WO2019244980A1 - Method for producing bonded multilayer body of polymer and adherend - Google Patents

Abstract

The present invention provides a method for easily producing a bonded multilayer body at low cost, which improves adhesion between a polymer and an adherend, with an adhesive being interposed therebetween. A production method according to the present invention is a method for producing a bonded multilayer body of a polymer and an adherend, which is characterized by comprising a surface treatment step wherein the polymer is reacted with halogen oxide radicals, and a bonding step wherein the polymer and the adherend are bonded to each other by applying an adhesive to at least one of the surface of the polymer after the surface treatment step or the surface of the adherend, and which is also characterized in that the polymer has an aromatic ring in the main chain.

Description

Method for producing adhesive laminate of polymer and adherend

The present invention relates to a method for producing an adhesive laminate of a polymer and an adherend.

(4) When bonding the polymer layer and the object to be bonded, the polymer layer is previously subjected to a treatment for enhancing the adhesiveness (Patent Documents 1 and 2, etc.).

JP 2012-251038 A JP 2013/091702 A

方法 The methods of Patent Documents 1 and 2 are methods using a modified polymer. However, this method requires special treatment at the stage of polymer synthesis, and has a limited range of application.

方法 Further, as a method for improving the adhesiveness of the polymer, for example, there are physical treatment methods such as corona discharge treatment, plasma discharge treatment, and grafting treatment. However, these methods have problems such as complicated operation, processing cost, and difficulty in controlling the reaction. On the other hand, as a chemical surface treatment method, there is a method using a heavy metal oxidant, but there is a problem such as a treatment cost of the heavy metal oxidant. Such a problem also applies to the case where the polymer and the object to be bonded are bonded with an adhesive.

Accordingly, an object of the present invention is to provide a method for producing an adhesive laminate by improving the adhesion between a polymer and an adherend via an adhesive easily and at low cost.

In order to achieve the object, the production method of the present invention is a method for producing an adhesive laminate of a polymer and an adherend,
Reacting the polymer with a halogen oxide radical, a surface treatment step, and
At least one of the surface of the polymer and the surface of the adherend after the surface treatment step, an adhesive is applied, including an adhesion step of adhering the polymer and the adherend,
The polymer is a polymer having an aromatic ring in the main chain.

According to the present invention, it is possible to easily and inexpensively manufacture an adhesive laminate in which the adhesion between a polymer and an object to be adhered via an adhesive is improved.

FIG. 1 is a diagram schematically showing an example of a surface treatment step in the method for producing an adhesive laminate of the present invention. FIG. 2 is a photograph showing the wettability of the film in Example 1. FIG. 3 is a perspective view schematically illustrating a method of laminating the adhesive body in the first embodiment.

に お い て In the present invention, according to the surface treatment step, the polymer can be modified. In the present specification, the surface treatment step may be referred to as a “modification treatment” or a “modification method”. When the polymer is oxidized by the surface treatment step, the surface treatment step can be said to be a method of oxidizing the polymer.

方法 In the method for producing an adhesive laminate according to the present invention, for example, the polymer is a liquid crystal polymer.

方法 In the method for producing an adhesive laminate according to the present invention, for example, the adhesive is a water-compatible adhesive.

は In the method for producing an adhesive laminate of the present invention, for example, the adhesive contains a monomer that is polymerized with water as an initiator.

方法 In the method for producing an adhesive laminate of the present invention, for example, the monomer is a cyanoacrylate monomer.

方法 In the method for producing an adhesive laminate of the present invention, for example, the adhesive is an epoxy-based adhesive.

は In the method for producing an adhesive laminate of the present invention, for example, the reaction system in the surface treatment step is a gas reaction system or a liquid reaction system.

は In the method for producing an adhesive laminate of the present invention, for example, the halogen oxide radical is a chlorine dioxide radical.

In the method for producing an adhesive laminate of the present invention, for example, the polymer to be subjected to the surface treatment step is selected from the group consisting of a sheet, a film, a plate, a tube, a pipe, a rod, a bead, a block, a woven fabric, a nonwoven fabric, and a yarn. At least one molded body.

In the method for producing an adhesive laminate according to the present invention, for example, the adherend is a metal or a polymer.

In the present invention, a chain compound (eg, alkane, unsaturated aliphatic hydrocarbon, etc.) or a chain substituent derived from the chain compound (eg, an alkyl group, a hydrocarbon group such as an unsaturated aliphatic hydrocarbon group, etc.) ) May be, for example, linear or branched, and the number of carbon atoms is not particularly limited. For example, 1 to 40, 1 to 32, 1 to 24, 1 to 18, 1 to 12, 1 to 6 And in the case of an unsaturated hydrocarbon group, the number of carbon atoms is, for example, 2 to 40, 2 to 32, 2 to 24, 2 to 18, 2 to 12, and 2 to 6. In the present invention, a cyclic compound (for example, a cyclic saturated hydrocarbon, a non-aromatic cyclic unsaturated hydrocarbon, an aromatic hydrocarbon, a heteroaromatic compound, etc.) or a cyclic group derived from a cyclic compound (for example, cyclic The number of ring members (the number of atoms constituting the ring) of the saturated hydrocarbon group, the non-aromatic cyclic unsaturated hydrocarbon group, the aryl group, the heteroaryl group and the like is not particularly limited, and is, for example, 5 to 32, 5 to 24, 6 to 18, 6 to 12, or 6 to 10. When an isomer is present in a substituent or the like, for example, the type of the isomer is not particularly limited. As a specific example, when simply referred to as “naphthyl group”, for example, it may be a 1-naphthyl group or a 2-naphthyl group .

In the present invention, the salt is not particularly limited, and may be, for example, an acid addition salt or a base addition salt. The acid forming the acid addition salt may be, for example, an inorganic acid or an organic acid, and the base forming the base addition salt may be, for example, an inorganic base or an organic base. The inorganic acid is not particularly limited, for example, sulfuric acid, phosphoric acid, hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, hypofluoric acid, hypochlorous acid, hypobromous acid, Iodic acid, fluoric acid, chlorous acid, bromous acid, iodic acid, fluoric acid, chloric acid, bromic acid, iodic acid, perfluorinated acid, perchloric acid, perbronic acid, periodic acid, etc. can give. The organic acid is not particularly restricted but includes, for example, p-toluenesulfonic acid, methanesulfonic acid, oxalic acid, p-bromobenzenesulfonic acid, carbonic acid, succinic acid, citric acid, benzoic acid and acetic acid. The inorganic base is not particularly limited and includes, for example, ammonium hydroxide, alkali metal hydroxide, alkaline earth metal hydroxide, carbonate, hydrogencarbonate and the like.More specifically, for example, water Examples include sodium oxide, potassium hydroxide, potassium carbonate, sodium carbonate, sodium bicarbonate, potassium bicarbonate, calcium hydroxide and calcium carbonate. The organic base is not particularly restricted but includes, for example, ethanolamine, triethylamine and tris (hydroxymethyl) aminomethane.

Hereinafter, embodiments of the present invention will be described more specifically with examples. The present invention is not limited to the following embodiments.

As described above, the production method of the present invention comprises a surface treatment step of reacting a polymer with a halogen oxide radical, and a surface and an adherend of the polymer (hereinafter also referred to as a treated polymer) after the surface treatment step. An adhesive is applied to at least one of the surfaces of the object to include an adhesive step of adhering the treated polymer and the object to be adhered, wherein the polymer is a polymer having an aromatic ring in its main chain. And According to the production method of the present invention, for example, the surface of the polymer can be modified by the surface treatment step, whereby the treated polymer and the adherend can be modified via the adhesive in the bonding step. And the adhesiveness between the treated polymer and the adherend is improved, so that an adhesive laminate can be manufactured.

(1) Polymer In the present invention, a polymer to be subjected to the surface treatment step (hereinafter, also referred to as a polymer before treatment) is a polymer having an aromatic ring in a main chain. According to the surface treatment step described later, for example, the side chain of the aromatic ring contained in the main chain of the polymer is modified. The type of the aromatic ring is not particularly limited, for example, naphthylene group, anthracenylene group, phenanthrylene group, chrysenylene group, pyrenylene group, benzoanthracenylene group, fluoranthenylene group, benzofluoranthenylene group, peryleneylene group, colonelylene Group, a picenylene group, a diphenylanthracenylene group, a fluorenylene group, a triphenylenylene group, a rubicenylene group, a phenylanthracenylene group, a bisanthracenylene group, a dianthracenylbenzinylene group, a dibenzoanthracenylene group, and the like. Examples thereof include a naphthylene group, an anthracenylene group, a phenanthrylene group, a chrysenylene group, a pyrenylene group, and a benzoanthracenylene group. Examples of the polymer before treatment include engineering plastics, and specific examples include liquid crystal polymers.

The present invention is particularly useful for application to the liquid crystal polymer. It is known that the liquid crystal polymer is extremely difficult to bond with an existing adhesive. Since it is difficult for the liquid crystal polymer to be chemically bonded to the object to be bonded, for example, with an adhesive, it is necessary to roughen the molded body of the liquid crystal polymer by physical treatment. Was. However, even if the surface of the molded body is roughened, it is difficult to adhere to the adherend with a sufficient adhesive force with the adhesive. The liquid crystal polymer and the like, for example, can be finely molded and have excellent functionality, and thus have been used for various devices such as smartphones, but adhesion is a major issue. According to the present invention, for example, even with the liquid crystal polymer, by performing the surface treatment step, the surface of the liquid crystal polymer can be modified, thereby improving the adhesiveness. No physical treatment is required, and sufficient adhesiveness can be obtained.

Examples of the liquid crystal polymer include a polymer having parahydroxybenzoic acid as a monomer, and specific examples thereof include a basic structure represented by the following formula. In the following formula, for example, type I is a polycondensate of phenol, phthalic acid and parahydroxybenzoic acid, type II is a polycondensate of 2,6-hydroxynaphthoic acid and parahydroxybenzoic acid, Type III is a polycondensate of ethylene terephthalate and parahydroxybenzoic acid. In the following formula, the repeating unit of the monomer structure is not particularly limited.

ポ リ マ ー Examples of the polymer before treatment include polycarbonate (PC), polyethylene terephthalate (PET), polyphenylene sulfide (PPS), polyurethane, and aromatic polyamide in addition to the liquid crystal polymer.

種類 The type of polymer contained in the polymer before treatment is not particularly limited, and may be, for example, one type or a mixture of two or more types. The polymer may be, for example, a polymer alloy or a polymer compound.

The polymer before treatment may be, for example, a polymer having fluidity, a semi-solid polymer, or a solid polymer. Examples of the polymer before the treatment include a polymer having a melting point of room temperature or higher, a solid, crystalline or amorphous polymer at room temperature, and a solid, crystalline or amorphous polymer at 0 ° C. or higher. When the polymer before treatment has a glass transition temperature, the glass transition temperature is not particularly limited, and is, for example, −150 ° C. or higher. For example, the polymer before treatment may have a relatively high crystallinity, and the crystallinity is, for example, 20% or more, 30% or more, or 35% or more.

The polymerization form of the polymer before treatment is not particularly limited, and may be, for example, a homopolymer (homopolymer) or a copolymer. The copolymer is not particularly limited, and examples thereof include a random copolymer, an alternating copolymer, a block copolymer, and a graft copolymer. In the copolymer, the number of repeating units (monomers) is, for example, two or more. Examples of the polymer before treatment include a linear polymer, a branched polymer, and a network polymer.

ポ リ マ ー The polymer before treatment may further contain, for example, other materials. The other material is not particularly limited, and is, for example, a material contained in a general polymer, and may be an inorganic substance or an organic substance. Examples of the inorganic substance include calcium carbonate, clay, talc, carbon fiber, glass fiber, aramid fiber, silicone, and zinc oxide. The other material may be, for example, an additive such as a flame retardant or an antistatic agent.

The form of the polymer before treatment is not particularly limited, and may be a molded article or an unmolded article. In the case of the molded article, for example, after performing the surface treatment step, it may be directly subjected to the next bonding step. In the case where the polymer before treatment is an unformed body, from the viewpoint of handleability, the polymer of the unformed body (treated polymer) subjected to the surface treatment is molded, for example, prior to the bonding step, and The polymer may be subjected to the following bonding step as a molded article. The unformed body is, for example, a polymer itself, and the formed body is, for example, a formed body formed from the polymer.

The molded body is not limited at all, for example, in a molding method, a shape and the like. The molded body can be obtained by a known method using, for example, the polymer to be treated. The molding method generally involves, for example, heat-melting a polymer, shaping the polymer into a desired shape, and cooling. Examples of the molding method include compression molding, transfer molding, extrusion molding, calendar molding, inflation molding, blow molding, vacuum molding, injection molding, casting molding, and the like.

大 き The size and shape of the compact are not particularly limited. Examples of the shape include a sheet, a film, a plate, a tube, a pipe, a rod, a bead, a block, a woven fabric, a nonwoven fabric, a thread, a fiber, and the like. For example, a nonporous body or a porous body may be used.

(2) Halogen oxide radical The halogen oxide radical is a radical of a halogen oxide, and its type is not particularly limited. For example, F ₂ O ^· (oxygen difluoride radical), F ₂ O ₂ ^· (Dioxygen difluoride radical), ClO ₂ ^· (chlorine dioxide radical), BrO ₂ ^· (bromine dioxide radical), I ₂ O ₅ ^· (iodine oxide (V) radical) and the like.

前 記 The halogen oxide radical used in the surface treatment step may be, for example, one type or a combination of two or more types. The halogen oxide radical can be appropriately selected depending on, for example, the type of the polymer to be modified and the reaction conditions.

(3) Reaction system The surface treatment step can be performed, for example, by allowing the halogen oxide radical to coexist in a reaction system in which the polymer before treatment is arranged. The polymer before treatment may be placed in a reaction system containing the halogen oxide. The halogen oxide radical may be included in the reaction system by being generated in the reaction system, for example, or the halogen oxide radical separately generated may be introduced into the reaction system. The method for generating the halogen oxide radical is not particularly limited, and a specific example will be described later. The reaction system may be, for example, a gas reaction system or a liquid reaction system.

In the surface treatment step, for example, the reaction system may or may not be irradiated with light. In the surface treatment step, for example, the polymer before treatment and the halogen oxide radical can be reacted with or without irradiating the reaction system with light. As will be described later, for example, when the halogen oxide radical is generated by light irradiation in the same reaction system, the halogen oxide radical generation step and the surface treatment step can be performed in parallel. May go. Hereinafter, an example in which light irradiation is performed will be described, but the present invention is not limited thereto.

(3-1) Gas Reaction System In the case of the gas reaction system, for example, the polymer before treatment is arranged in a gas reaction system containing the halogen oxide radical, and irradiated with light. The type of the gas phase in the gas reaction system is not particularly limited, and is, for example, air, nitrogen, a rare gas, oxygen, or the like. The reactor accommodating the gas reaction system is preferably, for example, a light-transmitting container when light irradiation is performed from the outside, and is not limited to a light-transmitting container when light irradiation is performed from the inside.

The halogen oxide radical may be introduced into the gas reaction system prior to the surface treatment step, or may be introduced into the gas reaction system simultaneously with the surface treatment step. The introduction of the halogen oxide radical can be performed, for example, by introducing a gas containing the halogen oxide radical into a gas phase. As a specific example, when the halogen oxide radical is the chlorine dioxide radical, for example, by introducing a chlorine dioxide gas into the gas phase, the gas reaction system can include the chlorine dioxide radical. In addition, the introduction of the halogen oxide radical is, for example, as described later, the halogen oxide radical is generated in a reaction system for radical generation in a liquid phase, and the generated halogen oxide radical is transferred to a gas phase. This may be introduced into the gas reaction system.

The halogen oxide radical may be generated, for example, in the gas reaction system. As a specific example, when the halogen oxide radical is a chlorine dioxide radical, it can be generated in a gas phase by, for example, an electrochemical method.

(3-2) Liquid reaction system The liquid reaction system includes, for example, an organic phase. The liquid reaction system may be, for example, a one-phase reaction system containing only the organic phase or a two-phase reaction system containing the organic phase and an aqueous phase.

In the case of the two-phase reaction system, for example, the halogen oxide radical is generated in the aqueous phase, and the generated halogen oxide radical is transferred to the organic phase. May be introduced. In the case of the one-phase reaction system, for example, the generated halogen oxide radical may be separately introduced into the organic phase. Specifically, for example, after separately generating the halogen oxide radical in an aqueous phase, mixing the organic phase with the aqueous phase, and dissolving the halogen oxide radical generated in the aqueous phase in the organic phase ( Extraction), separating the aqueous phase and the organic phase, and preparing the organic phase containing the halogen oxide radical as the one-phase reaction system.

、 In the case of the liquid reaction system, for example, the polymer before treatment is arranged in an organic phase containing the halogen oxide radical, and irradiated with light. The reactor accommodating the liquid reaction system is preferably, for example, a light-transmitting container when light irradiation is performed from the outside, and is not limited to a light-transmitting container when light irradiation is performed from the inside.

The polymer before treatment is immersed in the organic phase so that, for example, a desired region to be modified comes into contact with the halogen oxide radicals in the organic phase, for example, from the viewpoint of treatment efficiency, It is preferable to fix in the organic phase so as not to be exposed from the phase.

The organic phase is, for example, an organic solvent. As the organic solvent, for example, only one kind may be used, or two or more kinds may be used in combination. The organic solvent is not particularly limited, and examples thereof include a halogenated solvent and a fluorous solvent. When the liquid reaction system is the two-phase reaction system, the organic solvent is preferably, for example, a solvent that separates from the aqueous solvent constituting the aqueous phase, or a solvent that is hardly soluble or insoluble in the aqueous solvent.

<< "Halogenated solvent" refers to, for example, a solvent in which all or most of the hydrogen atoms of a hydrocarbon have been substituted with halogens. The halogenated solvent may be, for example, a solvent in which 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more of the number of hydrogen atoms of a hydrocarbon is substituted with a halogen. The halogenated solvent is not particularly limited, and examples thereof include methylene chloride, chloroform, carbon tetrachloride, carbon tetrabromide, and a fluorous solvent described below.

"Fluorous solvent" is one kind of the above-mentioned halogenated solvents, and refers to, for example, a solvent in which all or most of the hydrogen atoms of a hydrocarbon are substituted with fluorine atoms. The fluorous solvent may be, for example, a solvent in which 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more of the hydrogen atoms of the hydrocarbon are substituted with fluorine atoms. The fluorous solvent has, for example, a low reactivity of the solvent itself, so that a side reaction can be further suppressed or prevented. The side reaction is, for example, an oxidation reaction of the solvent, a hydrogen abstraction reaction or a halogenation reaction of the solvent with the halogen oxide radical (for example, a chlorination reaction), and a polymer derived from the polymer before treatment, as described later. A reaction between a radical and the solvent (for example, when the hydrocarbon group on the side chain or terminal of the polymer before treatment is an ethyl group, a reaction between an ethyl radical and the solvent) and the like. Since the fluorous solvent is hardly miscible with water, it is suitable for forming the two-phase reaction system, for example.

Examples of the fluorous solvent include solvents represented by the following chemical formulas (F1) to (F6), and preferably CF ₃ (CF ₂ ) ₄ CF ₃ where n = 4 in the following chemical formula (F1).

沸 The boiling point of the organic solvent is not particularly limited. The organic solvent can be appropriately selected depending on, for example, the temperature conditions in the surface treatment step. When the reaction temperature is set to a relatively high temperature in the surface treatment step, for example, a solvent having a relatively high boiling point may be selected as the organic solvent. In the present invention, in the surface treatment step, for example, as described later, heating is not essential, and can be performed, for example, at normal temperature and normal pressure. For this reason, as the organic solvent, for example, a solvent having a relatively high boiling point can be used from the viewpoint of easy handling.

The organic phase may contain, for example, only the polymer before treatment, the halogen oxide radical and the organic solvent, or may further contain other components. The other components are not particularly limited, and include, for example, Bronsted acid, Lewis acid, oxygen (O ₂ ), and the like. In the organic phase, the other component may be, for example, in a state of being dissolved in the organic solvent or in a state of not being dissolved. In the latter case, for example, the other component may be dispersed or precipitated in the organic solvent.

The aqueous phase is, for example, an aqueous solvent phase. The aqueous solvent is, for example, a solvent that separates from the solvent used in the organic phase. Examples of the aqueous solvent include water such as H ₂ O and D ₂ O.

The aqueous phase may contain, for example, an arbitrary component such as a Lewis acid, a Bronsted acid, and a radical generating source. In the aqueous phase, these optional components may be, for example, in a state of being dissolved in the aqueous solvent or in a state of not being dissolved. In the latter case, for example, the optional component may be in a dispersed state or a precipitated state in the aqueous solvent.

(4) Surface Treatment Step As described above, the surface treatment step comprises reacting the polymer before treatment with a halogen oxide radical to form a treated polymer having a modified surface (hereinafter also referred to as a modified polymer). This is the step of obtaining. According to the surface treatment step of the present invention, the surface of the polymer before treatment is reacted with the halogen oxide radical to obtain a modified polymer in which the surface of the polymer before treatment is modified. The degree of modification (for example, the degree of oxidation) of the modified polymer can be adjusted by, for example, the amount of the halogen oxide radical, the length of time of light irradiation, and the like. Further, by adjusting the degree of modification of the modified polymer, for example, it is possible to suppress the decomposition of the polymer in the modified polymer due to excessive modification, the characteristics inherent to the polymer before treatment in the modified polymer Can be maintained.

領域 A region to be surface-treated in the polymer before treatment is not particularly limited. For example, in the case of the molded body, a region to be brought into contact with the adherend may be included in a subsequent bonding step. Thereby, since the region of the molded body can be modified, the adhesiveness to the adherend via the adhesive can be improved.

In the surface treatment step, for example, from the halogen oxide radicals, radicals of the halogen (e.g., chlorine atom radical Cl ^·) and oxygen molecules O ₂ are generated, the reforming reaction (e.g., relative to the pretreatment polymer, oxidation reaction ) To modify the polymer.

に よ り By the surface treatment step, the pre-treatment polymer may have, for example, a change in a side chain or a change in a main chain (straight chain). The change in the main chain may be, for example, a change in the end of the main chain or a change in the inside of the main chain. The change (also referred to as modification) includes, for example, oxidation, halogenation, and the like. For example, the main chain is a chain of carbon atoms and / or heteroatoms, and the side chain is a chain (branched chain) branched from the main chain, and specifically, a carbon atom or a carbon atom constituting the main chain. A chain branched from the main chain, linked to a hetero atom.

As a specific example, when the polymer before treatment has a benzene ring as an aromatic ring of the main chain, hydrogen of ＣＨCH— of the benzene ring is oxidized to a hydroxyl group (—OH). This is presumed to be due to the following mechanism. That is, for example, electron transfer occurs from the aromatic ring (benzene ring) site in the polymer before treatment to a photoexcited state of chlorine dioxide, and thereafter, an addition reaction of a hydroxide ion (OH ⁻ ) derived from water in the reaction system. And a dehydrogenation reaction occur. As a result, the aromatic ring (benzene ring) is hydroxylated to form a phenol group (= C-OH).

に お い て In the surface treatment step, conditions for light irradiation are not particularly limited. The wavelength of the irradiation light is not particularly limited, the lower limit is, for example, 200 nm or more, the upper limit is, for example, 800 nm or less, the light irradiation time is not particularly limited, and the lower limit is, for example, 1 second or more. Yes, the upper limit is, for example, 1000 hours or less, the reaction temperature is not particularly limited, the lower limit is, for example, -20 ° C or more, and the upper limit is, for example, 100 ° C or less, 40 ° C or less. Is, for example, 0 to 100 ° C. and 0 to 40 ° C. The atmosphere pressure during the reaction is not particularly limited, and the lower limit is, for example, 0.1 MPa or more, and the upper limit is, for example, 100 MPa or less, 10 MPa or less, 0.5 MPa or less. The pressure is 1 to 100 MPa, 0.1 to 10 MPa, and 0.1 to 0.5 MPa. The reaction conditions in the surface treatment step include, for example, a temperature of 0 to 100 ° C. or 0 to 40 ° C., and a pressure of 0.1 to 0.5 MPa. In the present invention, the surface treatment step can be performed, for example, at normal temperature (room temperature) and normal pressure (atmospheric pressure) without performing heating, pressurizing, depressurizing, and the like. is there. “Room temperature” is not particularly limited, and is, for example, 5 to 35 ° C. For this reason, the present invention is applicable even if the polymer before treatment contains, for example, a polymer having low heat resistance. According to the present invention, for example, the surface treatment step or all the steps including the same can be performed in the air without performing inert gas replacement or the like.

The light source for the light irradiation is not particularly limited, and for example, visible light contained in natural light such as sunlight can be used. If natural light is used, for example, excitation can be easily performed. As the light source, for example, a light source such as a xenon lamp, a halogen lamp, a fluorescent lamp, a mercury lamp, and an LED lamp may be used instead of or in addition to the natural light. For the light irradiation, for example, a filter that cuts a wavelength other than the necessary wavelength may be appropriately used.

In the surface treatment step, for example, the polymer before treatment may be irradiated with light only to an arbitrary region. As described above, according to the surface treatment step, for example, the exposed surface of the polymer before treatment is contacted with a halogen oxide under light irradiation, so that the exposed surface can be modified. Therefore, for example, by irradiating only an arbitrary region on the exposed surface of the polymer before treatment, for example, only the arbitrary region can be modified. The method for selectively controlling light irradiation is not particularly limited. For example, light irradiation may be performed only on an arbitrary region, or masking may be performed only on a region that is not irradiated with light, and the entire region may be irradiated with light.

As described above, the surface treatment step may be performed in the liquid reaction system, or may be performed in a gas reaction system. When the polymer before treatment is easily dissolved in a liquid medium, for example, the gas phase reaction system Is preferred. When the reaction system is the liquid reaction system, in the surface treatment step, for example, at least the organic phase is irradiated with light. In the case of the one-phase reaction system, for example, the surface treatment step can be performed by irradiating the organic phase with light. In the case of the two-phase reaction system, for example, of the organic phase and the aqueous phase, only the organic phase may be irradiated with light, or both the organic phase and the aqueous phase may be irradiated with light. In the case of the liquid reaction system, for example, while contacting the liquid reaction system with air, the liquid reaction system may be irradiated with light, and in the case of the two-phase reaction system, oxygen is dissolved in the aqueous phase. Light irradiation may be performed.

In the surface treatment step, the polymer before treatment preferably has, for example, an exposed surface that comes into contact with the halogen oxide radical contained in the reaction system. The exposed surface of the polymer before treatment may be, for example, a surface exposed to the outside of the polymer before treatment, or a surface exposed inside such as a tube or a porous body. The surface treatment step can be said to be, for example, a surface modification step.

According to the surface treatment step, for example, the polymer before treatment can be modified without using a toxic heavy metal catalyst or the like, and the reaction can be performed, for example, under extremely mild conditions as described above. For this reason, according to the surface treatment step, for example, the polymer layer can be efficiently modified by a method having a very small load on the environment.

The method may further include a step of introducing a functional group into the modified region of the modified polymer after the surface treatment step, before the subsequent bonding step, and as described later. According to the present invention, since the surface treatment is modified, for example, according to the adhesive used, by introducing a functional group showing an affinity to the adhesive, to further improve the adhesiveness You can also.

(5) Adhering step In the adhering step, an adhesive is applied to at least one of the surface of the modified polymer after the surface treatment step and the surface of the adherend, and the polymer is adhered to the adherend. I do. According to the present invention, as described above, since the polymer can be modified by the surface treatment step, for example, for a polymer that could not adhere to the adherend even if an adhesive was applied, The affinity is improved, and the adhesion with the adherend by the adhesive becomes possible. The adherend and the adhesive are not particularly limited, and examples thereof include those described below.

The adhesive may be applied to either the surface of the modified polymer or the adherend, or may be applied to both. When applied to the surface of the modified polymer, for example, the adhesive is applied to a region that is in contact with the adherend and is modified by the surface treatment step, and the surface of the adherend is When the adhesive is applied, for example, the adhesive is applied to a region of the surface of the modified polymer that comes into contact with the modified region.

後 After applying the adhesive, for example, the modified polymer and the adherend may be brought into contact with each other via the adhesive and pressed. The contact between the modified polymer and the adherend is preferably performed, for example, after applying the adhesive and before the applied adhesive is completely cured.

In the pressure bonding, the pressure is not particularly limited, and the lower limit is, for example, 0.1 MPa or more, 0.5 MPa or more, 1 MPa or more, 5 MPa or more, or 10 MPa or more, and the upper limit is, for example, 100 MPa or less, 50 MPa or less, It is 40 MPa or less, 30 MPa or less, or 25 MPa or less. The time for applying pressure is not particularly limited. For example, the lower limit is 0.01 minutes or more, 0.1 minutes or more, 3 minutes or more, 5 minutes or more, or 10 minutes or more, and the upper limit is 60 minutes or less, 45 minutes. Hereinafter, it is 30 minutes or less, or 20 minutes or less. The pressing method is not particularly limited, and may be, for example, pressing by a roller, pressing by hand, or the like.

In the thus obtained adhesive laminate of the polymer and the object to be bonded, for example, the peeling force between the polymer and the object to be bonded is not particularly limited. The lower limit of the peel force, for example, 0.001 N / mm ² or more, 0.01 N / mm ² or more, 0.1 N / mm ² or more, 1N / mm ² or more, 5N / mm ² or more, or 10 N / mm ² The upper limit is, for example, 1000 N / mm ² or less, 500 N / mm ² or less, 100 N / mm ² or less, 50 N / mm ² or less, or 20 N / mm ² or less.

(6) Adhesive The adhesive is not particularly limited, and various adhesives can be used. According to the pretreatment step, for example, the modified polymer is modified (for example, oxidized) by a reaction with a halogen oxide radical. For this reason, the affinity with the adhesive can be improved by the functional group (for example, a hydroxy group) formed by the modification contained in the surface of the modified polymer. The adhesive is not particularly limited, and a commercially available adhesive may be used.

The adhesive is, for example, a water-friendly adhesive. When the modified polymer has a functional group (for example, a hydroxy group) by modification (for example, oxidation), for example, the water-adhesive is preferable. The adhesive may include, for example, a monomer that polymerizes with water as an initiator. The monomer is not particularly limited, and is, for example, a cyanoacrylate monomer. Examples of the adhesive having the cyanoacrylate monomer include Alon Alpha (trade name, manufactured by Toagosei Co., Ltd.) and Cemedine C (trade name, Cemedine Co., Ltd.).

The adhesive is not limited to these examples, and includes, for example, an epoxy adhesive, a vinyl acetate resin adhesive, a rubber adhesive, a urea resin adhesive, a melamine resin adhesive, and a phenol resin adhesive. , Vinyl acetate resin adhesive, EVA resin emulsion adhesive, acrylic resin emulsion adhesive, aqueous polymer-isocyanate adhesive, epoxy resin adhesive, cyanoacrylate adhesive, vinyl acetate resin adhesive Agents, polyurethane adhesives, modified silicone adhesives, silylated urethane adhesives, nitrocellulose adhesives, starch adhesives, polyvinyl alcohol adhesives, polyvinylpyrrolidone adhesives, vinyl resin adhesives, styrene Resin adhesives, silicone resin adhesives, Portland cement, plaster, plaster, magne Umm cement, litharge cement, dental cement, asphalt, glue, casein, also soy protein and the like can be used. As described above, since the modified polymer can further introduce a functional group after the modification, the adhesiveness can be further improved by appropriately introducing the functional group according to the adhesive to be used.

(7) Object to be adhered The object to be adhered is not particularly limited, and examples thereof include metal, polymer, ceramic, glass, cloth, and paper. The metal is not particularly limited, and examples thereof include aluminum, nickel, iron, gold, silver, copper, and the like, and alloys such as duralumin, high-tensile steel, and stainless steel. The polymer may be, for example, the same polymer as the pre-treatment polymer or another different polymer. The ceramic is not particularly limited, and examples thereof include zirconia, aluminum oxide, ferrite, barium titanate, boron nitride, silicon carbide, silicon nitride, and steatite.

The other polymer is not particularly limited, for example, polyolefin, polyvinyl chloride, polystyrene, polylactic acid, polyhydroxybutyric acid, silicone-based polymer, natural rubber, phenol resin, epoxy resin, diallyl phthalate resin, polycarbonate (PC), Acrylic polymer, polydimethylsiloxane (PDMS), polyarylate such as amorphous polyarylate, polyether sulfone, polyparaphenylene vinylene, polythiophene, polyfluorene, polyphenylene sulfide (PPS), liquid crystalline polyester, polyparaphenylene (PPP) A composite (PEDOT / PSS) composed of PEDOT (poly (3,4-ethylenedioxythiophene)) and PSS (polystyrenesulfonic acid), polyaniline / polystyrenesulfonic acid, Poly (3-hydroxyalkanoic acid), polyvinylidene chloride, styrene copolymer (eg, acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-styrene copolymer resin (AS), styrene-butadiene copolymer, etc.), Methacrylic resin, polyimide, polyetherimide, poly (trans-1,4-isoprene), urea resin, polyester (eg, polyethylene terephthalate, polybutylene terephthalate, polycaprolactone, polyethylene naphthalate, etc.), polyamide, polyetheretherketone, Cyclic cycloolefin polymer, polyethylene oxide, polypropylene oxide, polyacetal, fluorine-containing polymer (eg, Teflon (registered trademark), fluorine-containing synthetic rubber, etc.), and protein (eg, If, fibronectin, albumin, fibrin, keratin, cytochrome, cytokines, etc.) and the like. Examples of the acrylic polymer include polymethyl methacrylate (PMMA). The polyamide is, for example, nylon (trade name), and specific examples include 6-nylon and 6,6-nylon.

The polyolefin is, for example, a polymer of an olefin having 2 to 20 carbon atoms, and specific examples include polyethylene (PE) such as low-density polyethylene and high-density polyethylene, and polypropylene (PP). The polyolefin may be, for example, a copolymer.

場合 When the polymer is the homopolymer, for example, a repeating unit (monomer) forming a straight chain has a side chain. When the polymer is the copolymer, for example, in each of the repeating units (each monomer) forming a linear chain, one kind of monomer may have a side chain, or two or more kinds of monomers may have a side chain. May have.

The polymer includes, for example, polyimide, polyvinyl alcohol, ethylene vinyl alcohol polymer and the like.

形状 The shape, size and the like of the object to be bonded are not particularly limited, and examples similar to those of the polymer before treatment can be given. Examples of the shape include a sheet, a film, a plate, a tube, a pipe, a rod, a bead, a block, a woven fabric, a nonwoven fabric, a thread, a fiber, and the like. For example, a nonporous body or a porous body may be used.

組 み 合 わ せ The combination of the polymer before treatment and the object to be bonded is not particularly limited, and the combination of the polymer before treatment and the adhesive is not particularly limited.

(8) Generation Step of Halogen Oxide Radical The present invention may further include, for example, a generation step of generating the halogen oxide radical. The generation step may be performed, for example, before the surface treatment step, or may be performed simultaneously with the surface treatment step. The method for producing the halogen oxide radical is not particularly limited.

In the halogen oxide radical generation step, for example, the halogen oxide radical may be generated using a radical generation reaction system. The radical generation reaction system is, for example, an aqueous phase containing a source of the halogen oxide radical, and in the generation step, generates the halogen oxide radical from the source. The aqueous phase is, for example, a phase of an aqueous solvent, and the aqueous solvent is the same as described above.

As described above, the halogen oxide radical generated in the radical generation reaction system may be introduced into, for example, a reaction system (the gas reaction system or the liquid reaction system) in the surface treatment step, The radical generation reaction system may be used as it is in the surface treatment step as the liquid reaction system in the surface treatment step containing the halogen oxide radical.

When the halogen oxide radical is hydrophobic, for example, the radical generating reaction system is a two-phase reaction system including the organic phase and the aqueous phase, whereby the halogen oxide radical is converted to the organic phase. Can be migrated. In this case, for example, since the two-phase reaction system can be used as it is as a liquid reaction system in the pretreatment step, the production step and the surface treatment step can be performed continuously, and a better reaction efficiency can be obtained. Can be When the radical generation reaction system is the two-phase reaction system, for example, the halogen oxide radical is generated in the aqueous phase, dissolved (extracted) in the organic phase, and then the aqueous phase is removed. The organic phase may be used as a one-phase reaction system in the surface treatment step.

When the halogen oxide radical is hydrophobic, for example, the halogen oxide radical generated in the aqueous phase can transfer to the gas phase, so that the gas phase is used, for example, as a liquid reaction system in the pretreatment step. Can be used.

The source of the halogen oxide radical (radical generation source) is not particularly limited, and can be appropriately selected depending on, for example, the type of the halogen oxide radical. The source may be, for example, one type or a plurality of types.

The source is, for example, a compound containing oxygen and halogen, and specific examples include halogenous acid (HXO ₂ ) or a salt thereof. The salt of the halogenous acid is not particularly limited, and examples thereof include metal salts. Examples of the metal salt include alkali metal salts, alkaline earth metal salts, and rare earth salts. The source may be, for example, a compound containing oxygen, a halogen, and a Group 1 element (for example, at least one selected from the group consisting of H, Li, Na, K, Rb, and Cs). And the above-mentioned halogenous acid or an alkali metal salt thereof. When the halogen oxide radical is the chlorine dioxide radical, its source is not particularly limited, and is, for example, chlorite (HClO ₂ ) or a salt thereof, and specifically, for example, sodium chlorite ( NaClO ₂ ), lithium chlorite (LiClO ₂ ), potassium chlorite (KClO ₂ ), magnesium chlorite (Mg (ClO ₂ ) ₂ ), calcium chlorite (Ca (ClO ₂ ) ₂ ) and the like. . Among them, sodium chlorite (NaClO ₂ ) is preferable from the viewpoint of cost, ease of handling, and the like. The same method can be adopted for other halogen oxide radical sources. Examples of the other sources include bromates such as sodium bromite, and iodates such as sodium elementite.

In the aqueous phase of the radical generation reaction system, the concentration of the source is not particularly limited, and when converted to the halogen oxide ion concentration, for example, the lower limit is 0.0001 mol / L or more, and the upper limit is 1 mol / L or less, and when converted to the number of moles of the halogen oxide ion, for example, the lower limit is 1/100000 or more times the number of moles of the polymer to be pretreated, and the upper limit is 1000 times or less. It is. When the source is a halogenous acid or a halogenite (eg, chlorite or chlorite), its concentration is determined by the concentration of a halogenous ion (eg, chlorite ion (ClO ₂ ⁻ )). When converted to, for example, the lower limit is 0.0001 mol / L or more and the upper limit is 1 mol / L or less, which is converted into the number of moles of halogenous ion (eg, chlorite ion (ClO ₂ ⁻ )). In this case, for example, the lower limit is at least 1 / 100,000 times the number of moles of the polymer to be pretreated, and the upper limit is at most 1,000 times. For other sources, for example, the above concentrations can be used.

The aqueous phase may further include, for example, at least one of a Lewis acid and a Bronsted acid, and act on the halogen oxide ion to generate the halogen oxide radical. The Lewis acid and the Bronsted acid include, for example, the Group 1 element. The halogen oxide ion is, for example, chlorite ion (ClO ₂ ⁻ ). The aqueous phase may contain, for example, only one or both of the Lewis acid and the Bronsted acid, or one substance may serve as both the Lewis acid and the Bronsted acid. The Lewis acid or the Bronsted acid may be used alone or in combination of two or more. In the present invention, “Lewis acid” refers to, for example, a substance that acts as a Lewis acid for the above-mentioned source.

濃度 In the aqueous phase, the concentration of at least one of the Lewis acid and the Bronsted acid is not particularly limited, and can be appropriately set according to, for example, the type of the polymer to be pretreated. The lower limit of the concentration is, for example, 0.0001 mol / L or more, and the upper limit is 1 mol / L or less.

The Bronsted acid is not particularly limited, and may be, for example, an inorganic acid or an organic acid. Specific examples include, for example, trifluoromethanesulfonic acid, trifluoroacetic acid, acetic acid, hydrofluoric acid, hydrochloric acid, and hydrogen bromide. Acid, hydroiodic acid, sulfuric acid, sulfurous acid, nitric acid, nitrous acid, phosphoric acid, phosphorous acid and the like. Acid dissociation constant pK _a of the Bronsted acids are, for example, 10 or less, the lower limit is not particularly limited, for example, it is -10 or more.

The aqueous phase contains, for example, the halogen oxide ion and the Bronsted acid. Specifically, for example, water in which the source compound and a Bronsted acid (for example, hydrochloric acid) are dissolved in an aqueous solvent Phase. When the halogen oxide radical is a chlorine dioxide radical, the aqueous phase contains, for example, chlorite ion (ClO ₂ ⁻ ) and a Bronsted acid, and specifically, for example, contains the sodium chlorite (NaClO 2). ₂ ) An aqueous phase in which the Bronsted acid (for example, hydrochloric acid) is dissolved in an aqueous solvent.

に お い て In the aqueous phase, for example, the Lewis acid, the Bronsted acid, the generation source, and the like may be in a state of being dissolved or insoluble in the aqueous solvent. In the latter case, these may be, for example, in a state of being dispersed in an aqueous solvent or in a state of precipitation.

In the generation step, for example, the halogen oxide radical (for example, chlorine dioxide radical) can be spontaneously generated from the halogen oxide ion (for example, chlorite ion) by adding the source to the aqueous solvent. . The aqueous phase is preferably allowed to stand, for example. The aqueous phase can further promote the generation of the halogen oxide radical, for example, in the presence of at least one of the Lewis acid and the Bronsted acid. In the generation step, for example, the aqueous phase may be irradiated with light or not, and the halogen oxide radical can be generated in any case.

メ カ ニ ズ ム The mechanism by which the halogen oxide radicals are generated from the halogen oxide ions in the aqueous phase is presumed, for example, as follows. However, this description is an example and does not limit the present invention in any way.

FIG. 1 schematically shows an example of the production step and the surface treatment step using the two-phase reaction system. FIG. 1 shows, as specific examples, the chlorine dioxide radical as the halogen oxide radical and a polymer molded body as the polymer before treatment. In the two-phase reaction system, a lower organic phase 1 and an upper aqueous phase 2 are separated from each other and are in contact with each other at an interface in a reaction vessel. FIG. 1 is a cross-sectional view, but hatches of an organic phase 1 and an aqueous phase 2 are omitted. First, chlorite ion in the aqueous phase ₂ (ClO 2 ^-) reacts with the acid, chlorine dioxide radical (ClO ₂ ^·) is generated. Chlorine dioxide radical (ClO ₂ ^·), since the water is poorly soluble, are dissolved in the organic phase 1. Next, light irradiation to the organic phase 1 comprising chlorine dioxide radical (ClO ₂ ^·), by applying light energy, chlorine dioxide radicals in the organic phase 1 (ClO ₂ ^·) is decomposed, chlorine radicals (Cl ^· ) And oxygen molecules (O ₂ ) are generated. Thereby, the surface of the polymer molded body (polymer before treatment) in the organic phase 1 is modified by oxidation or the like.

(1) The two-phase reaction system is not limited to, for example, FIG. 1. For example, when the organic phase 1 has a lower density (specific gravity) than the aqueous phase 2, the organic phase 1 is an upper layer. When the polymer before treatment is the polymer molded article, for example, the polymer molded article may be immobilized in the reaction vessel so that the polymer molded article is immersed in the organic phase 1. The fixing portion for fixing the polymer molded body may be provided in, for example, the reaction vessel, or may be provided outside the reaction vessel. In the latter case, for example, a form in which the polymer body is suspended from the outside and immersed in the organic phase 1 can be used.

(9) Step of introducing a functional group The present invention may include, for example, a step of introducing a functional group into the modified region of the modified polymer after the pretreatment step, before the bonding step, and further. Good. According to the present invention, the physical properties of the modified polymer layer can be further changed by functionalization.

Hereinafter, embodiments of the present invention will be described. However, the present invention is not limited to the following examples.

[Example 1]
The liquid crystal polymer film was modified, and the adhesion to an object to be bonded via an adhesive was confirmed.

(1) Preparation of Modified Filter A liquid crystal polymer (LCP) film (trade name UENO LCP, 6030G-MF, manufactured by Ueno Pharmaceutical Co., Ltd.) having a length of 50 mm × a width of 15 mm × a thickness of 2 mm was prepared. The reforming treatment was performed as shown.

A small petri dish (diameter 30 mm × depth 10 mm) was used as a reaction vessel, and a hydrochloric acid-acidic NaClO ₂ aqueous solution was put therein. The aqueous solution of hydrochloric acid acidic NaClO ₂ was made up of H ₂ O (7 mL), NaClO ₂ (200 mg), and 35% HClaq. (100 μL). The small petri dish without the lid and the LCP film were placed in a large petri dish (700 mm diameter × 180 mm depth). The large petri dish was covered, and preheated by a heater at 90 ° C. for 5 minutes. Thereafter, light irradiation was performed at an output of 60 W for 5 minutes from above the lid of the large petri dish. The light source used was an LED lamp (manufactured by dotAqua) having a wavelength of 365 nm, and the distance between the light source and the lid of the large petri dish was 20 cm. By this light irradiation, chlorine dioxide radicals are generated from the NaClO ₂ aqueous solution in the small petri dish, and the chlorine dioxide radicals are transferred to the gas phase in the large petri dish. Was reacted with chlorine dioxide radicals to perform a surface treatment. The reaction was carried out in the atmosphere under a heating condition of 90 ° C. without pressurizing and depressurizing. The reaction was terminated when the yellow coloring derived from the chlorine dioxide radical in the aqueous NaClO ₂ solution disappeared. After completion of the reaction, the LCP film was washed with purified water and dried under reduced pressure overnight. The dried LCP film was used as a modified LCP film in the following steps. The generation of the chlorine dioxide radical has been confirmed by ESR (electron spin resonance).

(2) Evaluation of wettability The wettability of each surface of the modified LCP film and the unmodified LCP film was confirmed. Specifically, 5 μL of water was dropped on the surface of each film, and the wettability was determined from the shape of the water drop. FIG. 2A shows a photograph of the droplet on the unmodified LCP film, and FIG. 2B shows a photograph of the droplet on the modified LCP film. As shown in FIG. 2, since the contact angle of the droplet of the modified LCP film is smaller than that of the unmodified LCP film, it can be said that the wettability has been improved. The improvement in wettability is understood to mean that the modified LCP film has more hydroxyl groups introduced than the unmodified LCP.

(3) Adhesion with an adherend As shown in the perspective view of FIG. 3, the modified LCP film and the adherend were adhered to each other to produce a laminate.

Specifically, as the object to be adhered, an aluminum plate (length 50 mm × width 15 mm × thickness 2 mm), a copper plate (length 60 mm × width 20 mm × thickness 2 mm), and similarly modified An LCP film (length 50 mm × width 15 mm × thickness 2 mm) was prepared. Then, as shown in FIG. 3A, on the modified surface of the modified LCP film 10, a cyanoacrylate-based adhesive 11 (trade name: Aron Alpha, Toagosei Co., Ltd.) Co., Ltd.) was applied. The adhesive 11 was uniformly applied at 40 mg per 25 mm ² . Then, as shown in FIG. 3B, immediately after the application of the adhesive 11, the modified LCP film 10 is applied so that the modified LCP film 10 and the adherend 12 are in contact only in the application area. The adherend 12 was laminated thereon. Then, the layered portion was sandwiched between clips and allowed to stand at room temperature for 10 minutes. The laminate after standing was used for the following evaluation. In addition, as a comparative example, a laminate was similarly manufactured for an untreated LCP film that had not been subjected to a modification treatment, and evaluation was performed.

(4) Tensile Strength As shown in FIG. 3 (B), the end of the modified LCP film and the end of the adherend are each subjected to a tensile strength of 30 N / min in opposite directions. Tensile and tensile strength (shear stress) were measured. The results are shown in Table 1 below.

As shown in Table 1, since the surface of the modified LCP film is modified by oxidation, the affinity with the adhesive is increased, and as a result, the modified LCP film is sufficiently strong in strength with the adherend. It could be glued. On the other hand, when the LCP film not subjected to the modification treatment was used, the adhesive applied to the surface of the LCP film solidified in the form of droplets on the surface and peeled off from the LCP film. For this reason, the LCP film and the adherend did not adhere.

In addition, the aluminum plate and the modified LCP film were bonded in the same manner as above, except that an epoxy-based adhesive (Araldit Rapid, AR-R30, manufactured by Nichiban) was used as the adhesive, and the tensile strength was measured. did. The results are shown in Table 2 below.

[Example 2]
In place of the liquid crystal polymer film, a PET film was modified, and in the same manner as in Example 1, adhesion between the modified PET film and the unmodified PET film as the adherend was confirmed with an adhesive. . As a result, the interface between the unmodified PET film and the adherend (unmodified PET film) was peeled off, whereas the modified PET film was compared with the adherend (unmodified PET film). The adhesive was applied, and the tensile strength was 1.2 MPa (N / mm ² ).

Although the present invention has been described with reference to the exemplary embodiments, the present invention is not limited to the exemplary embodiments. Various changes that can be understood by those skilled in the art can be made to the configuration and details of the present invention within the scope of the present invention.

This application claims priority based on Japanese Patent Application No. 2018-117172 filed on June 20, 2018, the entire disclosure of which is incorporated herein.

As described above, according to the present invention, it is possible to easily and at low cost manufacture an adhesive laminate in which the adhesion between a polymer and an object to be bonded via an adhesive is improved.

DESCRIPTION OF SYMBOLS 1 Organic phase 2 Water phase 10 Modified LCP film 11 Adhesive 12 Adhesive

Claims (10)

1. Reacting the polymer with a halogen oxide radical, a surface treatment step, and
   At least one of the surface of the polymer and the surface of the adherend after the surface treatment step, an adhesive is applied, including an adhesion step of adhering the polymer and the adherend,
   The method for producing an adhesive laminate of the polymer and the adherend, wherein the polymer is a polymer having an aromatic ring in a main chain.
2. The method for producing an adhesive laminate according to claim 1, wherein the polymer is a liquid crystal polymer.
3. The method according to claim 1, wherein the adhesive is a water-compatible adhesive.
4. The method for producing an adhesive laminate according to claim 1, wherein the adhesive includes a monomer that polymerizes with water as an initiator.
5. The method for producing an adhesive laminate according to claim 4, wherein the monomer is a cyanoacrylate monomer.
6. The method for producing an adhesive laminate according to any one of claims 1 to 4, wherein the adhesive is an epoxy-based adhesive.
7. The method according to any one of claims 1 to 6, wherein the reaction system in the surface treatment step is a gas reaction system or a liquid reaction system.
8. The method for manufacturing an adhesive laminate according to any one of claims 1 to 7, wherein the halogen oxide radical is a chlorine dioxide radical.
9. The polymer to be subjected to the surface treatment step is at least one compact selected from the group consisting of a sheet, a film, a plate, a tube, a pipe, a rod, a bead, a block, a woven fabric, a nonwoven fabric, and a yarn. 9. The method for producing an adhesive laminate according to any one of items 1 to 8.
10. The method for producing an adhesive laminate according to any one of claims 1 to 9, wherein the adherend is a metal or a polymer.

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