded laminate according to the present invention. Therefore, according to the method for manufacturing a bonded structure of the present invention, even when a metal, an inorganic substance, or a thermosetting resin is present on the adherend surface of the adherend, these adherends are firmly formed. A bonded structure obtained by bonding can be obtained.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.
Unless otherwise indicated, the part and% in each example are based on mass.

[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, they were stacked so that the layers of the same component face each other, and these were thermally welded at 0.2 MPa for 1 second to obtain test pieces. At this time, the heat welding temperature was changed at intervals of 5 ° C. (for example, 140 ° C., 145 ° C., 150 ° C.) to obtain a plurality of test pieces.
Each of the obtained test pieces was 300 mm using a tensile testing machine (manufactured by A & D Co., Ltd., product name “Tensilon Universal Material Testing Machine”) in an environment of 23 ° C. and 50% humidity (relative humidity). A T-type peel test was performed under the conditions of / min and the respective adhesive strengths were measured.
Among the test pieces having an adhesive strength of 5 N / 25 mm or more, the heat welding temperature of the test piece having the lowest heat welding temperature was defined as “heat sealable temperature”.

[Production Example 1]
Using two types of polypropylene as molding materials, a co-extrusion method was used to obtain “first thermoplastic resin layer [polypropylene (PP) thickness 60 μm] / second thermoplastic resin layer [polypropylene (PP) thickness 50 μm]”. A multilayer film (1) having a layer structure of When the heat-sealable temperature of each layer was measured for the obtained multilayer film (1), the heat-sealable temperature of the first thermoplastic resin layer was 170 ° C., and the heat-sealable of the second thermoplastic resin layer was possible. The temperature was 145 ° C.

[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 listed in Table 1 were used.

[Production Example 3]
Using two types of polyethylene and nylon as a molding material, a “first thermoplastic resin layer [polyethylene (PE) thickness 25 μm] / second thermoplastic resin layer [nylon (Ny) thickness] A multilayer film (3) having a layer structure of “30 μm / polyethylene (PE) thickness 25 μm]” was obtained. About the obtained multilayer film (3), when the heat-sealable temperature of each layer was measured, the heat-sealable temperature of the first thermoplastic resin layer was 140 ° C., and the second thermoplastic resin layer (polyethylene layer) The heat sealable temperature of was 100 ° C.

[Production Example 4]
Using a polyester-based adhesive, a polyethylene film and an ethylene / vinyl acetate copolymer resin film are dry-laminated, and “first thermoplastic resin layer [polyethylene (PE) thickness 100 μm] / second thermoplastic resin layer” is obtained. A multilayer film (4) having a layer structure of [ethylene / vinyl acetate copolymer resin (EVA) thickness 50 μm] was obtained. Regarding the obtained multilayer film (4), when the heat-sealable temperature of each layer was measured, the heat-sealable temperature of the first thermoplastic resin layer was 140 ° C., and the heat-sealable of the second thermoplastic resin layer was possible. The temperature was 110 ° C.

Details of the multilayer films (1) to (5) are shown in Table 1.
In Table 1, 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 the above formula (10), in Table 2) And a molecular adhesive solution (solvent: ethanol, concentration 0.1 g / L).

[Production Example 1]
A laminate for bonding (1) was produced using the multilayer film (1) by the following method.
Corona treatment machine (manufactured by Shinko Electric Measurement Co., Ltd., product name “Corona Scanner ASA-4”, output voltage: 9 kV (surface voltage), oscillation frequency for the first thermoplastic resin layer of the multilayer film (1) : 20 kHz). Next, the surface of the surface subjected to corona irradiation was coated with the molecular adhesive solution obtained in Production Example 6 with a Meyer bar (No. 12), and the obtained coating film was dried at 80 ° C. for 60 seconds.
Next, using a UV irradiation device (product name “LIGHT HAMMER 10 MARK II” manufactured by Heraeus Co., Ltd., light source: mercury lamp), this coating film is irradiated with UV light to perform fixing treatment, and the molecular adhesive layer and A laminate (1) for bonding composed of the first thermoplastic resin layer and the second thermoplastic resin layer (multilayer film (1)) was obtained.
The ultraviolet irradiation conditions are an illuminance of 84 mW / cm ² and an amount of light of 29 mJ / cm ² , and the illuminance and the amount of light are measured in the UVC region using an illuminance / light meter (product name “UV Power Pack II” manufactured by EIT). Illuminance and light intensity were measured.

[Production Examples 2 to 4, Production Comparative Example 1]
In Production Example 1, for the joining, in the same manner as Production Example 1, except that the multilayer films (2) to (5) shown in Table 2 were used instead of the multilayer film (1). Laminated bodies (2) to (5) were obtained.

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

[Example 1]
Two laminates for bonding (1) (10 mm × 10 mm) obtained in Production Example 1 and two adherends [plasma-treated glass plate (30 mm × 70 mm × 2 mm)] were prepared.
The bonding laminate (1) and the adherend (glass plate) are stacked so that the molecular adhesive layer of the bonding laminate (1) faces the plasma-treated surface of the glass plate. Thermocompression bonding was performed for 5 minutes under the condition of 5 MPa (surface pressure) to obtain a laminate composed of an adherend / molecular adhesive layer / first thermoplastic resin layer / second thermoplastic resin layer.
Separately from this operation, the same operation was performed using the remaining bonded laminate (1) and the adherend to obtain another laminate.
Next, the second thermoplastic resin layers of the two obtained laminates were thermocompression bonded for 10 seconds under the conditions of 145 ° C. and 0.5 MPa (surface pressure) to obtain a bonded structure.

[Example 2]
Two laminates for bonding (2) (10 mm × 10 mm) obtained in Production Example 2 and two adherends [plasma-treated glass plate (30 mm × 70 mm × 2 mm)] were prepared.
Each molecular adhesive layer of the two bonding laminates (2) faces the plasma processing surface of the glass plate, and the second thermoplastic resin layers of the two bonding laminates (2) face each other. Thus, the adherend, the laminate for bonding (2), the laminate for bonding (2), and the adherend are stacked in this order, and this is laminated at 145 ° C. and 0.5 MPa (surface pressure) for 5 minutes. A bonded structure was obtained by thermocompression bonding.

[Examples 3 and 4, Comparative Example 1]
A joined structure was obtained in the same manner as in Example 2 except that the joining laminate described in Table 3 and the production conditions were used.

[Comparative Example 2]
Two multilayer films (1) (10 mm × 10 mm) obtained in Production Example 1 and two adherends [plasma-treated glass plates (30 mm × 70 mm × 2 mm)] were prepared.
The layers having a heat sealable temperature of 170 ° C. of the two multilayer films (1) are respectively opposed to the plasma treatment surface of the glass plate, and the heat sealable temperature of the two multilayer films (1) is 145 ° C. The adherend, the multilayer film (1), the multilayer film (1), and the adherend are stacked in this order so that the layers of each other face each other, and this is laminated at 145 ° C. and 0.5 MPa (surface pressure). The bonded structure was obtained by thermocompression bonding for a minute.

(Measurement of adhesive strength)
Using the bonded structures obtained in Examples 1 to 4 and Comparative Examples 1 and 2 as test pieces, bonding was performed with a universal tensile tester (Instron, Instron 5581) under a tensile speed of 50 mm / min. The strength was measured. Furthermore, the state of the test piece was observed after the test. The results are shown in Table 3.
In Comparative Example 2, the adherend and the multilayer film were not sufficiently bonded, and the adhesive strength could not be measured.

(Shape change evaluation)
Using the bonded structures obtained in Examples 1 to 4 and Comparative Examples 1 and 2 as test pieces, the seepage of the bonded laminate after thermocompression bonding was visually confirmed and evaluated according to the following criteria.
A: Exudation of the end due to deformation of the joining laminate could not be confirmed visually.
F: Exudation of the end portion due to deformation of the bonding laminate was visually confirmed.

Table 3 shows the following.
In Examples 1 to 4, the test piece after the measurement of the adhesive strength is broken in the layer derived from the bonding laminate or broken at the interface between the layer derived from the bonding laminate and the adherend. It has not occurred. Therefore, it can be seen that in Examples 1 to 4, the two adherends are firmly joined.
On the other hand, the bonding laminate used in Comparative Example 1 has the same heat-sealable temperature of the first thermoplastic resin layer and the heat-sealable temperature of the second thermoplastic resin layer. For this reason, deformation occurred during thermocompression bonding.
In Comparative Example 2, the adherend and the multilayer film are not sufficiently bonded. Therefore, it is difficult to join the glass plates by this method.

1: First thermoplastic resin layer 2: Second thermoplastic resin layer 3: Laminate 4 composed of first thermoplastic resin layer and second thermoplastic resin layer 4: Molecular adhesive layer 5: Bonding Laminate 6: Surface 7 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 bonding (A)
12.30.42: adherend (I)
13: Laminate 14.25.38: molecular adhesive layer (BM) resulting from step (L1)
15.26.39: first thermoplastic resin layer (B-1)
16.27.40: second thermoplastic resin layer (B-2)
17.28.41: laminate for bonding (B)
18.32.43: adherend (II)
19: Laminated body 20.33.45 as a result of the step (L2): Bonded structure 29: Laminated body 31 as a result of the step (M1): Laminated body 44 as a result of the step (M2): Obtained in step (N1)

Claims (11)

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 multilayer structure in this order, The molecular adhesive layer and the second thermoplastic resin layer are each a laminate for bonding that constitutes the outermost layer in use,
The molecular adhesive (M) includes 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 A compound having at least one reactive group (Zβ) selected from the group consisting of groups that generate silanol groups by reaction;
The first thermoplastic resin layer has at least a reactive partial structure (Zγ) capable of forming a chemical bond with the reactive group (Zα) of the molecular adhesive (M) on the surface in contact with the molecular adhesive layer. ) Having a thermoplastic resin (P ₁ ) having
Said first thermoplastic heat seal resin layer can temperature T _h1, the when the heat-sealable temperature of the second thermoplastic resin layer is T _h2, T _h1> T _h2 a is bonded laminate for. 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 is a thermoplastic resin (P ₁ ). The reactive partial structure (Zγ) of is at least one selected from the group consisting of a hydroxy group, a carboxy group, an aldehyde group, and an amino group, or
The reactive group (Zα) included in the molecular adhesive (M) is an azide group, and the reactive partial structure (Zγ) included in the thermoplastic resin (P ₁ ) includes a carbon-carbon single bond, a carbon-carbon two bond. The bonding laminate according to claim 1, which is at least one selected from the group consisting of a heavy bond and a carbon-hydrogen single bond. The laminated body for joining according to claim 1 or 2, 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, an azide group, a mercapto group, an isocyanate group, a ureido group and an epoxy group are excluded.) G represents a divalent organic group, X represents a hydroxy group, an alkoxy having 1 to 10 carbon atoms. And Y represents a hydrocarbon group having 1 to 20 carbon atoms, and a represents an integer of 1 to 3.) 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 claims 1 to 3. Laminate for bonding. The thermoplastic resin (P ₁ ) is at least one selected from the group consisting of olefin resins, cycloolefin resins, acrylic resins, olefin-vinyl acetate resins, olefin ionomer resins, and polyester resins. The bonding laminate according to any one of claims 1 to 4. The second thermoplastic resin layer has an olefin resin, a cycloolefin resin, an acrylic resin, an olefin-vinyl acetate resin, an olefin ionomer resin, and a polyester at least on the surface opposite to the molecular adhesive layer. The bonding laminate according to any one of claims 1 to 5, comprising at least one selected from the group consisting of resins. A method of joining an adherend (I) and an adherend (II) using two laminates for joining,
The bonding laminate according to any one of claims 1 to 6, wherein the two bonding laminates are each independently
The first bonding laminate includes a molecular adhesive layer (AM) including a molecular adhesive (M _A ), a first thermoplastic resin layer (A-1) having a single layer structure, and a single layer structure Alternatively, the second thermoplastic resin layer (A-2) having a multilayer structure is referred to as a bonding laminate (A) in this order, and the second bonding laminate includes a molecular adhesive (M _B ). 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 multilayer structure. When expressed as a laminate for bonding (B) in this order,
Any one selected from a process group including the following processes (L1) to (L3), a process group including the processes (M1) to (M3), and a process group including the processes (N1) and (N2). A method for joining the adherend (I) and the adherend (II), comprising performing a process group.
Step (L1): Step of bonding the molecular adhesive layer (AM) of the bonding laminate (A) and the adherend (I) Step (L2): Molecular adhesive of the bonding laminate (B) Step (L3) for bonding the layer (BM) and the adherend (II): the second thermoplastic resin layer (A-2) of the laminate obtained in the step (L1), and a step ( Step (M1) of heat-welding the second thermoplastic resin layer (B-2) of the laminate obtained in L2): the second thermoplastic resin layer (A- 2) and step (M2) of thermally welding the second thermoplastic resin layer (B-2) of the laminate for bonding (B): molecular adhesive layer of the laminate obtained in step (M1) Step (M3) for bonding (AM) and adherend (I): molecular adhesive layer (BM) and adherend (II) of the laminate obtained in step (M2) Process process ( 1) An arrangement in which the second thermoplastic resin layer (A-2) of the laminate for bonding (A) and the second thermoplastic resin layer (B-2) of the laminate for bonding (B) face each other. , Adherend (I), bonding laminate (A), bonding laminate (B), and adherend (II) are stacked in this order (step (N2): obtained in step (N1) Are heated, the adhesion between the molecular adhesive layer (AM) and the adherend (I), the adhesion between the molecular adhesive layer (BM) and the adherend (II), the second A step of simultaneously performing thermal welding between the thermoplastic resin layer (A-2) and the second thermoplastic resin layer (B-2). A method of joining the adherend (I) and the adherend (II), comprising performing a process group including the steps (L1) to (L3),
In the 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 step (L2), the temperature at which the molecular adhesive layer (BM) of the laminate for bonding (B) and the adherend (II) are bonded is T _L2 ,
In the step (L3), the temperature at which the second thermoplastic resin layer (A-2) and the second thermoplastic resin layer (B-2) are thermally welded is T _L3 ,
The heat-sealable temperature of the first thermoplastic resin layer (A-1) of the bonding laminate (A) is _Th1A , and the heat-sealable temperature of the second thermoplastic resin layer (A-2) is _Th2A . Yes,
The heat-sealable temperature of the first thermoplastic resin layer (B-1) of the bonding laminate (B) is _Th1B , and the heat-sealable temperature of the second thermoplastic resin layer (B-2) is _Th2B . When
The deposition according to claim 7, wherein both of the following formula (E-1) and formula (E-2) are satisfied, and at least one of the following formula (E-3) and formula (E-4) is satisfied. A method of joining the body (I) and the adherend (II).

A method of joining the adherend (I) and the adherend (II), comprising performing a process group including the steps (N1) and (N2),
The heat-sealable temperature of the first thermoplastic resin layer (A-1) of the bonding laminate (A) is _Th1A , and the heat-sealable temperature of the second thermoplastic resin layer (A-2) is _Th2A . Yes,
The heat-sealable temperature of the first thermoplastic resin layer (B-1) of the bonding laminate (B) is _Th1B , and the heat-sealable temperature of the second thermoplastic resin layer (B-2) is _Th2B . Yes,
In the step (N2), when the temperature at the time of heat welding is _TN2 ,
The method for joining the adherend (I) and the adherend (II) according to claim 7, wherein at least one of the following formula (E-5) and formula (E-6) is satisfied.

A method for producing a bonded structure having a layer structure of an adherend (I) / a laminate for bonding (A) and a layer derived from the laminate for bonding (B) / an adherend (II), A method for producing a bonded structure comprising bonding the adherend (I) and the adherend (II) using the method according to any one of 7 to 9. The adherend (I) and the adherend (II) each independently contain at least one selected from the group consisting of metals, inorganic substances, and thermosetting resins in at least the adherend surface. The manufacturing method of the joining structure of 10.

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