CN111902509B

CN111902509B - Laminate for bonding, method for bonding 2 adherends, and method for producing bonded structure

Info

Publication number: CN111902509B
Application number: CN201980023845.3A
Authority: CN
Inventors: 上村和惠; 宫田壮
Original assignee: Lintec Corp
Current assignee: Lintec Corp
Priority date: 2018-03-29
Filing date: 2019-03-28
Publication date: 2022-05-31
Anticipated expiration: 2039-03-28
Also published as: WO2019189667A1; CN111902509A; JPWO2019189667A1; JP6674594B2; KR102639338B1; TWI811324B; KR20200136379A; TW202003744A

Abstract

The present invention is a laminate for bonding, which comprises a molecular adhesive layer containing a specific molecular adhesive (M), a1 st thermoplastic resin layer containing a specific thermoplastic resin, and a 2 nd thermoplastic resin layer in this order, and in which the molecular adhesive layer and the 2 nd thermoplastic resin layer each constitute the outermost layer in use, wherein the heat-sealable temperature of the 1 st thermoplastic resin layer is T_h1The heat-sealable temperature of the 2 nd thermoplastic resin layer is T_h2When, T_h1＞T_h2. By using the laminate for bonding of the present invention, the thermal bonding step can be performed without adversely affecting the molecular adhesive layer.

Description

Laminate for bonding, method for bonding 2 adherends, and method for producing bonded structure

Technical Field

The present invention relates to a laminate for bonding having a molecular adhesive layer (which refers to a layer formed using a molecular adhesive, hereinafter the same), a method for bonding 2 adherends using the laminate for bonding, and a method for producing a bonded structure.

Background

Compounds having 2 or more reactive groups can form chemical bonds by utilizing the characteristics of each reactive group, and thus are useful as molecular adhesives.

For example, patent document 1 describes a bonding method for bonding a substrate a and a substrate B, the method including: forming a molecular adhesive layer on the surface of the substrate a using a specific molecular adhesive; disposing a substrate B so as to face the molecular adhesive on the surface of the substrate A; and a step of bonding the substrate A and the substrate B by applying a force to the substrate A and the substrate B.

Patent document 1 describes, as a method for forming a molecular adhesive layer on the surface of a substrate, a method in which a molecular adhesive solution in which a molecular adhesive is dissolved or dispersed is prepared, the substrate is immersed in the molecular adhesive solution, and then ultraviolet rays are irradiated thereto, thereby forming a chemical bond between the molecular adhesive and the surface of the substrate, thereby forming a molecular adhesive layer.

Documents of the prior art

Patent document

Patent document 1: WO2012/043631 (US 2013/177770A 1).

Disclosure of Invention

Problems to be solved by the invention

As described in patent document 1, a double-sided adhesive sheet having molecular adhesive layers on both sides of a base can be efficiently obtained by immersing the base in a molecular adhesive solution. Such a double-sided adhesive sheet can be used as a bonding material when 2 adherends are easily and firmly fixed.

However, in the case of using a roll-to-roll method for mass production of such a double-sided adhesive sheet, it is difficult to stably form the molecular adhesive layers on both sides of the base by the dipping method.

Therefore, a method capable of firmly bonding 2 adherends using an adhesive sheet having a molecular adhesive layer obtained by a roll-to-roll method is desired.

The present inventors have studied a method of bonding 2 adherends using a bonding laminate having a molecular adhesive layer on only one surface. As a result, it was found that 2 adherends can be firmly joined by preparing 2 joining laminates each having a molecular adhesive layer on a thermoplastic resin layer, adhering the respective molecular adhesive layers to the respective adherends, and further thermally bonding the 2 thermoplastic resin layers.

However, in this joining method, depending on the conditions for heat-welding 2 thermoplastic resin layers, the thermoplastic resin layers may be deformed greatly, and as a result, the molecular adhesive layer may be deformed, and the adhesive strength of the molecular adhesive layer may be reduced.

The present invention has been made to solve the above problems, and an object of the present invention is to provide a laminate for bonding having a molecular adhesive layer and a thermoplastic resin layer, which can be subjected to a thermal fusion bonding step without adversely affecting the molecular adhesive layer, a method for bonding 2 adherends using the laminate for bonding, and a method for producing a bonded structure.

Means for solving the problems

In order to solve the above problems, the present inventors have intensively studied a method for bonding 2 adherends using a laminate for bonding having a molecular adhesive layer and a thermoplastic resin layer.

As a result, they have found that the use of a laminate for bonding satisfying the following requirements (a) to (c) enables the thermal welding step to be performed without adversely affecting the molecular adhesive layer, and have completed the present invention.

Requirement (a): the thermoplastic resin layer is composed of a1 st thermoplastic resin layer and a 2 nd thermoplastic resin layer.

Essential element (b): the molecular adhesive layer is formed on the 1 st thermoplastic resin layer.

Requirement (c): the 2 nd thermoplastic resin layer is a layer capable of being thermally welded at a lower temperature than the 1 st thermoplastic resin layer.

Therefore, the present invention provides the following laminates for bonding (1) to (6), methods for bonding 2 adherends (7) to (9), and methods for producing bonded structures (10) to (11).

(1) A laminate for bonding which comprises a molecular adhesive layer containing a molecular adhesive (M), a1 st thermoplastic resin layer having a single-layer structure, and a 2 nd thermoplastic resin layer having a single-layer structure or a multilayer structure in this order, and in which the molecular adhesive layer and the 2 nd thermoplastic resin layer each constitute the outermost layer in use, wherein the molecular adhesive (M) has at least 1 reactive group (Z alpha) selected from the group consisting of an amino group, an azido group, a mercapto group, an isocyanate group, a ureido group, and an epoxy group, and is selected from the group consisting of silanolA compound containing a group and at least 1 reactive group (Z beta) among groups which form silanol groups by hydrolysis reaction, wherein the 1 st thermoplastic resin layer contains a thermoplastic resin (P) at least on the surface thereof which is in contact with the molecular adhesive layer₁) The thermoplastic resin (P)₁) A reactive partial structure (Z gamma) capable of forming a chemical bond with the reactive group (Z alpha) of the molecular adhesive (M), and the heat-sealable temperature in the 1 st thermoplastic resin layer is T_h1The heat-sealable temperature of the 2 nd thermoplastic resin layer is T_h2Time, T_h1＞T_h2。

(2) The laminate for bonding according to (1), wherein the reactive group (Z α) of the molecular adhesive (M) is at least 1 selected from the group consisting of an amino group, a mercapto group, an isocyanate group, a urea group and an epoxy group, and the thermoplastic resin (P)₁) The reactive partial structure (Z gamma) is at least 1 selected from the group consisting of a hydroxyl group, a carboxyl group, an aldehyde group and an amino group, or the reactive group (Z alpha) of the molecular binder (M) is an azide group and the thermoplastic resin (P)₁) Has a reactive partial structure (Z gamma) of at least 1 kind selected from the group consisting of a carbon-carbon single bond, a carbon-carbon double bond and a carbon-hydrogen single bond.

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

[ solution 1]

R¹The compound is characterized by representing a reactive group (Z alpha) selected from amino, azido, sulfydryl, isocyanate, carbamido and epoxy or a 1-valent group containing more than 1 of the reactive groups (wherein amino, azido, sulfydryl, isocyanate, carbamido and epoxy are excluded), G represents a 2-valent organic group, X represents hydroxyl, alkoxy with 1-10 carbon atoms or halogen atoms, Y represents a hydrocarbon group with 1-20 carbon atoms, and a represents an integer of 1-3.

(4) The laminate for bonding according to any one of (1) to (3), wherein the reactive group (Z α) of the molecular adhesive (M) and the thermoplastic resin (P)₁) The reactive moiety structure (Z γ) of (2) forms a chemical bond.

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

(6) The laminate for bonding according to any one of (1) to (5), wherein the 2 nd thermoplastic resin layer contains at least 1 selected from olefin resins, cycloolefin resins, acrylic resins, olefin-vinyl acetate resins, olefin ionomer resins, and polyester resins on at least the surface opposite to the molecular adhesive layer.

(7) A method for bonding an adherend (I) and an adherend (II) by using 2 bonding laminates, wherein the 2 bonding laminates are each independently the bonding laminate described in any one of (1) to (6), and the 1 st bonding laminate is represented by a laminate containing a molecular adhesive (M) in this order_A) The molecular adhesive layer (A-M), the 1 st thermoplastic resin layer (A-1) having a single-layer structure, and the 2 nd thermoplastic resin layer (A-2) having a single-layer structure or a multilayer structure, and the 2 nd laminate for bonding is represented by containing the molecular adhesive (M) in this order_B) In the case of the laminate (B) for bonding comprising the molecular adhesive layer (B-M), the 1 st thermoplastic resin layer (B-1) having a single-layer structure, and the 2 nd thermoplastic resin layer (B-2) having a single-layer structure or a multilayer structure, any one step group selected from the group consisting of the following steps (L1) to (L3), the group consisting of the steps (M1) to (M3), and the group consisting of the steps (N1) and (N2) is carried out,

step (L1): a step of bonding the molecular adhesive layer (A-M) of the bonding laminate (A) to the adherend (I)

Step (L2): a step of bonding the molecular adhesive layer (B-M) of the bonding laminate (B) to the adherend (II)

Step (L3): a step of thermally welding the 2 nd thermoplastic resin layer (A-2) of the laminate obtained in the step (L1) and the 2 nd thermoplastic resin layer (B-2) of the laminate obtained in the step (L2)

Step (M1): a step of thermally welding the 2 nd thermoplastic resin layer (A-2) of the laminate (A) for bonding and the 2 nd thermoplastic resin layer (B-2) of the laminate (B) for bonding

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

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

Step (N1): a step of sequentially stacking the adherend (I), the laminate for joining (A), the laminate for joining (B), and the adherend (II) in this order with the 2 nd thermoplastic resin layer (A-2) of the laminate for joining (A) and the 2 nd thermoplastic resin layer (B-2) of the laminate for joining (B) disposed so as to face each other

Step (N2): and (c) heating the product obtained in the step (N1) to simultaneously perform the steps of bonding the molecular adhesive layer (a-M) to the adherend (I), bonding the molecular adhesive layer (B-M) to the adherend (II), and thermally bonding the 2 nd thermoplastic resin layer (a-2) to the 2 nd thermoplastic resin layer (B-2).

(8) The method for bonding an adherend (I) and an adherend (II) according to (7), which is a method for bonding an adherend (I) and an adherend (II) by performing the steps comprising steps (L1) to (L3) described above, wherein,

the temperature at which the molecular adhesive layers (A-M) of the bonding laminate (A) are bonded to the adherend (I) in the step (L1) is T_L1And (L2) bonding the molecular adhesive layer (B-M) of the bonding laminate (B) to the adherend (II)Temperature of T_L2And the step (L3) wherein the temperature at which the 2 nd thermoplastic resin layer (A-2) and the 2 nd thermoplastic resin layer (B-2) are heat-welded is T_L3The heat-sealable temperature of the 1 st thermoplastic resin layer (A-1) of the laminate (A) for joining is T_h1AAnd the heat-sealable temperature of the 2 nd thermoplastic resin layer (A-2) is T_h2AThe heat-sealable temperature of the 1 st thermoplastic resin layer (B-1) of the laminate (B) for joining is T_h1BAnd the heat-sealable temperature of the 2 nd thermoplastic resin layer (B-2) is T_h2BWhen the compound satisfies both the following formulae (E-1) and (E-2), and at least one of the following formulae (E-3) and (E-4),

[ number 1]

(9) The method for bonding an adherend (I) and an adherend (II) according to (7), which is a method for bonding an adherend (I) and an adherend (II) by carrying out the step group comprising the steps (N1) and (N2) described above, wherein the heat-sealable temperature at the 1 st thermoplastic resin layer (A-1) of the laminate (A) for bonding is T_h1AAnd the heat-sealable temperature of the 2 nd thermoplastic resin layer (A-2) is T_h2AThe heat-sealable temperature of the 1 st thermoplastic resin layer (B-1) of the laminate (B) for joining is T_h1BAnd the heat-sealable temperature of the 2 nd thermoplastic resin layer (B-2) is T_h2BAnd the temperature in the heat welding in the step (N2) is T_N2When satisfying at least one of the following formulas (E-5) and (E-6),

[ number 2]

(10) A method for producing a bonded structure having a layer structure of an adherend (I)/a layer from a bonding laminate (A) and a bonding laminate (B)/an adherend (II), the method being characterized by bonding the adherend (I) and the adherend (II) by using any one of the methods (7) to (9).

(11) The method for producing a joined structure according to item (10), wherein the adherend (I) and the adherend (II) each independently contain at least 1 selected from the group consisting of a metal, an inorganic substance, and a thermosetting resin at least on the surface to be bonded.

In the present invention, the molecular binder means a compound having 2 or more reactive groups.

The "molecular adhesive-containing layer" of the "molecular adhesive-containing layer" means "a compound (for example, a compound in which a structure of a reactive group is changed by a reaction) containing a molecular adhesive and/or a molecule-derived adhesive".

The "1 st thermoplastic resin layer contains a thermoplastic resin having a reactive partial structure (Z γ)" means "containing a thermoplastic resin having a reactive partial structure (Z γ) and/or a resin derived from the thermoplastic resin (for example, a resin in which the structure of the reactive partial structure (Z γ) is changed by a reaction)".

The phrase "the molecular adhesive layer and the 2 nd thermoplastic resin layer constitute the outermost layers in use" means that each layer is the outermost layer when the molecular adhesive layer and the adherend are bonded or the 2 nd thermoplastic resin layers are thermally welded to each other. Therefore, the joining laminate may have a protective sheet or the like as the outermost layer until the use after the production of the joining laminate.

The "heat-sealable temperature" of the thermoplastic resin layer is a temperature required for heat-sealing in order to achieve sufficient heat-sealing strength, and specifically, the heat-sealable temperature can be determined by the method described in the examples.

The "temperature at the time of bonding the molecular adhesive layer to the adherend" and the "temperature at the time of thermally bonding the thermoplastic resin layer to the thermoplastic resin layer" refer to the surface temperature of the pressure-bonded member of the apparatus in the case of using a hot press or the like.

In this specification, the unit of temperature is "° c".

Effects of the invention

According to the present invention, there are provided a laminate for bonding having a molecular adhesive layer and a thermoplastic resin layer, which can be subjected to a thermal fusion bonding step without adversely affecting the molecular adhesive layer, a method for bonding 2 adherends using the laminate for bonding, and a method for producing a bonded structure.

Drawings

FIG. 1: the present invention is a laminate for bonding, which is produced by the above method.

FIG. 2: is a schematic diagram showing a step group including steps (L1) to (L3).

FIG. 3: is a schematic diagram showing a step group including steps (M1) to (M3).

FIG. 4: is a schematic diagram showing a step group including the steps (N1) and (N2).

Detailed Description

The present invention will be described in detail below in terms of 1) a laminate for bonding, 2) a method for bonding 2 adherends, and 3) a method for producing a bonded structure.

1) Laminate for bonding

The laminate for bonding of the present invention is a laminate for bonding comprising a molecular adhesive layer containing a molecular adhesive (M), a1 st thermoplastic resin layer having a single-layer structure, and a 2 nd thermoplastic resin layer having a single-layer structure or a multilayer structure in this order, wherein the molecular adhesive layer and the 2 nd thermoplastic resin layer each constitute the outermost layer in use, wherein the molecular adhesive (M) is a compound having at least 1 reactive group (Z alpha) selected from the group consisting of an amino group, an azido group, a mercapto group, an isocyanate group, a ureido group, and an epoxy group, and at least 1 reactive group (Z beta) selected from the group consisting of a silanol group and a group which generates a silanol group by a hydrolysis reaction, and the 1 st thermoplastic resin layer contains a thermoplastic resin (P) on at least the surface on the side in contact with the molecular adhesive layer₁) The thermoplastic resin (P)₁) Having a reactive partial structure (Z gamma) capable of forming a chemical bond with the reactive group (Z alpha) of the molecular adhesive (M) in the second step1 Heat-sealable temperature of thermoplastic resin layer of T_h1The heat-sealable temperature of the 2 nd thermoplastic resin layer is T_h2When, T_h1＞T_h2。

[ molecular adhesive layer ]

The molecular adhesive layer is a layer directly adjacent to the 1 st thermoplastic resin layer.

The molecular adhesive layer is a layer constituting one of the outermost layers when the bonding laminate is used.

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

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

The molecular binder (M) is a compound having at least 1 reactive group (Z α) selected from an amino group, an azido group, a mercapto group, an isocyanate group, a ureido group and an epoxy group, and at least 1 reactive group (Z β) selected from a silanol group and a group which generates a silanol group by a hydrolysis reaction. The "amino group" of the reactive group (Z α) includes: unsubstituted amino, mono-substituted amino, di-substituted amino, primary ammonium, secondary ammonium, tertiary ammonium, quaternary ammonium.

The reactive group (Z alpha) in the molecular adhesive (M) is capable of reacting with the thermoplastic resin (P) in the 1 st thermoplastic resin layer₁) The reactive moiety structure (Z γ) of (a) forms a chemical bond.

It is considered that the molecular adhesive (M) is chemically fixed to the surface of the 1 st thermoplastic resin layer by the chemical bond in the joining laminate. Examples of the chemical bond at this time include a covalent bond, a hydrogen bond, an ionic bond, an intermolecular force, and the like, and a covalent bond is preferable.

When the laminate for bonding is bonded to an adherend, the reactive group (Z β) in the molecular adhesive (M) is mainly used when a chemical bond is formed with the adherend. Therefore, the laminate for bonding is preferably used for an adherend having a group highly reactive with these groups on the surface.

Examples of the group which forms a silanol group by hydrolysis include groups having Si-X¹Groups of the partial structures shown. As X¹Examples thereof include alkoxy groups having 1 to 10 carbon atoms such as methoxy, ethoxy, n-propoxy and isopropoxy; halogen atoms such as fluorine atom, chlorine atom, and bromine atom; and the like.

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

[ solution 2]

R¹Represents a reactive group (Z alpha) or a 1-valent group having 1 or more reactive groups (Z alpha) (wherein the reactive group (Z alpha) itself is excluded), G represents a 2-valent organic group, X represents a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom, and Y represents a hydrocarbon group having 1 to 20 carbon atoms. a represents an integer of 1 to 3.

As R¹The 1-valent group having 1 or more reactive groups (Z α) of (A) includes, for example, groups represented by the following formulae (2) to (4).

[ solution 3]

In formulae (2) to (4), a represents a bond to G.

R²Represents a C1-10 2-valent hydrocarbon group, preferably a C2-valent hydrocarbon group having 2-6 carbon atoms. As R²Examples of the 2-valent hydrocarbon group of (a) include alkylene groups such as ethylene, trimethylene and propylene; arylene groups such as o-phenylene, m-phenylene, and p-phenylene.

R³、R⁴Each independently represents a hydrogen atom or a carbon atom of 1 to 20The hydrocarbon group is preferably a hydrocarbon group having 1 to 10 hydrogen atoms or carbon atoms.

As R³、R⁴Examples of the hydrocarbyl group of (b) include an alkyl group such as 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 tert-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, and an n-decyl group; alkenyl groups such as vinyl, 1-propenyl, 2-propenyl, isopropenyl, 3-butenyl, 4-pentenyl and 5-hexenyl; alkynyl groups such as ethynyl, propargyl, and butynyl; aryl groups such as phenyl, 1-naphthyl and 2-naphthyl; and the like.

Z represents a single bond, or-N (R)⁷) -the 2-valent radical represented. R⁷Represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. As R⁷The hydrocarbyl group of (A) may be mentioned as R³、R⁴The same hydrocarbon groups are shown.

R⁵、R⁶Each independently represents a reactive group (Z α) or a group represented by the above formula (2) (in this case, in formula (2), a bond to a carbon atom constituting an aromatic ring).

Examples of the organic group having a valence of 2 in G include a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynylene group having 2 to 20 carbon atoms, and a substituted or unsubstituted arylene group having 6 to 20 carbon atoms; and the like.

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

Examples of the alkenylene group having 2 to 20 carbon atoms for 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 of G include an ethynylene group, an propynyl group and the like.

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, a1, 5-naphthylene group and the like.

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

Examples of the substituent for the arylene group include a cyano group; a nitro group; halogen atoms such as fluorine atom, chlorine atom, and bromine atom; alkyl groups such as methyl and ethyl; alkoxy groups such as methoxy and ethoxy; alkylthio groups such as methylthio and ethylthio; and the like.

In the alkylene group, alkenylene group, alkynylene group, arylene group, and the like, these substituents may be bonded at arbitrary positions. The alkylene group and the like may have a plurality of substituents bonded thereto, which may be the same or different.

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

Examples of the halogen atom of X include a fluorine atom, a chlorine atom, a bromine atom and the like.

Examples of the hydrocarbon group having 1 to 20 carbon atoms of Y include the group R³、R⁴The same hydrocarbon groups as shown.

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

R such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyldiethoxymethylsilane, [ 3- (N, N-dimethylamino) propyl ] trimethoxysilane, [ 3- (phenylamino) propyl ] trimethoxysilane, trimethyl [ 3- (triethoxysilyl) propyl ] ammonium chloride, trimethyl [ 3- (trimethoxysilyl) propyl ] ammonium chloride and the like¹A molecular binder that is an amino group;

r such as (11-azidoundecyl) trimethoxysilane or (11-azidoundecyl) triethoxysilane¹A molecular binder that is an azide group;

3-mercaptopropyltrimethoxysilane, 3-mercaptosilaneR such as propyltriethoxysilane, 3-mercaptopropyldimethoxymethylsilane, etc¹A molecular binder which is a mercapto group;

r such as 3- (trimethoxysilyl) propyl isocyanate, 3- (triethoxysilyl) propyl isocyanate and the like¹A molecular binder which is an isocyanate group;

r such as 3-ureidopropyltrimethoxysilane and 3-ureidopropyltriethoxysilane¹A molecular binder that is urea;

r such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane¹A molecular binder that is an epoxy group;

r is selected from the group consisting of 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (2-aminoethylamino) propyltriethoxysilane, 3- (2-aminoethylamino) propyldimethoxymethylsilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, and compounds represented by the following formulae (5) to (13)¹A molecular binder which is a 1-valent group having 1 or more reactive groups (Z α);

[ solution 4]

The molecular binder (M) may be used alone in 1 kind or in combination of 2 or more kinds.

Of these compounds, the compound represented by the formula (1) is preferably R¹The compound having a group represented by the formula (4) is more preferably a compound represented by the formulae (5) to (13), and still more preferably a compound represented by the formulae (5) to (10).

These compounds are described in R¹Having a triazine ring. The molecular adhesive (M) having a triazine ring tends to be fixed more efficiently to the 1 st thermoplastic resin layer.

As the molecular binder (M), silane coupling agents known as silane coupling agents can be usedThe compound of (1). Furthermore, R¹The compound which is a group represented by formula (4) can be synthesized according to the methods described in WO2012/046651, WO2012/043631, WO2013/186941, and the like.

The molecular adhesive layer may contain a component other than the molecular adhesive (M). Examples of the component other than the molecular binder (M) include a catalyst and the like.

The catalyst may be suitably selected and used depending on the kind of the reactive group (Z α).

Since the adhesive strength of the molecular adhesive layer decreases if a component not involved in adhesion is contained, the content of the molecular adhesive (M) in the molecular adhesive layer is preferably 50 mass% or more, more preferably 70 mass% or more and 100 mass% or less, further preferably 90 mass% or more and 100 mass% or less, and particularly preferably 100 mass% based on the entire molecular adhesive layer.

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

[ 1 st thermoplastic resin layer ]

The 1 st thermoplastic resin layer is a layer adjacent to the molecular adhesive layer and plays a role of fixing the molecular adhesive (M).

The 1 st thermoplastic resin layer has a single-layer structure.

The 1 st thermoplastic resin layer may be uniform in composition or may be non-uniform in composition. For example, the 1 st thermoplastic resin layer may contain a large amount of a specific component in the vicinity of the surface of the layer, and the composition in the vicinity of the surface of the layer may be different from the composition in the interior of the layer.

The 1 st thermoplastic resin layer contains a thermoplastic resin (P) at least on the surface thereof in contact with the molecular adhesive layer₁) The thermoplastic resin (P)₁) Has a reactive partial structure (Z gamma) capable of forming a chemical bond with the reactive group (Z alpha) of the molecular binder (M). That is, the 1 st thermoplastic resin layer in the laminate for joining contains a thermoplastic resinResin (P)₁) (those in which the reactive partial structure (Z. gamma.) remains) with the thermoplastic resin (P)₁) At least one of the reaction products (those in which the reactive moiety structure (Z γ) is changed) of (a).

The "surface in contact with the molecular adhesive layer contains a thermoplastic resin (P)₁) "means that the thermoplastic resin (P) is present in the stage before the molecular adhesive layer is formed₁) Exposed on the surface of the 1 st thermoplastic resin layer.

By passing the thermoplastic resin (P) in a stage before forming the molecular adhesive layer₁) Thermoplastic resin (P) exposed on the surface of the No. 1 thermoplastic resin layer₁) The reactive partial structure (Z γ) of (A) can efficiently react with the reactive group (Z α) of the molecular binder (M).

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

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

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

Examples of the cycloolefin include cyclopentene, cyclooctene, norbornene monomers, and the like.

Examples of the α -olefin include ethylene and propylene.

Examples of the acrylic resin include homopolymers of (meth) acrylic monomers, copolymers of (meth) acrylic monomers, and copolymers of (meth) acrylic monomers and monomers copolymerizable with (meth) acrylic monomers.

Examples of the (meth) acrylic monomer include (meth) acrylic esters such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate; (meth) acrylic acid; and the like.

Examples of the monomer copolymerizable with the (meth) acrylic monomer include ethylene; aromatic vinyl monomers such as styrene, alpha-methylstyrene, chlorostyrene, and the like; cyano group-containing ethylenically unsaturated monomers such as acrylonitrile and methacrylonitrile; (meth) acrylamide monomers such as (meth) acrylamide, N-methylol (meth) acrylamide, and N-butoxymethyl (meth) acrylamide; and the like.

In the present specification, "(meth) acrylic acid" means "acrylic acid or methacrylic acid". The same applies to "(meth) acrylate", "(meth) acrylic acid", and "(meth) acrylate", and the like.

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

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

Examples of the olefin monomer include ethylene and propylene.

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

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

Examples of the metal ion include a sodium (I) ion, a potassium (I) ion, a lithium (I) ion, a calcium (II) ion, a magnesium (II) ion, a zinc (II) ion, a copper (I) ion, a copper (II) ion, a cobalt (III) ion, a nickel (II) ion, a manganese (II) ion, and an aluminum (III) ion.

Examples of the polyester resin include resins obtained by polycondensation reaction of a polycarboxylic acid and a polyhydric alcohol.

Examples of the polycarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanoic acid, 1, 4-cyclohexanedicarboxylic acid, 1, 4-naphthalenedicarboxylic acid, 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, 3-methyl-1, 5-pentanediol, 1, 2-hexanediol, 1, 6-hexanediol, 1, 9-nonanediol, 1, 4-cyclohexanedimethanol, diethylene glycol, polyethylene glycol, polypropylene glycol, polybutylene glycol, trimethylolpropane, glycerol, and the like.

Among the polyester resins, amorphous polyester resins are more preferable. The amorphous polyester resin means 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 ethylene glycol-modified polyethylene terephthalate (PETG), ethylene glycol-modified poly (1, 4-cyclohexanedimethanol terephthalate) (PCTG), acid-modified poly (1, 4-cyclohexanedimethanol terephthalate) (PCTA), and the like.

Thermoplastic resin (P)₁) The number of the compounds may be 1 or 2 or more.

Thermoplastic resin (P)₁) Has a reactive partial structure (Z gamma) capable of forming a chemical bond with the reactive group (Z alpha) of the molecular binder (M).

By a thermoplastic resin (P)₁) Having a reactive partial structure (Z γ), the molecular adhesive (M) can be immobilized with good efficiency.

As a thermoplastic resin (P)₁) Examples of the reactive partial structure (Z.gamma.) include a hydroxyl group, a carboxyl group, an aldehyde group, an amino group, a carbon-carbon single bond, a carbon-carbon double bond, a carbon-hydrogen single bond and the like. As described later, they can be appropriately selected depending on the reactive group (Z α) in the molecular binder (M).

In the thermoplasticSex resin (P)₁) Is a thermoplastic resin (P) having a functional group such as a hydroxyl group, a carboxyl group, an aldehyde group, an amino group or the like as a reactive partial structure (Z.gamma.₁') case of the thermoplastic resin (P)₁') can be formed by a known method.

For example, by using a monomer having a functional group such as a hydroxyl group, a carboxyl group, an aldehyde group, an amino group, etc., in the polymerization reaction, a thermoplastic resin (P γ ') having a reactive partial structure (Z γ') can be produced₁'). Further, by subjecting a polymer obtained by polymerization reaction without using such a monomer to modification treatment such as maleic anhydride modification, a thermoplastic resin (P γ ') having a reactive partial structure (Z γ') can be produced₁’）。

By subjecting the thermoplastic resin (P) obtained by these methods to₁') can be used as a molding material to efficiently form the 1 st thermoplastic resin layer.

Further, no thermoplastic resin (P) is formed₁') and then subjecting the thermoplastic resin layer to surface treatment, hydroxyl groups and carboxyl groups may be formed on the surface of the thermoplastic resin layer. That is, by performing the surface treatment, the thermoplastic resin layer becomes to satisfy the requirements required for the 1 st thermoplastic resin layer.

The surface treatment is not particularly limited as long as hydroxyl groups and carboxyl groups are mainly formed. Examples of the surface treatment include corona treatment, plasma treatment, ultraviolet irradiation treatment, electron beam irradiation treatment, ozone treatment, excimer ultraviolet treatment, acid treatment, alkali treatment, and the like.

These surface treatments may be carried out according to known methods.

The 1 st thermoplastic resin layer may further contain a thermoplastic resin (P) as long as adhesion to the molecular adhesive layer is not inhibited₁) Other components.

As a thermoplastic resin (P)₁) Examples of the other components include an ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent, a lubricant (スリップ agent), an antiblocking agent, and a colorant.

Their content may be determined as appropriate depending on the purpose.

Thermoplastic resin (P) in the No. 1 thermoplastic resin layer₁) The content of (B) is usually 50 to 100% by mass, preferably 80 to 100% by mass.

The thickness of the 1 st thermoplastic resin layer is usually 5 to 150 μm, preferably 10 to 120 μm, and more preferably 15 to 80 μm.

When the thickness of the 1 st thermoplastic resin layer is 5 μm or more, the deterioration of the performance of the molecular adhesive layer due to heating in the heat-fusion step can be sufficiently suppressed. Further, by setting the thickness of the 1 st thermoplastic resin layer to 80 μm or less, the joint portion (between the adherends) can be thinned.

The heat-sealable temperature of the No. 1 thermoplastic resin layer is usually 100 to 200 ℃, preferably 120 to 180 ℃.

The heat-sealable temperature of the 1 st thermoplastic resin layer is 100 ℃ or higher, whereby the shape of the 1 st thermoplastic resin layer can be suppressed from being changed during heat-sealing. Further, the heat-sealable temperature of the 1 st thermoplastic resin layer is 200 ℃ or lower, whereby the influence on the molecular adhesive layer at the time of heat-sealing can be suppressed.

The heat-sealable temperature of the 1 st thermoplastic resin layer is a property influenced by the kind of the thermoplastic resin, the molecular weight of the thermoplastic resin, the content of the thermoplastic resin, the kind of the additive, the content of the additive, the crystallinity of the 1 st thermoplastic resin layer, the density of the 1 st thermoplastic resin layer, and the like.

Therefore, for example, after the thermoplastic resin used is determined, by adjusting the kind and amount of the additive, the 1 st thermoplastic resin layer having the target heat-sealable temperature can be formed.

[ 2 nd thermoplastic resin layer ]

The 2 nd thermoplastic resin layer is a layer adjacent to the 1 st thermoplastic resin layer and constitutes one of the outermost layers when the laminate for bonding is used. An adhesive layer may be present between the 1 st thermoplastic resin layer and the 2 nd thermoplastic resin layer.

As described later, the 2 nd thermoplastic resin layer is used for thermal welding with the 2 nd thermoplastic resin layer of the other joining laminate.

The 2 nd thermoplastic resin layer may have a single-layer structure or a multi-layer structure. The composition of the 2 nd thermoplastic resin layer in the case where the 2 nd thermoplastic resin layer has a single-layer structure and the composition of the 2 nd thermoplastic resin layer in the case where the 2 nd thermoplastic resin layer has a multilayer structure may be uniform or nonuniform. For example, the layers may contain a large amount of a particular composition near the surface of the layer, which may be different from the composition of the central portion of the layer.

The 2 nd thermoplastic resin layer preferably contains a thermoplastic resin that can be melted at a relatively low temperature and cured in a short time (hereinafter, sometimes referred to as "thermoplastic resin (P)") at least on the surface opposite to the 1 st thermoplastic resin layer₂）”）。

By containing a thermoplastic resin (P) on the surface opposite to the 1 st thermoplastic resin layer₂) This step can be performed more efficiently when the thermoplastic resin layer of the laminate for other bonding is thermally welded.

"comprises a thermoplastic resin (P) on the surface opposite to the 1 st thermoplastic resin layer₂) "means a thermoplastic resin (P)₂) Exposed on the surface opposite to the 1 st thermoplastic resin layer.

As a thermoplastic resin (P)₂) Examples thereof include olefin resins, cycloolefin resins, acrylic resins, olefin-vinyl acetate resins, olefin ionomer resins, and polyester resins.

Specific examples of the thermoplastic resin include a thermoplastic resin (P)₁) But the same resin is shown.

Thermoplastic resin (P)₂) Can be used alone, or in combination of 2 or more.

The 2 nd thermoplastic resin layer may further contain a thermoplastic resin (P) as long as the heat-fusion property is not hindered₂) Other components.

As a thermoplastic resin (P)₂) Examples of the other components include an ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent, and a lubricant: (A)スリップ agents), anti-caking agents, colorants, and the like.

Their content may be determined as appropriate depending on the purpose.

When the 2 nd thermoplastic resin layer has a single-layer structure, examples of the 2 nd thermoplastic resin layer include: containing a thermoplastic resin (P)₂) At least the surface opposite to the 1 st thermoplastic resin layer contains a thermoplastic resin (P)₂) Non-uniform layer of (a).

Thermoplastic resin (P) in 2 nd thermoplastic resin layer having single-layer structure₂) The content of (B) is usually 50 to 100% by mass, preferably 80 to 100% by mass.

The thickness of the 2 nd thermoplastic resin layer having a single-layer structure is usually 5 to 150 μm, preferably 10 to 120 μm, and more preferably 15 to 80 μm.

The 2 nd thermoplastic resin layer having a single-layer structure has a thickness of 5 μm or more, and thus can be sufficiently heat-welded. Further, by setting the thickness of the 2 nd thermoplastic resin layer to 150 μm or less, the joint portion (between the adherends) can be made thin.

When the 2 nd thermoplastic resin layer has a multilayer structure, examples of the 2 nd thermoplastic resin layer include: the outermost layer opposite to the 1 st thermoplastic resin layer (the outermost layer not in contact with the 1 st thermoplastic resin layer out of the 2 nd outermost layers of the 2 nd thermoplastic resin layer having a multilayer structure) contains a thermoplastic resin (P) on the surface opposite to the 1 st thermoplastic resin layer₂) The layers of the multilayer structure of (1).

The thermoplastic resin (P) contained in the outermost layer of the 2 nd thermoplastic resin layer having a multilayer structure on the opposite side of the 1 st thermoplastic resin layer₂) The content of (b) is usually 50 to 100% by mass, preferably 80 to 100% by mass based on the entire outermost layer.

The thickness of the entire 2 nd thermoplastic resin layer having a multilayer structure is usually 3 to 150 μm, preferably 10 to 120 μm, and more preferably 15 to 80 μm.

The 2 nd thermoplastic resin layer having a multilayer structure has a thickness of 3 μm or more as a whole, and thus can be sufficiently heat-welded. Further, by setting the thickness of the 2 nd thermoplastic resin layer to 150 μm or less, the joint portion (between the adherends) can be made thin.

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

The heat-sealable temperature of the 2 nd thermoplastic resin layer is usually 50 to 180 ℃, preferably 70 to 150 ℃.

When the heat-sealable temperature of the second thermoplastic resin layer 2 is 50 ℃ or higher, the workability at room temperature becomes good. Further, when the heat-sealable temperature of the 2 nd thermoplastic resin layer is 180 ℃ or lower, the layers of the 2 nd thermoplastic resin layers can be firmly bonded to each other and the 2 adherends can be more firmly bonded to each other when the laminate for bonding of the present invention is used.

The heat-sealable temperature of the 2 nd thermoplastic resin layer can be adjusted by the same method as the method for adjusting the heat-sealable temperature of the 1 st thermoplastic resin layer.

When the 2 nd thermoplastic resin layer has a multilayer structure, the heat-sealable temperature of the 2 nd thermoplastic resin layer is the heat-sealable temperature of the outermost layer on the opposite side of the 1 st thermoplastic resin layer.

[ laminate for joining ]

The laminate for bonding can be produced by forming a molecular adhesive layer directly on the 1 st thermoplastic resin layer of a laminate (hereinafter, sometimes referred to as "laminate (η)") composed of the 1 st thermoplastic resin layer and the 2 nd thermoplastic resin layer.

For example, as shown in fig. 1, a laminate (5) for bonding is obtained by directly forming a molecular adhesive layer (4) on the 1 st thermoplastic resin layer (1) of a laminate (3) composed of the 1 st thermoplastic resin layer (1) and the 2 nd thermoplastic resin layer (2).

As described above, in the laminate (3), the 1 st thermoplastic resin layer (1) contains the thermoplastic resin (P) on the surface (6) on the side in contact with the molecular adhesive layer (4)₁). Further, the 2 nd thermoplastic resin layer (2) of the laminate (3) is preferably thermoplastic with the 1 st thermoplastic resin layerThe surface (7) of the opposite side of the sex resin layer (1) comprises thermoplastic resin (P)₂）。

The method for producing the laminate (η) is not particularly limited.

For example, the thermoplastic resin (P) may be contained₁) The pellets of (A) and the thermoplastic resin (P) -containing resin₂) The pellets of (a) are each melted, they are simultaneously extruded from a multilayer die, and the resulting coextruded multilayer film is used as a laminate (η).

Further, a thermoplastic resin (P) may be contained₁) And a resin film containing a thermoplastic resin (P)₂) The resin films of (3) are laminated, and the obtained multilayer film is used as a laminate (η).

Further, the thermoplastic resin (P) may be contained₁) Coating the No. 1 thermoplastic resin layer (resin film) with a thermoplastic resin (P)₂) The coating liquid of (2) or containing a thermoplastic resin (P) by drying the obtained coating film₂) Coating the second thermoplastic resin layer (resin film) containing the thermoplastic resin (P)₁) The coating liquid of (3) is dried to form a1 st thermoplastic resin layer, and the multilayer film obtained thereby is used as a laminate (η).

Among these, a coextruded multilayer film is preferably used as the laminate (η) because interlayer peeling between the 1 st thermoplastic resin layer and the 2 nd thermoplastic resin layer is less likely to occur.

In the present specification, the resin film in a state where no other layer is formed may be referred to as "1 st thermoplastic resin layer" or "2 nd thermoplastic resin layer".

In the production of the laminate (η), the composition of each layer may be determined so that the heat-sealable temperature of the 1 st thermoplastic resin layer is higher than the heat-sealable temperature of the 2 nd thermoplastic resin layer.

That is, the heat-sealable temperature of the joining laminate of the present invention in the 1 st thermoplastic resin layer is T_h1And the heat-sealable temperature of the 2 nd thermoplastic resin layer is T_h2When, T_h1＞T_h2。

As described later, when 2 adherends are joined using the joining laminate of the present invention, the heat-sealable temperature of the 1 st thermoplastic resin layer is higher than the heat-sealable temperature of the 2 nd thermoplastic resin layer, whereby the heat-sealing step can be performed without adversely affecting the molecular adhesive layer.

The reactive group (Z α) of the molecular adhesive (M) used for forming the molecular adhesive layer and the thermoplastic resin (P) in the 1 st thermoplastic resin layer may be considered₁) The combination of the reactive partial structures (Z γ) is appropriately selected.

Among them, the reactive group (Z α) and the reactive partial structure (Z γ) preferably satisfy the following requirement (Q1).

Element (Q1):

the reactive group (Z alpha) of the molecular adhesive (M) is at least 1 selected from the group consisting of an amino group, a mercapto group, an isocyanate group, a urea group and an epoxy group, and the thermoplastic resin (P)₁) Having a reactive partial structure (Z gamma) of at least 1 selected from the group consisting of a hydroxyl group, a carboxyl group, an aldehyde group and an amino group, or,

the reactive group (Z alpha) of the molecular adhesive (M) is an azide group, and the thermoplastic resin (P)₁) Has a reactive partial structure (Z gamma) of at least 1 kind selected from the group consisting of a carbon-carbon single bond, a carbon-carbon double bond and a carbon-hydrogen single bond.

In the laminate for bonding of the present invention, it is considered that the reactive group (Z α) of the molecular adhesive (M) and the thermoplastic resin (P) are bonded to each other via the reactive group (Z α)₁) The reactive partial structure (Z γ) of (1) forms a chemical bond, and the molecular binder (M) is fixed to the first thermoplastic resin layer.

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

When the reactive group (Z α) is at least 1 selected from the group consisting of an amino group, a mercapto group, an isocyanate group, a urea group and an epoxy group, as a preferable combination of the reactive group (Z α) and the reactive partial structure (Z γ) [ reactive group (Z α)/reactive partial structure (Z γ) ], there can be mentioned: (amino/hydroxyl), (amino/carboxyl), (isocyanate/hydroxyl), (isocyanate/carboxyl), (hydroxyl/carboxyl), and the like.

When the reactive group (Z α) is an azide group, the azide group is activated by irradiation with light as described later. In this case, the nitrene as a reaction intermediate can react with a carbon-carbon single bond, a carbon-carbon double bond, or a carbon-hydrogen single bond, and thus is used as a thermoplastic resin (P)₁) The reactive partial structure (Z γ) of (2) is preferably at least 1 selected from the group consisting of a carbon-carbon single bond, a carbon-carbon double bond and a carbon-hydrogen single bond.

The thermoplastic resin generally 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 thermoplastic resin (P)₁) The kind of (b) is not particularly limited.

The method for forming the molecular adhesive layer is not particularly limited. For example, a molecular adhesive layer can be formed by preparing a molecular adhesive solution containing the molecular adhesive (M), applying the solution to the 1 st thermoplastic resin layer, and then performing a drying process of the obtained coating film and a process of fixing the molecular adhesive (M) to the 1 st thermoplastic resin layer.

The solvent used in preparing the molecular binder solution is not particularly limited. As the solvent, an alcohol-based solvent such as methanol, ethanol, isopropanol, ethylene glycol, diethylene glycol, or the like; ketone solvents such as acetone and methyl ethyl ketone; ester solvents such as ethyl acetate and butyl acetate; halogen-containing compound solvents such as methylene chloride; aliphatic hydrocarbon solvents such as butane and hexane; ether solvents such as tetrahydrofuran and butyl ether; aromatic solvents such as benzene and toluene; amide solvents such as N, N-dimethylformamide and N-methylpyrrolidone; water; and the like.

These can be used alone in 1, or in combination of 2 or more.

The concentration of the molecular binder (M) in the molecular binder solution is not particularly limited. The concentration is preferably 0.005 to 1.000mol/L, more preferably 0.050 to 0.500 mol/L. By setting the concentration of the molecular adhesive (M) to 0.005mol/L or more, the molecular adhesive layer can be efficiently formed on the 1 st thermoplastic resin layer. Further, by setting the molecular binder solution to 1.000mol/L or less, an undesired reaction of the molecular binder solution can be suppressed, and the solution stability is excellent.

The method of applying the molecular binder 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 coating, blade coating, dip coating, curtain coating, die coating, and gravure coating, and the bar coating method and the gravure coating method are preferable.

After the molecular binder solution is applied, it is usually necessary to dry the resulting coating film by natural drying or by introducing it into a drying mechanism. Among them, the drying treatment by the charging drying means is preferable from the viewpoint of improving productivity. Examples of the drying mechanism include a batch-type drying mechanism such as an air oven, and a continuous-type drying mechanism such as a heat roller/hot air passing mechanism (a device in which a subject to be dried moves and passes through an open-type drying furnace while being heated by being subjected to air blowing), and the like. Note that, as a device which can be used as a part of the drying means, for example, a heat medium circulation type heater such as high-frequency heating and an oil heater, or a heater itself such as a far-infrared heater can be used as the drying means. Among them, the hot air passing mechanism is preferable from the viewpoint of improving productivity.

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

In forming the molecular adhesive layer, a process of fixing the molecular adhesive (M) to the 1 st thermoplastic resin layer (hereinafter, may be referred to as a fixing process) is generally performed. The fixing treatment can be appropriately selected depending on the characteristics of the reactive group (Z α) of the molecular binder (M). In general, since chemical bonds are generated by applying the molecular adhesive (M) to the 1 st thermoplastic resin layer and the generation of chemical bonds is promoted by heating, it is preferable to perform a heating treatment from the viewpoint of improving productivity. The heating temperature is usually 40 to 250 ℃, preferably 60 to 200 ℃, and more preferably 80 to 120 ℃. The heating time is usually 1 second to 120 minutes, preferably 1 to 60 minutes, and more preferably 1 to 30 minutes.

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

When the reactive group (Z α) has photoreactivity like an azide group, a light irradiation treatment is performed as an immobilization treatment. As the light to be irradiated, ultraviolet rays are generally used. In this case, the fixation treatment after the drying treatment is preferable from the viewpoint of improving the reactivity of the reactive group (Z α) and the reactive group (Z γ).

The ultraviolet irradiation can be performed by an ultraviolet irradiation apparatus using a light source such as a mercury lamp, a metal halide lamp, an ultraviolet LED, or an electrodeless lamp.

The treatment conditions for the light irradiation treatment are not particularly limited as long as the target photoreaction can be performed.

In 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 2 adherends

The method of bonding 2 adherends of the present invention is a method of bonding an adherend (I) and an adherend (II), which is a method of bonding an adherend (I) and an adherend (II) using 2 bonding laminates, and is characterized in that the 2 bonding laminates are each independently a bonding laminate of the present invention, and the 1 st bonding laminate is represented as having a molecular adhesive (M) contained therein in this order_A) The molecular adhesive layer (A-M), the 1 st thermoplastic resin layer (A-1) having a single-layer structure, and the 2 nd thermoplastic resin layer (A-2) having a single-layer structure or a multilayer structure, and the 2 nd laminate for bonding is represented by containing the molecular adhesive (M) in this order_B) A molecular adhesive layer (B-M), a1 st thermoplastic resin layer (B-1) having a single-layer structure, and a thermoplastic resin composition having a single-layer structure orIn the laminate (B) for joining the 2 nd thermoplastic resin layer (B-2) having a multilayer structure,

the method comprises performing any one step selected from the group consisting of steps (L1) to (L3), steps (M1) to (M3), and steps (N1) and (N2),

Step (M2): a step of bonding the molecular adhesive layers (A-M) of the laminate obtained in the step (M1) to the adherend (I)

The laminate (A) for bonding comprises a molecular adhesive (M)_A) The molecular adhesive layer (A-M), the 1 st thermoplastic resin layer (A-1), and the 2 nd thermoplastic resin layer (A-2).

In the joining method of the present invention, the joining laminate (a) is used for bonding to an adherend (I).

The laminate (B) for bonding comprises a molecular adhesive (M)_B) The laminate (B) for bonding a molecular adhesive layer (B-M), a1 st thermoplastic resin layer (B-1), and a 2 nd thermoplastic resin layer (B-2).

In the joining method of the present invention, the joining 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.

When the 2 nd thermoplastic resin layer (A-2) of the laminate (A) for joining contains a thermoplastic resin (P) on the surface opposite to the 1 st thermoplastic resin layer (A-1)₂) (hereinafter, the thermoplastic resin (P) contained in the 2 nd thermoplastic resin layer (A-2) may be₂) Expressed as "thermoplastic resin (P)_2A) ") the 2 nd thermoplastic resin layer (B-2) of the laminate (B) for bonding comprises a thermoplastic resin (P) on the surface opposite to the 1 st thermoplastic resin layer (B-1)₂) (hereinafter, the thermoplastic resin (P) contained in the 2 nd thermoplastic resin layer (B-2) may be₂) Expressed as "thermoplastic resin (P)_2B) ") the thermoplastic resin (P) is preferred_2A) (the 2 nd thermoplastic resin layer (A-2) contains 2 or more thermoplastic resins (P)_2A) In the case of the most content) with the thermoplastic resin (P)_2B) (the 2 nd thermoplastic resin layer (B-2) contains 2 or more thermoplastic resins (P)_2B) The highest content) are the same. By a thermoplastic resin (P)_2A) With a thermoplastic resin (P)_2B) Similarly, 2 adherends can be more firmly joined.

Thermoplastic resin (P)_2A) (the 2 nd thermoplastic resin layer (A-2) contains 2 or more thermoplastic resins (P)_2A) When it is in contentMaximum) with a thermoplastic resin (P)_2B) (the 2 nd thermoplastic resin layer (B-2) contains 2 or more thermoplastic resins (P)_2B) The largest content in the case of the thermoplastic resin), when these thermoplastic resins are crystalline resins, it is preferable that the difference between their melting points is small. By using a combination of thermoplastic resins (P) having close melting points_2A) With a thermoplastic resin (P)_2B) The thermal welding can be performed more efficiently.

Thermoplastic resin (P)_2A) Melting point of (2) and thermoplastic resin (P)_2B) The difference in melting point of (A) is preferably 40 ℃ or less, more preferably 20 ℃ or less, and particularly preferably 0 ℃.

Thermoplastic resin (P)_2A) (the 2 nd thermoplastic resin layer (A-2) contains 2 or more thermoplastic resins (P)_2A) At the most content) with the thermoplastic resin (P)_2B) (the 2 nd thermoplastic resin layer (B-2) contains 2 or more thermoplastic resins (P)_2B) The highest content) are different, it is preferable that the interaction distance Ra of their hansen solubility parameters is small. Thermoplastic resins (P) having close interaction distances Ra by using Hansen solubility parameters in combination_2A) With a thermoplastic resin (P)_2B) The thermal welding can be performed more efficiently.

Thermoplastic resin (P)_2A) With a thermoplastic resin (P)_2B) The interaction distance Ra of the hansen solubility parameter of (a) 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 by the following formula.

[ number 3]

In the above formula, δ D_ARepresents a thermoplastic resin (P)_2A) Dispersion component of Hansen solubility parameter, delta D_BRepresents a thermoplastic resin (P)_2B) Dispersion component of Hansen solubility parameter, delta P_AIndicating heatPlastic resin (P)_2A) Polar component of the Hansen solubility parameter, δ P_BRepresents a thermoplastic resin (P)_2B) Polar component of the Hansen solubility parameter, δ H_ARepresents a thermoplastic resin (P)_2A) Hydrogen bond component of hansen solubility parameter, δ H_BRepresents a thermoplastic resin (P)_2B) Hydrogen bonding component of hansen solubility parameter.

In the bonding method of the present invention, the molecular adhesive layers (a-M) of the bonding laminate (a) are used for bonding to the adherend (I), and the molecular adhesive layers (B-M) of the bonding laminate (B) are used for bonding to the adherend (II).

The adhesion between the molecular adhesive layer (A-M) and the adherend (I), and the adhesion between the molecular adhesive layer (B-M) and the adherend (II) are generally achieved by the molecular adhesive (M)_A) Or (M)_B) The reactive group (Z β) in (b) reacts with a functional group in a compound constituting the adherend (I) or the adherend (II) to form a chemical bond.

Therefore, as the adherend (I) or the adherend (II), those having a reactive group with the reactive group (Z β) on the surface thereof are generally used.

Examples of such adherends include members having a metal-containing surface, members having an inorganic substance-containing surface, and members having a silicone resin-containing surface.

Examples of the metal include aluminum, chromium, manganese, iron, cobalt, nickel, copper, zinc, silver, and gold.

Examples of the inorganic substance include glass, inorganic oxides (excluding glass), and the like.

Surface treatment may be applied to these members. Members having hydroxyl groups, carboxyl groups, or the like formed by surface treatment are more suitable as adherends.

Further, by utilizing the surface treatment technique, a member whose surface contains a thermoplastic resin, a thermosetting resin can also be used as an 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, alkali treatment, and the like. These surface treatments can be carried out according to known methods.

Further, the surface of the adherend may be provided with a primer layer as needed.

[ Steps comprising Steps (L1) to (L3) ]

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

In step (L1), the molecular adhesive layer (a-M) (8) of the bonding laminate (a) (11) having the molecular adhesive layer (a-M) (8), the 1 st thermoplastic resin layer (a-1) (9), and the 2 nd thermoplastic resin layer (a-2) (10) is bonded to the adherend (I) (12), to obtain a laminate (13) [ fig. 2 (a) ].

The step (L1) can be performed using, for example, a hot press, an autoclave apparatus, a vacuum laminator, a three-dimensional vacuum thermoforming machine (TOM molding machine), a heating laminator, or the like.

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

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

The bonding temperature in the step (L1) is usually 40 to 200 ℃, preferably 50 to 170 ℃, and more preferably 60 to 140 ℃.

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

In step (L2), the molecular adhesive layer (B-M) (14) of the bonding laminate (B) (17) having the molecular adhesive layer (B-M) (14), the 1 st thermoplastic resin layer (B-1) (15), and the 2 nd thermoplastic resin layer (B-2) (16) is bonded to the adherend (II) (18), to obtain a laminate (19) [ fig. 2 (B) ].

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

In step (L3), the 2 nd thermoplastic resin layer (a-2) (10) of the laminate (13) obtained in step (L1) and the 2 nd thermoplastic resin layer (B-2) (16) of the laminate (19) obtained in step (L2) are heat-welded to obtain a joined structure (20) [ fig. 2 (c) ].

The step (L3) can be performed using, for example, a hot press, an autoclave apparatus, a vacuum laminator, a three-dimensional vacuum thermoforming machine (TOM molding machine), a heating laminator, or the like.

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

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

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

The treatment time in the step (L3) is usually 1 second to 1 minute, preferably 3 to 30 seconds.

In the case where the step group including steps (L1) to (L3) is performed, the temperature at which the molecular adhesive layer (a-M) of the laminate (a) for bonding is bonded to the adherend (I) in step (L1) is T_L1And (L2) wherein the temperature at which the molecular adhesive layer (B-M) of the bonding laminate (B) is bonded to the adherend (II) is T_L2And the step (L3) wherein the temperature at which the 2 nd thermoplastic resin layer (A-2) and the 2 nd thermoplastic resin layer (B-2) are heat-welded is T_L3The heat-sealable temperature of the 1 st thermoplastic resin layer (A-1) of the laminate (A) for joining is T_h1AAnd the heat-sealable temperature of the 2 nd thermoplastic resin layer (A-2) is T_h2AThe heat-sealable temperature of the 1 st thermoplastic resin layer (B-1) of the laminate (B) for joining is T_h1BAnd the heat-sealable temperature of the 2 nd thermoplastic resin layer (B-2) is T_h2BIn this case, it is preferable that 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.

[ number 4]

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

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

By satisfying at least one of the formulae (E-3) and (E-4), the 2 nd thermoplastic resin layer (A-2) of the laminate for joining (A) and the 2 nd thermoplastic resin layer (B-2) of the laminate for joining (B) can be thermally welded efficiently.

The 2 nd thermoplastic resin layer (a-2) of the joining laminate (a) and the 2 nd thermoplastic resin layer (B-2) of the joining laminate (B) can be thermally welded more efficiently, and therefore it is more preferable that both the formulas (E-3) and (E-4) are satisfied.

[ Steps containing Steps (M1) to (M3 ]

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

In the step (M1), the 2 nd thermoplastic resin layer (a-2) (23) of the joining laminate (a) (24) having the molecular adhesive layer (a-M) (21), the 1 st thermoplastic resin layer (a-1) (22) and the 2 nd thermoplastic resin layer (a-2) (23) is heat-welded to the 2 nd thermoplastic resin layer (B-2) (27) of the joining laminate (B) (28) having the molecular adhesive layer (B-M) (25), the 1 st thermoplastic resin layer (B-1) (26) and the 2 nd thermoplastic resin layer (B-2) (27), to obtain a laminate (29) [ fig. 3 (a) ].

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

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

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

Each of the steps (M2) and (M3) can be performed by the same method and under the same conditions as in the step (L1).

Note that, the step (M2) and the step (M3) may be performed simultaneously. For example, the step (M2) and the step (M3) can be performed simultaneously by stacking the adherend (I), the laminate obtained in the step (M1), and the adherend (II) in this order and subjecting them to pressure bonding treatment.

[ group of steps including steps (N1), (N2 ]

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

In the step (N1), the adherends (I) (42), the joining laminate (a) (35), the joining laminate (B) (41), and the adherends (II) (43) are sequentially stacked in this order with the 2 nd thermoplastic resin layer (a-2) (36) of the joining laminate (a) (37) having the molecular adhesive layer (a-M) (34), the 1 st thermoplastic resin layer (a-1) (35), and the 2 nd thermoplastic resin layer (a-2) (36) facing the 2 nd thermoplastic resin layer (B-2) (40) of the joining laminate (B) (41) having the molecular adhesive layer (B-M) (38), the 1 st thermoplastic resin layer (B-1) (39), and the 2 nd thermoplastic resin layer (B-2) (40) (fig. 4 (a)).

In the step (N2), the product (44) obtained in the step (N1) is heated to simultaneously perform adhesion of the molecular adhesive layer (a-M) to the adherend (I), adhesion of the molecular adhesive layer (B-M) to the adherend (II), and thermal fusion bonding of the 2 nd thermoplastic resin layer (a-2) to the 2 nd thermoplastic resin layer (B-2), thereby obtaining a joined structure (45) [ fig. 4 (B) ].

Step (N2) may be performed using, for example, a hot press, an autoclave apparatus, a vacuum laminator, a three-dimensional vacuum thermoforming machine (TOM molding machine), a heat lamination apparatus, or the like.

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

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

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

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

In the case where the step group including the steps (N1), (N2) is performed, the heat-sealable temperature of the 1 st thermoplastic resin layer (A-1) of the laminate (A) for joining is T_h1AAnd the heat-sealable temperature of the 2 nd thermoplastic resin layer (A-2) is T_h2AThe heat-sealable temperature of the 1 st thermoplastic resin layer (B-1) of the laminate (B) for joining is T_h1BAnd the heat-sealable temperature of the 2 nd thermoplastic resin layer (B-2) is T_h2BAnd the temperature in the heat welding in the step (N2) is T_N2In this case, at least one of the following formulae (E-5) and (E-6) is preferably satisfied.

[ number 5]

By satisfying at least one of the formulae (E-5) and (E-6), the 2 nd thermoplastic resin layer (A-2) of the laminate for joining (A) and the 2 nd thermoplastic resin layer (B-2) of the laminate for joining (B) can be thermally welded efficiently.

The 2 nd thermoplastic resin layer (a-2) of the joining laminate (a) and the 2 nd thermoplastic resin layer (B-2) of the joining laminate (B) can be thermally welded more efficiently, and therefore it is more preferable that both the formulas (E-5) and (E-6) are satisfied.

When the adherend (I) is joined to the adherend (II), it is preferable to perform the step group including the steps (L1) to (L3) or the step group including the steps (N1) and (N2).

In the step group including the steps (L1) to (L3), the bonding treatment of the molecular adhesive layer and the adherend is performed before the thermal fusion treatment. Therefore, the bonding treatment of the molecular adhesive layer and the adherend can be performed without thermal deformation of the thermoplastic resin layer accompanying the thermal welding treatment, and therefore the molecular adhesive layer and the adherend can be more firmly bonded.

In the step group including the steps (N1) and (N2), the bonding treatment of the molecular adhesive layer and the adherend and the heat fusion treatment of the thermoplastic resin layers are performed simultaneously. Therefore, 2 adherends can be bonded more efficiently.

3) Method for manufacturing bonded structure

The method for producing a bonded structure of the present invention is a method for producing a bonded structure having a layer structure of adherend (I)/layer from bonding laminate (a) and bonding laminate (B)/adherend (II), characterized in that adherend (I) and adherend (II) are bonded using the bonding method of the present invention.

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

As the adherend (I) and the adherend (II), those shown in the invention of the method of joining 2 adherends can be used.

Among them, as the adherend (I) and the adherend (II), those containing at least 1 kind selected from metals, inorganic substances, and thermosetting resins at least on the adherend surface are each independently preferable.

When adherends have an adherend surface formed of a thermoplastic resin, the adherends may be directly thermally fused and bonded to each other without using the bonding laminate of the present invention.

On the other hand, when a metal, an inorganic substance, or a thermosetting resin is present on the surface to be bonded of the adherend, it is difficult to firmly bond the adherend by this method.

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

Examples

The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to the following examples.

In each example, parts and% are by mass unless otherwise specified.

[ measurement of Heat-sealable temperature of layers of multilayer film ]

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

2 sheets of the multilayer film (25 mm. times.150 mm) were prepared, and the layers of the same composition were stacked so as to face each other, and they were heat-welded under conditions of 0.2MPa and 1 second to obtain a test piece. At this time, the heat-sealing temperature was changed at 5 ℃ intervals (e.g., 140 ℃, 145 ℃, 150 ℃) to obtain a plurality of test pieces.

The obtained test pieces were subjected to a T-type peel test under conditions of 300 mm/min using a tensile tester (a universal tester for seeds and seeds, plant and plant society エー, アンド, plant and plant デイ, and plant name テンシロン) under an environment of 23 ℃ and a humidity of 50% (relative humidity), and the respective adhesive strengths were measured.

In the test piece having an adhesive strength of 5N/25mm or more, the heat-sealing temperature of the test piece having the lowest heat-sealing temperature was defined as the "heat-sealable temperature".

[ production example 1]

A multilayer film (1) having a layer structure of "1 st thermoplastic resin layer [ polypropylene (PP) having a thickness of 60 μm ]/2 nd thermoplastic resin layer [ polypropylene (PP) having a thickness of 50 μm ] was obtained by a coextrusion method using 2 kinds of polypropylene as molding materials. As a result of measuring the heat-sealable temperature of each layer of the obtained multilayer film (1), the heat-sealable temperature of the 1 st thermoplastic resin layer was 170 ℃ and the heat-sealable temperature of the 2 nd thermoplastic resin layer was 145 ℃.

[ production examples 2 and 5]

Multilayer films (2) and (5) were obtained in the same manner as in production example 1, except that the molding materials shown in table 1 were used.

[ production example 3]

A multilayer film (3) having a layer structure of "1 st thermoplastic resin layer [ Polyethylene (PE) thickness 25 μm ]/2 nd thermoplastic resin layer [ nylon (Ny) thickness 30 μm/Polyethylene (PE) thickness 25 μm ] was obtained by a co-extrusion method using 2 types of polyethylene and nylon as molding materials. As a result of measuring the heat-sealable temperature of each layer of the obtained multilayer film (3), the heat-sealable temperature of the 1 st thermoplastic resin layer was 140 ℃ and the heat-sealable temperature of the 2 nd thermoplastic resin layer (polyethylene layer) was 100 ℃.

[ production example 4]

A polyethylene film and an ethylene/vinyl acetate copolymer resin film were dry-laminated using a polyester adhesive to obtain a multilayer film (4) having a layer structure of "1 st thermoplastic resin layer [ Polyethylene (PE) having a thickness of 100 μm ]/2 nd thermoplastic resin layer [ ethylene/vinyl acetate copolymer resin (EVA) having a thickness of 50 μm ]. As a result of measuring the heat-sealable temperature of each layer of the obtained multilayer film (4), the heat-sealable temperature of the 1 st thermoplastic resin layer was 140 ℃ and the heat-sealable temperature of the 2 nd thermoplastic resin layer was 110 ℃.

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

In table 1, the resin component names are abbreviated as follows.

Polypropylene: PP (polypropylene)

Polyethylene: PE (polyethylene)

Nylon: ny

Ethylene-vinyl acetate copolymer resin: EVA.

[ Table 1]

[ production example 6 ]

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

[ production example 1]

The multilayer film (1) for bonding was produced by the following method.

The 1 st thermoplastic resin layer of the multilayer film (1) was subjected to corona irradiation with a corona treatment machine (product name "コロナ seed スキャナー ASA-4" manufactured by shin-optical electrical measurements, Ltd., output voltage; 9kV (surface voltage), oscillation frequency: 20 kHz). Subsequently, the molecular adhesive solution obtained in production example 6 was applied to the surface subjected to corona irradiation with a meyer rod (No. 12), and the resulting coating film was dried at 80 ℃ for 60 seconds.

Subsequently, the coating film was irradiated with ultraviolet light using an ultraviolet irradiation apparatus (product name "ライトハンマー 10 MARK II" manufactured by ヘレウス K., light source: mercury lamp) to perform fixing treatment, thereby obtaining a laminate (1) for bonding comprising the molecular adhesive layer, the 1 st thermoplastic resin layer and the 2 nd thermoplastic resin layer (multilayer film (1)).

The ultraviolet irradiation conditions were set to 84mW/cm illuminance²Light quantity 29mJ/cm²The illuminance and the light intensity were measured in the UVC region using an illuminance/seed meter (product name "UV Power Puck II" manufactured by EIT corporation).

(production examples 2 to 4, production comparative example 1)

Laminates (2) to (5) for bonding were obtained in the same manner as in production example 1, except that the multilayer films (2) to (5) shown in table 2 were used instead of the multilayer film (1) in production example 1.

The details of the joining laminates (1) to (5) obtained in production examples 1 to 4 and production comparative example 1 are shown in table 2.

[ Table 2]

[ example 1]

2 pieces of the laminate for bonding (1) (10 mm. times.10 mm) obtained in production example 1 and 2 pieces of an adherend [ a plasma-treated glass plate (30 mm. times.70 mm. times.2 mm) ] were prepared.

The laminate (1) for bonding and the adherend (glass plate) were stacked so that the molecular adhesive layer of the laminate (1) for bonding and the plasma-treated surface of the glass plate were opposed to each other, and thermocompression bonding was performed at 100 ℃ and 0.5MPa (surface pressure) for 5 minutes to obtain a laminate composed of the adherend/molecular adhesive layer/1 st thermoplastic resin layer/2 nd thermoplastic resin layer.

The same operation was carried out using the remaining laminate for bonding (1) and the adherend except for this operation, and another 1 laminate was obtained.

Next, the 2 nd thermoplastic resin layers of the 2 laminates thus obtained were thermocompression bonded to each other at 145 ℃ and 0.5MPa (surface pressure) for 10 seconds to obtain a bonded structure.

[ example 2]

2 pieces of the laminate for bonding (2) (10 mm. times.10 mm) obtained in production example 2 and 2 pieces of an adherend [ a plasma-treated glass plate (30 mm. times.70 mm. times.2 mm) ] were prepared.

The adherend, the laminate for bonding (2), and the adherend were stacked in this order so that the molecular adhesive layers of the 2 laminates for bonding (2) faced the plasma-treated surface of the glass plate, and so that the 2 nd thermoplastic resin layers of the 2 laminates for bonding (2) faced each other, and were subjected to thermocompression bonding at 145 ℃ and 0.5MPa (surface pressure) for 5 minutes to obtain a bonded structure.

[ 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 production conditions described in table 3 were used.

[ comparative example 2]

2 pieces of the multilayer film (1) (10 mm. times.10 mm) obtained in production example 1 and 2 pieces of an adherend [ plasma-treated glass plate (30 mm. times.70 mm. times.2 mm) ] were prepared.

An adherend, the multilayer film (1), and the adherend were stacked in this order so that 2 layers of the multilayer film (1) having a heat-sealable temperature of 170 ℃ were opposed to the plasma-treated surface of the glass plate, and 2 layers of the multilayer film (1) having a heat-sealable temperature of 145 ℃ were opposed to each other, and were subjected to thermocompression bonding at 145 ℃ and 0.5MPa (surface pressure) for 5 minutes to obtain a bonded structure.

[ measurement of adhesive Strength ]

The bonding structures obtained in examples 1 to 4 and comparative examples 1 and 2 were used as test pieces, and the adhesive strength was measured by a universal tensile tester (product of インストロン, インストロン 5581) at a tensile rate of 50 mm/min. Further, 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 was not measured.

[ evaluation of Change in shape ]

The bonded structures obtained in examples 1 to 4 and comparative examples 1 and 2 were used as test pieces, and the bleeding of the bonded laminate after thermocompression bonding was visually observed and evaluated according to the following criteria.

A: the end portions of the joining laminate were visually checked for bleeding due to deformation.

F: the end portions of the joining laminate were visually checked for bleeding due to deformation.

[ Table 3]

The following facts are clear from Table 3.

In examples 1 to 4, the test pieces after the measurement of the adhesive strength did not cause the destruction in the layer of the joining laminate or the destruction at the interface between the layer of the joining laminate and the adherend. Thus, it was found that in examples 1 to 4, 2 adherends were firmly bonded.

On the other hand, in the laminate for bonding used in comparative example 1, the heat-sealable temperature of the 1 st thermoplastic resin layer was the same as the heat-sealable temperature of the 2 nd thermoplastic resin layer. Therefore, deformation occurs at the time of thermocompression bonding.

In comparative example 2, the adherend and the multilayer film were not sufficiently adhered. Therefore, this method is difficult to join glass plates.

Description of the symbols

1: 1 st thermoplastic resin layer

2: 2 nd thermoplastic resin layer

3: laminate comprising 1 st thermoplastic resin layer and 2 nd thermoplastic resin layer

4: molecular adhesive layer

5: laminate for bonding

6: surface of the side in contact with the molecular adhesive layer

7: the surface opposite to the 1 st thermoplastic resin layer

8.21.34: molecular adhesive layer (A-M)

9.22.35: no. 1 thermoplastic resin layer (A-1)

10.23.36: no. 2 thermoplastic resin layer (A-2)

11.24.37: laminate for bonding (A)

12.30.42: adherend (I)

13: laminate as a result of step (L1)

14.25.38: molecular adhesive layer (B-M)

15.26.39: the 1 st thermoplastic resin layer (B-1)

16.27.40: no. 2 thermoplastic resin layer (B-2)

17.28.41: laminate for bonding (B)

18.32.43: adherend (II)

19: laminate as a result of step (L2)

20.33.45: joint structure

29: laminate as a result of step (M1)

31: laminate as a result of step (M2)

44: the product obtained in step (N1)

Claims

1. A laminate for bonding, which comprises a molecular adhesive layer containing a molecular adhesive (M), a1 st thermoplastic resin layer having a single-layer structure, and a 2 nd thermoplastic resin layer having a single-layer structure or a multilayer structure in this order, and in which the molecular adhesive layer and the 2 nd thermoplastic resin layer each constitute the outermost layer in use,

the molecular binder M is a compound having at least 1 reactive group Z alpha selected from the group consisting of an amino group, an azido group, a mercapto group, an isocyanate group, a ureido group and an epoxy group, and at least 1 reactive group Z beta selected from the group consisting of a silanol group and a group which generates a silanol group by a hydrolysis reaction,

the 1 st thermoplastic resin layer contains a thermoplastic resin P at least on the surface thereof in contact with the molecular adhesive layer₁The thermoplastic resin P₁Having a reactive partial structure Z gamma capable of forming a chemical bond with the reactive group Z alpha of the molecular binder M,

the heat-sealable temperature of the 1 st thermoplastic resin layer is T_h1The heat-sealable temperature of the 2 nd thermoplastic resin layer is T_h2When, T_h1＞T_h2。

2. The laminate for joining of claim 1, wherein the reactive group Z α of the molecular adhesive M is at least 1 selected from the group consisting of an amino group, a mercapto group, an isocyanate group, a urea group and an epoxy group, and the thermoplastic resin P₁Having a reactive moiety structure Z gamma of at least 1 kind selected from the group consisting of a hydroxyl group, a carboxyl group, an aldehyde group and an amino group, or,

the reactive group Z alpha of the molecular adhesive M is an azide group, and the thermoplastic resin composition is thermoplasticResin P₁Has a reactive partial structure Z gamma of at least 1 kind selected from the group consisting of a carbon-carbon single bond, a carbon-carbon double bond and a carbon-hydrogen single bond.

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

[ solution 1]

R¹The compound is characterized by representing a reactive group Z alpha selected from amino, azido, sulfydryl, isocyanate, carbamido and epoxy or a 1-valent group containing more than 1 of the reactive groups, G represents a 2-valent organic group, X represents a hydroxyl group, an alkoxy group with 1-10 carbon atoms or a halogen atom, Y represents a hydrocarbon group with 1-20 carbon atoms, and a represents an integer of 1-3, wherein the 1-valent group excludes amino, azido, sulfydryl, isocyanate, carbamido and epoxy.

4. The laminate for bonding of claim 1 or 2, wherein the reactive group Z α of the molecular adhesive M and the thermoplastic resin P are₁The reactive moiety structure Z γ forms a chemical bond.

5. The laminate for joining according to claim 1 or 2, wherein the thermoplastic resin P is₁Is at least 1 selected from olefin resin, cycloolefin resin, acrylic resin, olefin-vinyl acetate resin, olefin ionomer resin and polyester resin.

6. The laminate for bonding according to claim 1 or 2, wherein the 2 nd thermoplastic resin layer comprises at least 1 selected from the group consisting of olefin resins, cycloolefin resins, acrylic resins, olefin-vinyl acetate resins, olefin ionomer resins, and polyester resins on at least the surface opposite to the molecular adhesive layer.

7. A method for bonding an adherend I and an adherend II, which is a method for bonding an adherend I and an adherend II using 2 bonding laminates, characterized in that,

the 2 laminates for bonding are each independently the laminate for bonding according to any one of claims 1 to 6,

the laminate for bonding 1 is represented as having a molecular adhesive M_AThe molecular adhesive layer A-M, the 1 st thermoplastic resin layer A-1 having a single-layer structure, and the 2 nd thermoplastic resin layer A-2 having a single-layer structure or a multi-layer structure, and the 2 nd bonding laminate is represented as having the molecular adhesive layer M contained therein in this order_BThe molecular adhesive layer B-M, the 1 st thermoplastic resin layer B-1 having a single-layer structure, and the 2 nd thermoplastic resin layer B-2 having a single-layer structure or a multi-layer structure,

the method performs any one step group selected from the group consisting of steps L1 to L3, steps M1 to M3 and steps N1 and N2,

step L1: bonding the molecular adhesive layers A-M of the bonding laminate A to the adherend I

Step L2: bonding the molecular adhesive layers B-M of the bonding laminate B to the adherend II

Step L3: a step of heat-welding the 2 nd thermoplastic resin layer A-2 of the laminate obtained in the step L1 with the 2 nd thermoplastic resin layer B-2 of the laminate obtained in the step L2

Step M1: a step of heat-welding the 2 nd thermoplastic resin layer A-2 of the laminate A for joining and the 2 nd thermoplastic resin layer B-2 of the laminate B for joining

Step M2: a step of bonding the molecular adhesive layers A to M of the laminate obtained in the step M1 to the adherend I

Step M3: a step of bonding the molecular adhesive layers B to M of the laminate obtained in the step M2 to the adherend II

Step N1: a step of sequentially stacking an adherend I, a laminate A for bonding, a laminate B for bonding, and an adherend II in such a manner that the 2 nd thermoplastic resin layer A-2 of the laminate A for bonding and the 2 nd thermoplastic resin layer B-2 of the laminate B for bonding are arranged to face each other

Step N2: the product obtained in step N1 is heated to simultaneously perform the steps of bonding the molecular adhesive layer a-M to the adherend I, bonding the molecular adhesive layer B-M to the adherend II, and heat-bonding the 2 nd thermoplastic resin layer a-2 to the 2 nd thermoplastic resin layer B-2.

8. The method for bonding an adherend I and an adherend II as recited in claim 7, which is a method for bonding an adherend I and an adherend II by performing the step set including the steps L1 to L3, wherein,

the temperature at which the molecular adhesive layers A to M of the bonding laminate A are bonded to the adherend I in step L1 is T_L1、

The temperature at which the molecular adhesive layers B to M of the bonding laminate B are bonded to the adherend II in step L2 is T_L2、

The temperature T at which the 2 nd thermoplastic resin layer A-2 and the 2 nd thermoplastic resin layer B-2 are thermally welded in step L3_L3、

The heat-sealable temperature of the 1 st thermoplastic resin layer A-1 of the laminate A for bonding was T_h1AAnd the heat-sealable temperature of the 2 nd thermoplastic resin layer A-2 is T_h2A、

The heat-sealable temperature of the 1 st thermoplastic resin layer B-1 of the laminate B for bonding was T_h1BAnd the heat-sealable temperature of the 2 nd thermoplastic resin layer B-2 is T_h2BWhen the temperature of the water is higher than the set temperature,

satisfies both of the following formulas E-1 and E-2, and at least one of the following formulas E-3 and E-4,

[ number 1]

。

9. The method for bonding adherend I and adherend II as recited in claim 7 which is a method for bonding adherend I and adherend II wherein the step set comprising steps N1, N2 is carried out,

the heat-sealable temperature of the 1 st thermoplastic resin layer A-1 in the laminate A for joining is T_h1AAnd the heat-sealable temperature of the 2 nd thermoplastic resin layer A-2 is T_h2A、

The heat-sealable temperature of the 1 st thermoplastic resin layer B-1 of the laminate B for bonding was T_h1BAnd the heat-sealable temperature of the 2 nd thermoplastic resin layer B-2 is T_h2B、

The temperature at the time of heat fusion in step N2 is T_N2When the temperature of the water is higher than the set temperature,

satisfies at least one of the following formulas E-5 and E-6,

[ number 2]

。

10. A method for producing a bonded structure having a layer structure of an adherend I/a layer from a bonding laminate A and a bonding laminate B/an adherend II, characterized in that the adherend I and the adherend II are bonded by the method according to any one of claims 7 to 9.

11. The method for producing a joined structure according to claim 10, wherein each of the adherend I and adherend II contains at least 1 selected from an inorganic substance and a thermosetting resin on at least the adherend surface independently of the adherend II.

12. The method for manufacturing a joined structure according to claim 11, wherein the inorganic substance is a metal.