JP6674594B2 - Bonding laminate, method of bonding two adherends, and method of manufacturing bonded structure - Google Patents

Description

  The present invention relates to a bonding laminate having a molecular adhesive layer (referred to as a layer formed using a molecular adhesive; the same applies hereinafter), a method of bonding two adherends using the bonding laminate, Further, the present invention relates to a method for manufacturing a joint structure.

A compound having two or more types of reactive groups is useful as a molecular adhesive because it can form a chemical bond by utilizing the characteristics of each reactive group.
For example, Patent Literature 1 discloses a method of joining a substrate A and a substrate B, in which a step of forming a molecular adhesive layer on the surface of the substrate A using a specific molecular adhesive, And a step of applying a force to the substrates A and B to bond the substrates A and B to each other.

  Patent Literature 1 discloses a method of forming a molecular adhesive layer on the surface of a substrate by preparing a molecular adhesive solution in which a molecular adhesive is dissolved or dispersed, and immersing the substrate in the molecular adhesive solution. A method is described in which a chemical bond is formed between a molecular adhesive and a surface of a substrate by irradiating the substrate with ultraviolet light to form a molecular adhesive layer.

WO2012 / 043631 (US2013 / 177770 A1)

As described in Patent Document 1, by immersing a substrate in a molecular adhesive solution, a double-sided adhesive sheet having a molecular adhesive layer on both surfaces of the substrate can be efficiently obtained. Such a double-sided adhesive sheet is useful as a joining 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 a molecular adhesive layer on both surfaces of a 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 adopting a roll-to-roll method.

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

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

  The present invention has been made to solve this problem, 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 bonding laminate capable of performing a heat welding process, a method for bonding two adherends using the bonding laminate, and a method for manufacturing a bonding structure.

Means for Solving the Problems In order to solve the above problems, the present inventors have intensively 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 bonding laminate that satisfies the following requirements (a) to (c), a heat welding step can be performed without adversely affecting the molecular adhesive layer, and the present invention is completed. Reached.
Requirement (a): The thermoplastic resin layer is composed of a first thermoplastic resin layer and a second thermoplastic resin layer.
Requirement (b): a molecular adhesive layer is formed on the first thermoplastic resin layer.
Requirement (c): The second thermoplastic resin layer is a layer that can be thermally welded at a lower temperature than the first thermoplastic resin layer.

  Thus, according to the present invention, the following bonding laminates (1) to (6), a method for bonding two adherends (7) to (9), and a bonding structure (10) to (11) A method of making 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 bonding laminates each constituting an outermost layer at the time of use, and the molecular adhesive (M) is an amino group, an azide group, a mercapto group. At least one reactive group (Zα) selected from the group consisting of a group, an isocyanate group, a ureido group and an epoxy group, and at least one group selected from the group consisting of a silanol group and a group that forms a silanol group by a hydrolysis reaction. The first thermoplastic resin layer has at least a reactive group (Z) 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 of when the heat-sealable temperature is _{T h2, T h1>} bonded laminate for a _{T h2.}
(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 ureide 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 of the molecular adhesive (M) The reactive group (Zα) is an azide group, and the reactive partial structure (Zγ) of the thermoplastic resin (P ₁ ) is formed from a carbon-carbon single bond, a carbon-carbon double bond, and a carbon-hydrogen single bond. The bonding laminate according to (1), which is at least one member 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 ureide group, and an epoxy group, or a monovalent group having at least one of these reactive groups. (However, excluding an amino group, an azide group, a mercapto group, an isocyanate group, a ureide group and an epoxy group), G represents a divalent organic group, X represents a hydroxy group, an alkoxy group having 1 to 10 carbon atoms. Represents a group or a halogen atom, 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. The bonding laminate according to any one of the above.
(5) The thermoplastic resin (P ₁ ) is at least one selected from the group consisting of an olefin resin, a cycloolefin resin, an acrylic resin, an olefin-vinyl acetate resin, an olefin ionomer resin, and a polyester resin. The bonding laminate according to any one of (1) to (4).
(6) The second thermoplastic resin layer has an olefin-based resin, a cycloolefin-based resin, an acrylic-based resin, an olefin-vinyl acetate-based resin, and an olefin-based ionomer resin on at least a surface opposite to the molecular adhesive layer. And the bonding laminate according to any one of (1) to (5), which comprises at least one selected from the group consisting of polyester resin.
(7) A method of joining an adherend (I) and an adherend (II) using two joining laminates, wherein the two joining laminates are each independently: (1) a bonding laminate according to any one of the - (6), the first bonding laminate molecular adhesive layer comprising molecules adhesive (M _a) (a-M), 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. represents the second bonding laminate molecular adhesive layer comprising molecules adhesive _{(M B) (B-M} ), the first thermoplastic resin layer having a single layer structure (B-1), and a single When the second thermoplastic resin layer (B-2) having a layered structure or a multilayered structure is expressed as a bonding laminate (B) having this order, the following steps (L1) to (L3) ), A step group including steps (M1) to (M3), and a step group including steps (N1) and (N2). Bonding the adherend (I) and the adherend (II).
Step (L1): Step of bonding molecular adhesive layer (AM) of bonding laminate (A) to adherend (I) Step (L2): Molecular adhesive of bonding laminate (B) Step (L3) of bonding the layer (BM) and the adherend (II): the second thermoplastic resin layer (A-2) of the laminate obtained in the step (L1); Step (M1) of heat-welding the laminate obtained in L2) to the second thermoplastic resin layer (B-2): the second thermoplastic resin layer (A-) of the bonding laminate (A) 2) a step of thermally welding the second thermoplastic resin layer (B-2) of the bonding laminate (B) to the second thermoplastic resin layer (B-2): the molecular adhesive layer of the laminate obtained in the step (M1) Step (M3) of bonding (AM) and adherend (I): the molecular adhesive layer (BM) of the laminate obtained in step (M2) and adherend (II) Bonding process ( 1): Arrangement in which 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) face each other. Step (N2) of stacking the adherend (I), the laminate for joining (A), the laminate for joining (B), and the adherend (II) in this order: Step (N1): Obtained in Step (N1) Is 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), and the second Step (8) of simultaneously performing the thermal welding of the thermoplastic resin layer (A-2) and the second thermoplastic resin layer (B-2), and performing a step group including the steps (L1) to (L3). A method for joining an adherend (I) and an adherend (II),
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 , and in the step (L2), the bonding laminate The temperature at the time of bonding the molecular adhesive layer (BM) of the body (B) and the adherend (II) is T _L2 , and in the step (L3), the second thermoplastic resin layer (A-2) The temperature at the time of heat-welding the first thermoplastic resin layer (A-1) to the second thermoplastic resin layer (B-2) is T _L3 , and the heat-sealable temperature of the first thermoplastic resin layer (A-1) of the bonding laminate (A). Is _Th1A , the heat sealable temperature of the second thermoplastic resin layer (A-2) is _Th2A , and the heat seal of the first thermoplastic resin layer (B-1) of the bonding laminate (B) is _Th1A. 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), which satisfies both 1) and formula (E-2), and satisfies at least one of the following formulas (E-3) and (E-4). A method of bonding with the adherend (II).

(9) A method of joining an adherend (I) and an adherend (II) by performing a step group including the steps (N1) and (N2), wherein the method comprises: The heat-sealable temperature of the first thermoplastic resin layer (A-1) is _Th1A , the heat-sealable temperature of the second thermoplastic resin layer (A-2) is _Th2A , and the bonding laminate (B) is used. The heat sealable temperature of the first thermoplastic resin layer (B-1) is _Th1B , 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, and the adherend (I) and the adherend (I) described in (7) are satisfied. A method of joining the body (II).

(10) A method for producing a joint structure having a layer structure of an adherend (I) / a laminate for joining (A) and a layer / adherend (II) derived from a laminate for joining (B). , (7) to (9), a method of manufacturing a bonded structure, comprising bonding the adherend (I) and the adherend (II).
(11) The adherend (I) and the adherend (II) each independently include at least one selected from the group consisting of a metal, an inorganic substance, and a thermosetting resin on at least the surface to be adhered. , (10).

In the present invention, the molecular adhesive refers to a compound having two or more reactive groups.
“Including a molecular adhesive” in the “molecular adhesive layer containing a molecular adhesive” means “molecular adhesive and / or a compound derived from the molecular adhesive (for example, the structure of a reactive group is changed through a reaction. Compounds).
“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 a resin derived from this thermoplastic resin. Resin (for example, a resin in which the structure of the reactive partial structure (Zγ) has been changed through a reaction) ”.
“The molecular adhesive layer and the second thermoplastic resin layer constitute the outermost layers when used, respectively” means that the molecular adhesive layer is bonded to the adherend or the second thermoplastic resin layers are bonded to each other. It means that each layer is the outermost layer during thermal welding. Therefore, between the time of manufacturing and use of the bonding laminate, the bonding laminate may have a protective sheet or the like as the outermost layer.
The “heat-sealable temperature” of the thermoplastic resin layer is a temperature required at the time of heat welding in order to achieve sufficient heat-sealing strength. Specifically, according to the method described in Examples, heat-sealing is performed. The possible temperature can be determined.
`` Temperature at the time of bonding the molecular adhesive layer and the adherend '' and `` Temperature at the time of heat welding the thermoplastic resin layer and the thermoplastic resin layer '', when using a heating press machine, etc. It means 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, without adversely affecting the molecular adhesive layer, a bonding laminate capable of performing a heat welding step, A method for joining two adherends using the joining laminate and a method for manufacturing a joined structure are provided.

It is a mimetic diagram showing an example of a manufacturing process of a layered product for junction of the present invention. It is a schematic diagram showing the process group containing process (L1)-(L3). It is a schematic diagram showing the process group containing process (M1)-(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 bonding, 2) a method for bonding two adherends, and 3) a method for manufacturing a bonded 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. A bonding laminate having a second thermoplastic resin layer in this order, wherein the molecular adhesive layer and the second thermoplastic resin layer each constitute an outermost layer when used, and (M) is 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 ureide group and an epoxy group, a silanol group, and a silanol group by a hydrolysis reaction. And a compound having at least one type of reactive group (Zβ) selected from the group consisting of groups that form the first thermoplastic resin layer, wherein the first thermoplastic resin layer has at least a surface on the side in contact with the molecular adhesive layer, The 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 possible temperature _{T h1,} when the heat-sealable temperature of the second thermoplastic resin layer is _{T h2,} a T _{h1> T h2} a is bonded laminate for.

(Molecular adhesive layer)
The molecular adhesive layer is a layer directly adjacent to the first thermoplastic resin layer.
The molecular adhesive layer is a layer that constitutes one of the outermost layers when the bonding laminate is used.
The molecular adhesive layer is used for adhesion to an 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 has a reaction product of the molecular adhesive (M) (having the reactive group remaining) and the molecular adhesive (M) (the structure of the reactive group changes). ).

  The molecular adhesive (M) comprises 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 ureide group and an epoxy group, a silanol group, and a hydrolysis reaction. And a compound having at least one type of reactive group (Zβ) selected from the group consisting of groups that form a silanol group. The “amino group” of the reactive group (Zα) includes an unsubstituted amino group, a monosubstituted amino group, a disubstituted amino group, a primary ammonium group, a secondary ammonium group, a tertiary ammonium group, and a quaternary ammonium group. Shall be included.

The reactive group (Zα) in the molecular adhesive (M) can form a chemical bond with the reactive partial structure (Zγ) of the thermoplastic resin (P ₁ ) in the _first thermoplastic resin layer. .
In the bonding laminate, it is considered that the molecular bond (M) is chemically fixed to the surface of the first thermoplastic resin layer by the chemical bonding. The chemical bond at this time includes a covalent bond, a hydrogen bond, an ionic bond, an intermolecular force and the like, but 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 bonding the bonding laminate to the adherend. . Therefore, the bonding laminate is preferably used for an adherend having a group having high reactivity with these groups on the surface.

The group for forming a silanol group by hydrolysis, a group having a partial structure represented by Si-X ^1. X ¹ is a C1-C10 alkoxy group 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; No.

  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) (however, 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, and a represents an integer of 1 to 3 .)

Examples of the monovalent group having at least ^one reactive group (Zα) of R ¹ include groups represented by the following formulas (2) to (4).

In the formulas (2) to (4), * represents a bond to 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 an alkylene group such as an ethylene group, a trimethylene group, and a propylene group; and an arylene group such as an o-phenylene group, an m-phenylene group, and a p-phenylene group.

R ³ and R ⁴ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms is preferable.
Examples of the hydrocarbon group for R ³ and R ⁴ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, and 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, An alkenyl group such as a 4-pentenyl group and a 5-hexenyl group; an alkynyl group such as an ethynyl group, a propargyl group and a butynyl group; an aryl group such as a phenyl group, a 1-naphthyl group and a 2-naphthyl group;

Z is a single bond, or, -N ^(R 7) - represents a, in the divalent groups represented. R ⁷ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. As the hydrocarbon group for R ^7, the same groups as the hydrocarbon groups for R ³ and R ⁴ can be mentioned.
R ⁵ and R ⁶ are each independently a reactive group (Zα) or a group represented by the formula (2) (in this case, in the formula (2), * represents a bond to a carbon atom constituting an aromatic ring) Hand.)

  As the divalent organic group for G, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, having a substituent, or having an unsubstituted alkenylene group having 2 to 20 carbon atoms, having 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;

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 a vinylene group, a propenylene group, a butenylene group, and a pentenylene group.
Examples of the alkynylene group having 2 to 20 carbon atoms for G include an ethynylene group and a propynylene group.
Examples of the arylene group having 6 to 20 carbon atoms of G include an o-phenylene group, an m-phenylene group, a p-phenylene group, a 2,6-naphthylene group, and a 1,5-naphthylene group.

  Examples of the substituent of 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; An alkoxycarbonyl group such as an ethoxycarbonyl group; and the like.

Examples of the substituent of 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; , An alkylthio group such as an ethylthio group;
These substituents may be bonded to any position in groups such as an alkylene group, alkenylene group, alkynylene group and arylene group. Also, a plurality of the same or different substituents may be bonded to a group such as an alkylene group.

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

Specific examples of the molecular adhesive (M) include the following, but are not limited thereto.
3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyldiethoxymethylsilane, [3- (N, N-dimethylamino) propyl] trimethoxysilane, A molecule 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;

A molecular adhesive in which R ¹ is an azido group, such as (11-azidoundecyl) trimethoxysilane and (11-azidoundecyl) triethoxysilane;

A molecular adhesive wherein R ¹ is a mercapto group, such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyldimethoxymethylsilane;

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

A molecular adhesive wherein R ¹ is a ureido group, such as 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane;

A molecule in which R ¹ is an epoxy group, such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, etc. 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 at least one reactive group (Zα), such as cyclohexyl) ethyltrimethoxysilane and compounds represented by the following formulas (5) to (13);

The molecular adhesive (M) can be used alone or in combination of two or more.
Among these compounds, as the compound represented by the formula (1), a compound in which R ¹ is a group represented by the formula (4) is preferable, and the compounds represented by the formulas (5) to (13) are more preferable. And compounds represented by formulas (5) to (10) are more preferred.
These compounds having a triazine ring in R ^1. The molecular adhesive (M) having a triazine ring tends to be fixed more efficiently on the first thermoplastic resin layer.

As the molecular adhesive (M), a compound known as a silane coupling agent can be used. Further, the compound in which R ¹ is a group represented by the formula (4) can be synthesized according to the method described in WO2012 / 046661, WO2012 / 043631, WO2013 / 18641 and the like.

The molecular adhesive layer may contain components other than the molecular adhesive (M). Examples of the component other than the molecular adhesive (M) include a catalyst and the like.
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% based on the molecular adhesive layer as a whole, since a component that does not participate in adhesion decreases the adhesive force of the molecular adhesive layer. It is preferably at least 70 mass%, more preferably at least 70 mass% and not more than 100 mass%, further preferably at least 90 mass% and not more than 100 mass%, particularly preferably 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. The thickness of the molecular adhesive layer is preferably 0.5 nm or more, 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 has a role of fixing the molecular adhesive (M).
The first thermoplastic resin layer has a single-layer structure.
The composition of the first thermoplastic resin layer may be uniform or may not be uniform. For example, the first thermoplastic resin layer may contain many specific components near the surface of the layer, and the composition near the surface of the layer may be different from the composition inside the layer.

The first thermoplastic resin layer has at least a reactive partial structure (Zγ) capable of forming a chemical bond with a reactive group (Zα) of the molecular adhesive (M) on a surface in contact with the molecular adhesive layer. And a thermoplastic resin (P ₁ ) having the following formula: That is, the first thermoplastic resin layer in the bonding laminate is formed by reaction between the thermoplastic resin (P ₁ ) (having the reactive partial structure (Zγ) remaining) and the thermoplastic resin (P ₁ ). (At least one of which has a changed reactive partial structure (Zγ)).
It should be noted that “including the thermoplastic resin (P ₁ ) on the surface in contact with the molecular adhesive layer” means that the thermoplastic resin (P ₁ ) is formed on the surface of the first thermoplastic resin layer before the molecular adhesive layer is formed. This shows a state where the resin (P ₁ ) is exposed.
At the stage before the formation of the molecular adhesive layer, since the thermoplastic resin (P ₁ ) is exposed on the surface of the first thermoplastic resin layer, the reactive partial structure 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 an olefin resin, a cycloolefin resin, an acrylic resin, an olefin-vinyl acetate resin, an olefin ionomer resin, and a polyester resin.

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

Examples of the cycloolefin resin include a cycloolefin addition polymer, a copolymer of a cycloolefin and an α-olefin, and a ring-opening polymer of a norbornene monomer.
Examples of the cycloolefin include cyclopentene, cyclooctene, norbornene-based monomers, and the like.
Examples of the α-olefin include ethylene and propylene.

As the acrylic resin, a homopolymer of a (meth) acrylic monomer, a copolymer of a (meth) acrylic monomer, a (meth) acrylic monomer, and a monomer copolymerizable therewith And a copolymer with a polymer.
As the (meth) acrylic monomer, 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.
Examples of monomers copolymerizable with the (meth) acrylic monomer include ethylene; aromatic vinyl monomers such as styrene, α-methylstyrene, and chlorostyrene; and cyano group-containing ethylene such as acrylonitrile and methacrylonitrile. (Meth) acrylamide-based monomers such as (meth) acrylamide, N-methylol (meth) acrylamide, and N-butoxymethyl (meth) acrylamide.
In this specification, “(meth) acrylic acid” means “acrylic acid or methacrylic acid”. The same applies to similar descriptions such as “(meth) acrylate”, “(meth) acryl”, “(meth) acrylate” and the like.

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

Examples of the olefinic ionomer resin include a copolymer having a repeating unit derived from an olefinic monomer and a repeating unit derived from a carboxy group-containing monomer, and a resin having an ionic cross-linking link between the copolymer chains. Can be
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 olefinic ionomer resin is composed of a carboxylate ion formed by deprotonating the carboxy group of the carboxy group-containing monomer and a metal ion.
Examples of the metal ion include sodium (I), potassium (I), lithium (I), calcium (II), magnesium (II), zinc (II), copper (I), and 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 between a polycarboxylic acid and a polyhydric alcohol.
Examples of polycarboxylic acids 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 the polyhydric alcohol include ethylene glycol, propylene glycol, 1,4-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, and 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. The amorphous polyester resin refers to a polyester resin which does not show a clear crystallization or crystal melting peak by DSC (differential scanning calorimetry).
Examples of the amorphous polyester resin include glycol-modified polyethylene terephthalate (PETG), glycol-modified poly (1,4-cyclohexane dimethylene terephthalate) (PCTG), and acid-modified poly (1,4-cyclohexane dimethylene terephthalate) (PCTA). Is mentioned.

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

The thermoplastic resin (P ₁ ) has a reactive partial structure (Zγ) capable of forming a chemical bond with the reactive group (Zα) of the molecular adhesive (M).
When 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 below, 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, or 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, by using a monomer having a functional group such as a hydroxy group, a carboxy group, an aldehyde group, or an amino group, a thermoplastic resin (P ₁ ) having a reactive partial structure (Zγ ′) can be obtained. ') Can be manufactured. Further, by subjecting a polymer obtained by performing a polymerization reaction without using these monomers to a modification treatment such as maleic anhydride modification, a polymer having a reactive partial structure (Zγ ′) is obtained. A plastic resin (P ₁ ′) can be manufactured.
By using the thermoplastic resin (P ₁ ′) obtained by these methods as a molding material, the first thermoplastic resin layer can be efficiently formed.

Further, after forming a thermoplastic resin layer containing no thermoplastic resin (P ₁ ′), the thermoplastic resin layer is subjected to a surface treatment to generate a hydroxy group or a carboxy group on the surface of the layer. You may. 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 a known method.

The first thermoplastic resin layer may contain a component other than the thermoplastic resin (P ₁ ) as long as the adhesion to the molecular adhesive layer is not hindered.
Components other than the thermoplastic resin (P ₁ ) include an ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent, a slip agent, an antiblocking agent, and a coloring agent.
These contents can be appropriately determined according to the purpose.

The content of the thermoplastic resin (P1) 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.
When the thickness of the first thermoplastic resin layer is 5 μm or more, it is possible to sufficiently prevent the performance of the molecular adhesive layer from deteriorating due to heating in the heat welding step. In addition, when the thickness of the first thermoplastic resin layer is 80 μm or less, the joining portion (between the adherends) can be made thin.

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, a change in the shape of the first thermoplastic resin layer during thermal welding can be suppressed. Further, since the heat-sealable temperature of the first thermoplastic resin layer is 200 ° C. or less, the influence on the molecular adhesive layer during thermal welding can be suppressed.
The heat sealable temperature of the first thermoplastic resin layer is determined by the type of the thermoplastic resin, the molecular weight of the thermoplastic resin, the content of the thermoplastic resin, the type of the additive, the content of the additive, and the first thermoplastic resin. The characteristics are affected 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, by adjusting the type and amount of the additive, the first thermoplastic resin layer having the target heat sealable temperature can be formed.

[Second thermoplastic resin layer]
The second thermoplastic resin layer is a layer adjacent to the first thermoplastic resin layer and is one of the outermost layers when the bonding laminate is used. Note that an adhesive layer may be present 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 another bonding laminate.

  The second thermoplastic resin layer may have a single-layer structure or a multi-layer structure. The second thermoplastic resin layer in the case where the second thermoplastic resin layer has a single-layer structure, and the respective layers in the case where the second thermoplastic resin layer has a multilayer structure, even if the composition is uniform. The composition may not be uniform. For example, these layers may contain a large amount of 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 formed on at least a surface opposite to the first thermoplastic resin layer by a thermoplastic resin that can be melted at a relatively low temperature and solidified in a short time (hereinafter referred to as “thermoplastic resin”). _{(P 2)} "may be referred to.) it is preferable to include.
By including the thermoplastic resin (P ₂ ) on the surface on the side opposite to the first thermoplastic resin layer, the step is efficiently performed when the thermoplastic resin layer of another bonding laminate is thermally welded. be able to.
“Including the thermoplastic resin (P ₂ ) 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 that it is exposed.

Examples of the thermoplastic resin (P ₂ ) include an olefin resin, a cycloolefin resin, an acrylic resin, an olefin-vinyl acetate resin, an olefin ionomer resin, and a polyester resin.
Specific examples of these thermoplastic resins include those similar to the thermoplastic resins (P ₁ ).
The thermoplastic resin (P ₂ ) can be used alone or in combination of two or more.

The second thermoplastic resin layer may contain a component other than the thermoplastic resin (P ₂ ) as long as the thermal welding property is not impaired.
Components other than the thermoplastic resin (P ₂ ) include an ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent, a slip agent, an antiblocking agent, and a coloring agent.
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 a first thermoplastic resin. A non-uniform layer containing a thermoplastic resin (P ₂ ) on the surface opposite to the resin layer may be used.
The content of the thermoplastic resin (P2) in the _second thermoplastic resin layer having a single-layer structure is usually 50 to 100% by mass, and 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. In addition, when the thickness of the second thermoplastic resin layer is 150 μm or less, the bonding portion (between the adherends) can be reduced.

When the second thermoplastic resin layer has a multilayer structure, the second thermoplastic resin layer may be an outermost layer on the side opposite to the first thermoplastic resin layer (a second thermo-resin layer having a multilayer structure). Of 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 on the side 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 on the side opposite to the first thermoplastic resin layer is based on the entire outermost layer. , Usually 50 to 100% by mass, preferably 80 to 100% by mass.
The thickness of the entire second thermoplastic resin layer having a multilayer structure is usually from 3 to 150 μm, preferably from 10 to 120 μm, more preferably from 15 to 80 μm.
When the entire thickness of the second thermoplastic resin layer having a multilayer structure is 3 μm or more, sufficient thermal welding can be performed. In addition, when the thickness of the second thermoplastic resin layer is 150 μm or less, the bonding portion (between the adherends) can be reduced.
In the second thermoplastic resin layer having a multilayer structure, the number of layers is not particularly limited. The number of layers of the second thermoplastic resin layer having a multilayer structure is usually 2 to 10, 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 room temperature is improved. Further, since the heat-sealable temperature of the second thermoplastic resin layer is 180 ° C. or less, when the bonding laminate of the present invention is used, the layers between the second thermoplastic resin layers are firmly adhered to each other. Thus, the two adherends can be more firmly joined.
The heat sealable temperature of the second thermoplastic resin layer can be adjusted by the same method as the method of adjusting the heat sealable temperature of the first thermoplastic resin layer.
When the second thermoplastic resin layer has a multilayer structure, the heat-sealable temperature of the second thermoplastic resin layer is the heat-sealing temperature of the outermost layer on the side opposite to the first thermoplastic resin layer. This refers to the sealable temperature.

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

For example, as shown in FIG. 1, a first thermoplastic resin layer (1) of a laminate (3) composed of a first thermoplastic resin layer (1) and a second thermoplastic resin layer (2). By directly forming the molecular adhesive layer (4) thereon, the bonding laminate (5) is obtained.
As described above, in the laminate (3), the first thermoplastic resin layer (1) includes the thermoplastic resin (P ₁ ) on the surface (6) on the side in contact with the molecular adhesive layer (4). . Further, the second thermoplastic resin layer (2) of the laminate (3) includes a thermoplastic resin (P ₂ ) on the surface (7) opposite to the first thermoplastic resin layer (1). Is preferred.

The method for producing the laminate (η) is not particularly limited.
For example, a pellet containing the thermoplastic resin (P ₁ ) and a pellet containing the thermoplastic resin (P ₂ ) are each melted, and a co-extruded multilayer film obtained by simultaneously extruding these from a multilayer die is used as a laminate. (Η).
In addition, a multilayer film obtained by laminating a resin film containing a thermoplastic resin (P ₁ ) and a resin film containing a thermoplastic resin (P ₂ ) can be used as a laminate (η). .

Further, a coating solution containing a thermoplastic resin (P ₂ ) is applied on a first thermoplastic resin layer (resin film) containing a thermoplastic resin (P ₁ ), and the obtained coating film is dried. To form a second thermoplastic resin layer, or apply a coating solution containing a thermoplastic resin (P ₁ ) on a second thermoplastic resin layer (resin film) containing a thermoplastic resin (P ₂ ). A multilayer film obtained by coating and drying the obtained coating film to form a first thermoplastic resin layer can be used as a laminate (η).

  Among these, it is preferable to use a co-extruded 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 another layer is not yet formed may be referred to as a “first thermoplastic resin layer” or a “second thermoplastic resin layer”.

When manufacturing the laminate (η), the components of each layer are so selected 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, in the bonding laminate of the present invention, 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 , _Th1 > _Th2 .
As described below, when two adherends are joined using the joining 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 the height higher than that, the heat welding step can be performed without adversely affecting the molecular adhesive layer.

The molecular adhesive (M) used for forming the molecular adhesive layer is formed by 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 in consideration of the combination with ()).
Among them, the reactive group (Zα) and the reactive partial structure (Zγ) preferably satisfy the following requirement (Q1).
Requirements (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 ureide group and an epoxy group, and the thermoplastic resin (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 reactive group (Zα) of the molecular adhesive (M) is an azide group, and the reactive partial structure (Zγ) of the thermoplastic resin (P ₁ ) is a carbon-carbon single bond, a carbon-carbon It is at least one selected from the group consisting of a heavy bond and a carbon-hydrogen single bond.

In the bonding laminate according to 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 to form a molecular bond. It is considered that the adhesive (M) is fixed to the first thermoplastic resin layer.
By satisfying the above requirement (Q1), it is considered that this chemical bond can be efficiently formed.

  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 ureide 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 light irradiation as described later. In this case, nitrene, which is a reaction intermediate, can react with a carbon-carbon single bond, a carbon-carbon double bond, or a carbon-hydrogen single bond, so that the reactive partial structure (Zγ) of the thermoplastic resin (P ₁ ) 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 is used.
If it is a thermoplastic resin, it usually contains at least one of a carbon-carbon single bond, a carbon-carbon double bond, and a carbon-hydrogen single bond. Therefore, when 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 a molecular adhesive (M) is prepared, this solution is applied on the first thermoplastic resin layer, and then the obtained coating film is subjected to a drying treatment or a molecular adhesive ( By performing the process of fixing M) to the first thermoplastic resin layer, a molecular adhesive layer can be formed.

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 compound solvents such as benzene and toluene; amide solvents such as N, N-dimethylformamide and N-methylpyrrolidone; 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. When the concentration of the molecular adhesive (M) is 0.005 mol / L or more, the molecular adhesive layer can be efficiently formed on the first thermoplastic resin layer. Further, when the content is not more than 1.000 mol / L, an unintended reaction of the molecular adhesive solution can be suppressed, and the stability of the solution is excellent.

  The method for applying 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. Etc., but a bar coating method and a gravure coating method are preferred.

After the application of the molecular adhesive solution, a drying process is usually required to dry the obtained coating film by natural drying or feeding to a drying mechanism. Among these, it is preferable to carry out the drying treatment by feeding into the drying mechanism from the viewpoint of improving the productivity. Examples of the drying mechanism include a batch-type drying mechanism such as an air oven, a heat roll, and a hot air-through mechanism (where the object to be dried moves and passes through an open-type drying furnace while being heated and dried while being blown. And a continuous drying mechanism. Note that a device that can be used as a part of these drying mechanisms, for example, a heating medium circulation heater such as a high-frequency heating or an oil heater, and a heater itself such as a far-infrared heater can also 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 the molecular adhesive layer is formed, 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) on the first thermoplastic resin layer, and the generation of the chemical bond is accelerated by heating. It is preferable from the viewpoint of the improvement of. The heating temperature is usually 40 to 250C, preferably 60 to 200C, more preferably 80 to 120C. The heating time is generally 1 second to 120 minutes, preferably 1 to 60 minutes, more preferably 1 to 30 minutes.
The heating method is not particularly limited, and a mechanism and an apparatus similar to the above-described drying mechanism can be used.

When the reactive group (Zα) has photoreactivity like an azide group, a light irradiation treatment is performed as the fixing treatment. As the light to be irradiated, ultraviolet rays are usually used. In this case, it is preferable to perform the fixing treatment after the drying treatment from the viewpoint of improving the reactivity between the reactive group (Zα) and the reactive group (Zγ).
Irradiation with ultraviolet light can be performed using an ultraviolet light irradiation device using a light source such as a mercury lamp, a metal halide lamp, an ultraviolet LED, and an electrodeless lamp.
The treatment conditions of the light irradiation treatment are not particularly limited as long as a desired light reaction can be performed.

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

2) Method for joining two adherends The method for joining two adherends according to the present invention uses the two laminates for joining to form an adherend (I) and an adherend (II). Wherein the two joining laminates are each independently the joining laminate of the present invention, and the first joining laminate 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. represents the bonding laminate comprising in the order as (a), the second of the bonding laminate molecular adhesive layer comprising molecules adhesive _{(M B) (B-M} ), the first 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 group of steps including the following steps (L1) to (L3), a group of steps including steps (M1) to (M3), and a group of steps including steps (N1) and (N2). A method for joining an adherend (I) and an adherend (II), which comprises performing a process group.
Step (L1): Step of bonding molecular adhesive layer (AM) of bonding laminate (A) to adherend (I) Step (L2): Molecular adhesive of bonding laminate (B) Step (L3) of bonding the layer (BM) and the adherend (II): the second thermoplastic resin layer (A-2) of the laminate obtained in the step (L1); Step (M1) of heat-welding the laminate obtained in L2) to the second thermoplastic resin layer (B-2): the second thermoplastic resin layer (A-) of the bonding laminate (A) 2) a step of thermally welding the second thermoplastic resin layer (B-2) of the bonding laminate (B) to the second thermoplastic resin layer (B-2): the molecular adhesive layer of the laminate obtained in the step (M1) Step (M3) of bonding (AM) and adherend (I): the molecular adhesive layer (BM) of the laminate obtained in step (M2) and adherend (II) Bonding process ( 1): Arrangement in which 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) face each other. Step (N2) of stacking the adherend (I), the laminate for joining (A), the laminate for joining (B), and the adherend (II) in this order: Step (N1): Obtained in Step (N1) Is 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), and the second Step of simultaneously performing thermal welding of the thermoplastic resin layer (A-2) and the second thermoplastic resin layer (B-2)

Bonding the laminate (A) has a molecular adhesive layer comprising molecules adhesive _{(M A) (A-M} ), the first thermoplastic resin layer (A-1), and a second thermoplastic resin layer ( A-2) A bonding laminate having A-2) in this order.
In the bonding method of the present invention, the bonding laminate (A) is used for bonding to the adherend (I).

Bonding the laminate (B), the molecular adhesive layer comprising molecules adhesive _{(M B) (B-M} ), the first thermoplastic resin layer (B-1), and a second thermoplastic resin layer ( This is a bonding laminate (B) having B-2) in this order.
In the bonding method of the present invention, the bonding laminate (B) is used for bonding to the adherend (II).

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

The second thermoplastic resin layer (A-2) of the bonding laminate (A) has a thermoplastic resin (P ₂ ) (hereinafter referred to as “P _2” ) on the surface opposite to the first thermoplastic resin layer (A-1). , The thermoplastic resin (P ₂ ) contained in the second thermoplastic resin layer (A-2) is sometimes referred to as “thermoplastic resin (P _2A )”. The second thermoplastic resin layer (B-2) of the laminate (B) has a thermoplastic resin (P ₂ ) (hereinafter, referred to as a thermoplastic resin (P ₂ )) 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) contains a thermoplastic resin (P _2B ), the thermoplastic resin (P ₂ ) may be used. _2A ) (when the second thermoplastic resin layer (A-2) contains two or more kinds of thermoplastic resins (P _2A ), the content is the largest). The same thermoplastic resin (P _2B ) (the one with the highest content when the second thermoplastic resin layer (B-2) contains two or more types of thermoplastic resins (P _2B )) Is preferred. Since the thermoplastic resin (P _2A ) and the thermoplastic resin (P _2B ) are the same, the two adherends can be more firmly joined.

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

A thermoplastic resin (P _2A ) (when the second thermoplastic resin layer (A-2) contains two or more types of thermoplastic resins (P _2A ), the content is highest) and a thermoplastic resin (P _2A ) _2B ) (when the second thermoplastic resin layer (B-2) contains two or more kinds of thermoplastic resins (P _2B ), the content is the largest), when the Hansen solubility parameters are different from each other. The working distance Ra is preferably small. By using a combination of the thermoplastic resin (P _2A ) and the thermoplastic resin (P _2B ) having a short interaction distance Ra of the Hansen solubility parameter, heat welding can be performed more efficiently.
The interaction distance Ra of the Hansen solubility parameter of the thermoplastic resin (P _2A ) and that of 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 formula, [delta] D _A is dispersive component Hansen solubility parameter of the thermoplastic resin _{(P 2A),} [delta] D _B is dispersive component Hansen solubility parameter of the thermoplastic resin _{(P 2B),} [delta] P _A, the thermoplastic resin ( polar component Hansen solubility parameter P _2A), the [delta] P _B, the polar component Hansen solubility parameter of the thermoplastic resin _{(P 2B), δH a} hydrogen bonding component Hansen solubility parameter of the thermoplastic resin _{(P 2A),} δH _B represents the 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) is performed. 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 performed by molecular adhesion. agent (M _a) or (M _B) reactive groups in (Zβ) reacts with the functional group in the compound constituting the adherend (I) or adherend (II), a chemical bond is formed This is done by:
Therefore, usually, as the adherend (I) or the adherend (II), a substance 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 the inorganic substance include glass and inorganic oxides (excluding glass).
These members may be subjected to a surface treatment. A member having a hydroxy group, a carboxy group, or the like generated by the surface treatment is more preferably used as an adherend.
Further, by using the surface treatment technology, a member having a surface containing a thermoplastic resin or a thermosetting resin can also be used as the adherend.
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 a known method.
Further, a primer layer may be provided on the surface of the adherend as necessary.

[Step group including steps (L1) to (L3)]
FIG. 2 shows each step of a step group including the 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) ( The molecular adhesive layer (AM) (8) of the bonding laminate (A) (11) having 10) is adhered to the adherend (I) (12) to obtain a laminate (13). [FIG. 2 (a)].

  The step (L1) can be performed using, for example, a heating press machine, an autoclave device, a vacuum bonding machine, a three-dimensional vacuum heating molding machine (TOM molding machine), a heating laminating device, 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 a 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 still more preferably 0.4 to 1 MPa.

The bonding temperature in the step (L1) is usually 40 to 200 ° C, preferably 50 to 170 ° C, and more preferably 60 to 140 ° C.
The processing time of 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) ( The molecular adhesive layer (BM) (14) of the bonding laminate (B) (17) having the composition (16) and the adherend (II) (18) are adhered to obtain a laminate (19). [FIG. 2 (b)].
Step (L2) can be performed by a method and under the same conditions as in 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) 2) is thermally welded to the second thermoplastic resin layer (B-2) (16) to obtain a joint structure (20) [FIG. 2 (c)].

The step (L3) can be performed using, for example, a heating press machine, an autoclave device, a vacuum bonding machine, a three-dimensional vacuum heating molding machine (TOM molding machine), a heating laminating device, 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 a surface pressure is applied in the step (L3), the pressure is generally 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 processing time of the step (L3) is usually 1 second to 1 minute, preferably 3 to 30 seconds.

When performing a process group including the processes (L1) to (L3), in the process (L1), the molecular adhesive layer (AM) of the bonding laminate (A) and the adherend (I) are bonded. The temperature at the time is T _L1 , and the temperature at the time of bonding the molecular adhesive layer (BM) of the bonding laminate (B) and the adherend (II) in the step ( _L2 ) is T _L2 , L3), the temperature at the time of thermally welding the second thermoplastic resin layer (A-2) and the second thermoplastic resin layer (B-2) is _TL3 , and the joining laminate (A) The heat-sealable temperature of the first thermoplastic resin layer (A-1) is _Th1A , the heat-sealable temperature of the second thermoplastic resin layer (A-2) is _Th2A , and the bonding laminate ( In B), the heat-sealable temperature of the first thermoplastic resin layer (B-1) is _Th1B , and the heat sealable temperature of the second thermoplastic resin layer (B-2) is _Th1B . When the sealable temperature is _Th2B , _both of the following equations (E-1) and (E-2) are satisfied, and at least one of the following equations (E-3) and (E-4) is satisfied. Preferably, it is satisfied.

By satisfying the expression (E-1), the deformation of the first thermoplastic resin layer (A-1) of the bonding laminate (A) in the step (L1) is suppressed.
By satisfying the expression (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 the formula (E-3) and the formula (E-4), the second thermoplastic resin layer (A-2) of the bonding laminate (A) and the bonding laminate (B) of the bonding laminate (B) can be formed. The second thermoplastic resin layer (B-2) can be efficiently heat-welded to the second thermoplastic resin layer (B-2).
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 formulas (E-3) and (E-4) are satisfied.

[Step group including steps (M1) to (M3)]
FIG. 3 shows each step of the step group including the 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 bonding laminate (A) (24) having the molecular adhesive layer (BM) (25), and the first thermoplastic resin layer. The second thermoplastic resin layer (B-) of the bonding laminate (B) (28) having the resin layer (B-1) (26) and the second thermoplastic resin layer (B-2) (27). 2) and (27) are thermally welded to obtain a laminate (29) [FIG. 3 (a)].
Step (M1) can be performed by a method and under the same conditions as in step (L3).

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

The step (M2) and the step (M3) can be performed by the same method and the same conditions as the step (L1).
Step (M2) and step (M3) may be performed simultaneously. For example, the adherend (I), the laminate obtained in the step (M1) and the adherend (II) are superposed in this order, and a crimping process is performed on the laminate to obtain the step (M2). Step (M3) can be performed simultaneously.

[Steps including steps (N1) and (N2)]
FIG. 4 shows each step of the step group including the steps (N1) and (N2).
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), and the first thermoplastic resin. The second thermoplastic resin layer (B-) of the bonding laminate (B) (41) having the resin layer (B-1) (39) and the second thermoplastic resin layer (B-2) (40). 2) In the arrangement in which (40) faces each other, the adherend (I) (42), the laminate for joining (A) (35), the laminate for joining (B) (41), and the adherend (II) ( 43) are superposed 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 the adherend (II), and heat welding between the second thermoplastic resin layer (A-2) and the second thermoplastic resin layer (B-2) at the same time, and joining. A structure (45) is obtained (FIG. 4B).

  The step (N2) can be performed using, for example, a heating press, an autoclave, a vacuum bonding machine, a three-dimensional vacuum heating molding machine (TOM molding machine), a heating laminating machine, 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 a 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 processing time of the step (N2) is usually 1 second to 1 hour, preferably 5 seconds to 30 minutes, more preferably 10 seconds to 10 minutes.

When performing the process group including the processes (N1) and (N2), the heat-sealable temperature of the first thermoplastic resin layer (A-1) of the bonding laminate (A) is _Th1A , and the second thermoplastic resin is the second thermoplastic resin. The heat sealable temperature of the resin layer (A-2) is _Th2A , the heat sealable temperature of the first thermoplastic resin layer (B-1) of the bonding laminate (B) is _Th1B , and the second temperature is _Th2B . 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 that at least one of E-6) is satisfied.

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

When joining the adherend (I) and the adherend (II), a step group including the steps (L1) to (L3) or a step group including the steps (N1) and (N2) is used. It is preferred to do so.
In the step group including the steps (L1) to (L3), the bonding treatment between the molecular adhesive layer and the adherend is performed before performing the heat welding treatment. Therefore, the bonding treatment between the molecular adhesive layer and the adherend can be performed in a state where the thermoplastic resin layer does not undergo thermal deformation due to the heat welding treatment. It can be bonded more firmly.

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

3) Method for Manufacturing Bonded Structure The method for manufacturing a bonded structure according to the present invention includes a method for manufacturing a layer / adhered body (II) derived from the adherend (I) / the bonded laminate (A) and the bonded laminate (B). A) a method of manufacturing a joint structure having a layer structure, wherein the adherend (I) and the adherend (II) are joined by using the joint method of the present invention.

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

As the adherend (I) and the adherend (II), those shown in the invention of the method for joining two adherends can be used.
Among these, as the adherend (I) and the adherend (II), at least one selected from the group consisting of a metal, an inorganic substance, and a thermosetting resin is independently applied to at least the surface to be adhered. Is preferred.

When the adherend has a surface to be adhered formed of a thermoplastic resin, the adherends can be directly thermally welded and joined together 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 is present on the surface to be adhered of the adherend, it is difficult to firmly join these adherends by this method.

  The method for producing a joined structure of the present invention uses the joining laminate of the present invention. Therefore, according to the method for manufacturing a joint structure of the present invention, even when a metal, an inorganic substance, or a thermosetting resin is present on the surface to be bonded of the adherend, these adherends are firmly bonded. A joined structure that is joined 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.
Parts and% in each example are based on mass unless otherwise specified.

[Measurement of heat sealable temperature of each layer of multilayer film]
The heat sealable temperature of each layer of the multilayer films (1) to (5) was determined by the following method.
Two multi-layer films (25 mm × 150 mm) were prepared, they were overlapped so that the layers of the same components faced each other, and they were thermally welded at 0.2 MPa for 1 second to obtain a test piece. At this time, a plurality of test pieces were obtained by changing the heat welding temperature at 5 ° C intervals (for example, 140 ° C, 145 ° C, 150 ° C).
Each of the obtained test pieces was 300 mm in an environment of 23 ° C. and 50% humidity (relative humidity) using a tensile tester (trade name “Tensilon Universal Material Tester” manufactured by A & D Corporation). 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 a molding material, 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]”. To obtain a multilayer film (1). 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 temperature of the second thermoplastic resin layer was The temperature was 145 ° C.

[Production Examples 2 and 5]
Except that the molding materials shown in Table 1 were used, multilayer films (2) and (5) were obtained in the same manner as in Production Example 1.

[Production Example 3]
By using two types of polyethylene and nylon as molding materials, a co-extrusion method is used to obtain “first thermoplastic resin layer [polyethylene (PE) thickness 25 μm] / second thermoplastic resin layer [nylon (Ny) thickness] 30 μm / polyethylene (PE) thickness 25 μm] ". When the heat-sealable temperature of each layer was measured for the obtained multilayer film (3), the heat-sealable temperature of the first thermoplastic resin layer was 140 ° C., and the second thermoplastic resin layer (polyethylene layer) was obtained. 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 the “first thermoplastic resin layer [polyethylene (PE) thickness 100 μm] / second thermoplastic resin layer” [Ethylene / vinyl acetate copolymer resin (EVA) thickness 50 μm] ”to obtain a multilayer film (4). When the heat-sealable temperature of each layer of the obtained multilayer film (4) was measured, the heat-sealable temperature of the first thermoplastic resin layer was 140 ° C, and the heat-sealable temperature of the second thermoplastic resin layer was The temperature was 110 ° C.

Table 1 shows details of the multilayer films (1) to (5).
In Table 1, the names of the resin components 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 / 0466651, 6- (3-triethoxysilylpropyl) amino-1,3,5-triazine-2,4-diazide (the compound represented by the formula (10), in Table 2 , "PTES") was obtained (solvent: ethanol, concentration 0.1 g / L).

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

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

  Table 2 shows details of the bonding laminates (1) to (5) obtained in Production Examples 1 to 4 and Production Comparative Example 1.

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

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

[Examples 3 and 4, Comparative Example 1]
A bonded structure was obtained in the same manner as in Example 2, except that the bonding laminate and the manufacturing conditions shown in Table 3 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) face the plasma-treated surface of the glass plate, respectively, and the heat-sealable temperatures of the two multilayer films (1) are 145 ° C. And the multilayer film (1), the multilayer film (1), and the adherend are stacked in this order such that the layers oppose each other, and these are laminated under the conditions of 145 ° C. and 0.5 MPa (surface pressure). The bonded structure was obtained by thermocompression bonding for minutes.

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

(Shape change evaluation)
Using the joint structures obtained in Examples 1 to 4 and Comparative Examples 1 and 2 as test pieces, seepage of the joint laminate after thermocompression bonding was visually confirmed and evaluated according to the following criteria.
A: No exudation at the end due to deformation of the bonding laminate was visually observed.
F: The exudation of the end due to deformation of the bonding laminate was visually confirmed.

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

1: a first thermoplastic resin layer 2: a second thermoplastic resin layer 3: a laminate composed of a first thermoplastic resin layer and a second thermoplastic resin layer 4: a molecular adhesive layer 5: bonding Laminate 6: Surface 7 in contact with molecular adhesive layer 7: Surface opposite to 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 obtained as a result of the step (L1) 14.25.38: molecular adhesive layer (BM)
15.26.39: First thermoplastic resin layer (B-1)
16.27.40: Second thermoplastic resin layer (B-2)
17.28.41: Laminate for bonding (B)
18.32.43: Adherend (II)
19: Laminated body 200.33.45 resulting from step (L2): Joint structure 29: Laminated body 31 resulting from step (M1): Laminated body 44 resulting from step (M2): What was 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. The molecular adhesive layer and the second thermoplastic resin layer are bonding laminates each constituting an outermost layer during use,
The molecular adhesive (M) comprises 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 ureide group, and an epoxy group, a silanol group, and hydrolysis. A compound having at least one type of reactive group (Zβ) selected from the group consisting of a group that forms a silanol group by a reaction,
The first thermoplastic resin layer has at least a reactive partial structure (Zγ) capable of forming a chemical bond with a reactive group (Zα) of the molecular adhesive (M) on a surface in contact with the molecular adhesive layer. ) Having a thermoplastic resin (P ₁ ),
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 , _Th1 > _Th2 . 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 ureide group and an epoxy group, and the thermoplastic resin (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 reactive group (Zα) of the molecular adhesive (M) is an azide group, and the reactive partial structure (Zγ) of the thermoplastic resin (P ₁ ) is a carbon-carbon single bond, a carbon-carbon The bonding laminate according to claim 1, wherein the bonding laminate is at least one selected from the group consisting of a heavy bond and a carbon-hydrogen single bond. The bonding laminate 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 ureide group, and an epoxy group, or a monovalent group having at least one of these reactive groups. (However, excluding an amino group, an azide group, a mercapto group, an isocyanate group, a ureide group and an epoxy group), G represents a divalent organic group, X represents a hydroxy group, an alkoxy group having 1 to 10 carbon atoms. Represents a group or a halogen atom, 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. Laminate for bonding. The thermoplastic resin (P ₁ ) is at least one selected from the group consisting of an olefin resin, a cycloolefin resin, an acrylic resin, an olefin-vinyl acetate resin, an olefin ionomer resin, and a polyester resin; The bonding laminate according to claim 1.   The second thermoplastic resin layer has an olefin-based resin, a cycloolefin-based resin, an acrylic-based resin, an olefin-vinyl acetate-based resin, an olefin-based ionomer resin, and a polyester on at least a surface opposite to the molecular adhesive layer. The bonding laminate according to any one of claims 1 to 5, wherein the bonding laminate includes at least one selected from the group consisting of resins. A method of joining an adherend (I) and an adherend (II) using two joining laminates,
The two joining laminates are each independently the joining laminate according to any one of claims 1 to 6,
A first bonding laminate molecular adhesive layer comprising molecules adhesive _{(M A) (A-M} ), the first thermoplastic resin layer having a single-layer structure (A-1), and a single-layer structure or it represents a second thermoplastic resin layer having a multilayer structure bonding laminate comprising (a-2) in this order (a), comprising a second bonding laminate 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 bonding laminate (B) having this order,
Any one selected from a group of steps including the following steps (L1) to (L3), a group of steps including steps (M1) to (M3), and a group of steps including steps (N1) and (N2). A method for joining an adherend (I) and an adherend (II), comprising performing a process group.
Step (L1): Step of bonding molecular adhesive layer (AM) of bonding laminate (A) to adherend (I) Step (L2): Molecular adhesive of bonding laminate (B) Step (L3) of bonding the layer (BM) and the adherend (II): the second thermoplastic resin layer (A-2) of the laminate obtained in the step (L1); Step (M1) of heat-welding the laminate obtained in L2) to the second thermoplastic resin layer (B-2): the second thermoplastic resin layer (A-) of the bonding laminate (A) 2) a step of thermally welding the second thermoplastic resin layer (B-2) of the bonding laminate (B) to the second thermoplastic resin layer (B-2): the molecular adhesive layer of the laminate obtained in the step (M1) Step (M3) of bonding (AM) and adherend (I): the molecular adhesive layer (BM) of the laminate obtained in step (M2) and adherend (II) Bonding process ( 1): Arrangement in which 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) face each other. Step (N2) of stacking the adherend (I), the laminate for joining (A), the laminate for joining (B), and the adherend (II) in this order: Step (N1): Obtained in Step (N1) Is 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), and the second Step of simultaneously performing thermal welding of the thermoplastic resin layer (A-2) and the second thermoplastic resin layer (B-2) A method of joining an adherend (I) and an adherend (II), which performs a step 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) is bonded to the adherend (I) is T _L1 ,
In the step (L2), the temperature at which the molecular adhesive layer (BM) of the bonding laminate (B) is bonded to the adherend (II) 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 . At one time,
The adhesion according to claim 7, wherein both 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. A method of joining the body (I) and the adherend (II).

A method of joining an adherend (I) and an adherend (II), which performs a group of steps 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 step (N2), when the temperature at the time of thermal welding is T _N2 ,
The method for bonding an adherend (I) and an adherend (II) according to claim 7, wherein at least one of the following equations (E-5) and (E-6) is satisfied.

  A method for producing a bonding structure having a layer structure of an adherend (I) / a bonding laminate (A) and a layer / adherend (II) derived from a bonding laminate (B). A method for producing a joined structure, comprising joining 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 include at least one selected from the group consisting of a metal, an inorganic substance, and a thermosetting resin on at least a surface to be adhered. 11. The method for manufacturing a joined structure according to item 10.

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