JP2007126579A - Adhesive for lactone ring-containing polymer and laminated product using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adhesive for a lactone ring-containing polymer capable of firmly bonding the lactone ring-containing polymer to other thermoplastic resins and base materials other than the thermoplastic resins, and a laminated product using the same. <P>SOLUTION: The adhesive for a lactone ring-containing polymer is an adhesive for bonding a layer containing a thermoplastic resin having a lactone ring-containing polymer as the major component and comprises a polyalkyleneimine and a crosslinking agent. The laminated product is obtained by bonding the layer containing a thermoplastic resin having a lactone ring-containing polymer as the major component to a base material with the use of this adhesive. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an adhesive for a lactone ring-containing polymer and a laminate using the same.

  A lactone ring-containing polymer obtained by subjecting a polymer having a hydroxyl group and an ester group in a molecular chain to a lactone cyclocondensation reaction has transparency equivalent to that of a methacrylic resin that has been widely used in the past, In terms of higher heat resistance and superior surface gloss and mechanical strength compared to resin, the lactone ring-containing polymer is included in the thermoplastic resin if it is bonded to other thermoplastic resins to form a laminate. Excellent properties can be imparted.

  For example, Patent Documents 1 to 3 disclose a laminate of a lactone ring-containing polymer and another thermoplastic resin. As a lamination method, for example, any one resin is made into a film, a sheet, or a foam, and the other resin is thermocompression-bonded thereto. After applying an adhesive to at least one resin, the other resin is applied thereto. A method of thermocompression bonding, a method in which both resins are coextruded from an extruder into a film or a sheet, and an in-mold molding method in which a molded product is produced from a lactone ring-containing polymer and another thermoplastic resin is injection-molded on the surface. For example, a method of preparing a molded product from another thermoplastic resin and applying a coating resin solution of a lactone ring-containing polymer is used.

However, no matter which method is used, the adhesive strength between the lactone ring-containing polymer and the other thermoplastic resin in the obtained laminate is not sufficient, and there is room for improvement. The method has not been studied in detail. In addition, the adhesion between the lactone ring-containing polymer and the base material other than the thermoplastic resin has not been considered at all, and if such adhesion becomes possible, there is a field where the lactone ring-containing polymer is applied. Will spread.
JP 2002-254544 A JP 2002-120326 A JP-A-2005-146084

  Under the circumstances described above, the problem to be solved by the present invention is that the lactone ring-containing polymer can be firmly bonded to other thermoplastic resins and other substrates. And providing a laminate using the same.

  As a result of various studies, the present inventors have made use of an adhesive having a specific composition comprising a polyalkyleneimine and a crosslinking agent as essential components, so that a lactone ring-containing polymer and other thermoplastic resins, paper, glass, etc. As a result, the present invention was completed.

  That is, the present invention is an adhesive for adhering a layer containing a thermoplastic resin containing a lactone ring-containing polymer as a main component to a substrate, and that a polyalkyleneimine and a crosslinking agent are blended. Provided is an adhesive for a lactone ring-containing polymer.

  In the lactone ring-containing polymer adhesive of the present invention, the lactone ring-containing polymer is preferably the following formula (1):

[Wherein, R ^1, R ² and R ³ are, independently of one another, represents a hydrogen atom or an organic residue having 1 to 20 carbon atoms; The organic residue may contain an oxygen atom
Having a lactone ring structure.

  The polyalkyleneimine is preferably polyethyleneimine or a derivative thereof. The weight average molecular weight of the polyalkyleneimine is preferably 100 to 100,000, more preferably 200 to 90,000, still more preferably 500 to 80,000.

  Furthermore, the crosslinking agent is preferably an epoxy crosslinking agent and / or an isocyanate crosslinking agent. The functional group ratio of the epoxy group in the epoxy-based crosslinking agent to the amino group in the polyalkyleneimine is preferably a molar ratio of 0.05 to 2.0. The functional group ratio of the isocyanate group in the isocyanate-based crosslinking agent to the amino group in the polyalkyleneimine is preferably a molar ratio of 0.5 to 2.0.

  Further, the present invention provides a laminate comprising a layer containing a thermoplastic resin containing a lactone ring-containing polymer as a main component and a substrate bonded with the lactone ring-containing polymer adhesive. I will provide a.

  In the laminate of the present invention, the substrate is preferably selected from the group consisting of a styrene resin, a vinyl chloride resin, a polycarbonate resin, a polyester resin, a (meth) acrylic resin, a polyolefin resin, and a polyamide resin. Or at least one material selected from the group consisting of thermosetting resin, metal, wood, paper, glass and ceramics. contains.

  According to the lactone ring-containing polymer adhesive of the present invention, since the polyalkyleneimine and the crosslinking agent are blended, the adhesive strength with the lactone ring-containing polymer is very high, and the lactone ring-containing polymer is the main component. The layer containing the thermoplastic resin and the base material can be firmly bonded, and the lactone ring-containing polymer has excellent properties such as transparency, heat resistance, surface gloss, mechanical strength, etc. A laminate is obtained.

≪Adhesive≫
The adhesive of the present invention is an adhesive for a lactone ring-containing polymer (hereinafter sometimes simply referred to as “adhesive”), and more specifically, a thermoplastic resin mainly composed of a lactone ring-containing polymer. An adhesive for adhering a containing layer (hereinafter sometimes simply referred to as a “thermoplastic resin layer”) to a substrate, characterized in that it contains a polyalkyleneimine and a crosslinking agent.

<Polyalkyleneimine>
The adhesive of the present invention contains polyalkyleneimine as an essential component. Examples of the polyalkyleneimine can be obtained by polymerizing an alkyleneimine such as ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine, 1,1-dimethylethyleneimine by a conventional method. . Among these polyalkyleneimines, polyethyleneimine is preferable because it is easily available industrially. The polyalkyleneimine is three-dimensionally crosslinked by polymerization, and usually a primary amino group and a secondary amino group, which are active hydrogen-containing amino groups, are introduced into the structure in addition to a tertiary amino group.

  A polyalkyleneimine derivative obtained by addition-polymerizing an alkylene oxide to a polyalkyleneimine can also be suitably used. Examples of the alkylene oxide include ethylene oxide, propylene oxide, isobutylene oxide, 1-butene oxide, 2-butene oxide, trimethylethylene oxide, tetramethylene oxide, tetramethylethylene oxide, butadiene monooxide, octylene oxide, styrene oxide, 1,1. -Diphenylethylene oxide etc. are mentioned. The polyether chain may be obtained by homopolymerizing one of these or by random polymerization or block polymerization of two or more. Preferred polyether chains are those obtained by homopolymerizing ethylene oxide or propylene oxide, or those obtained by random polymerization or block polymerization of ethylene oxide and propylene oxide.

  The weight average molecular weight of the polyalkyleneimine and derivatives thereof is preferably 100 to 100,000, more preferably 200 to 90,000, still more preferably 500 to 80,000.

<Crosslinking agent>
The adhesive contains a cross-linking agent for cross-linking polyethyleneimine. By adding a crosslinking agent, the adhesive strength between the adhesive layer and the substrate, the durability of the adhesive layer, the mechanical strength, and the like can be improved. The crosslinking agent is not particularly limited as long as it has a functional group capable of reacting with an amino group of polyethyleneimine to form a crosslinked structure. Examples of functional groups capable of forming a crosslinked structure include aldehydes, ketones, alkyl halides, isocyanates, thioisocyanates, double bonds, epoxies, acids, acid anhydrides, acyl halides, esters, and the like. Are used.

  As an epoxy type crosslinking agent, a water-soluble polyepoxy compound is preferable. The water-soluble polyepoxy compound is generally a polyglycidyl ether of a low molecular weight aliphatic polyol, but it must have a sufficiently high solubility in water to dissolve in the aqueous phase of the adhesive composition in the amount added. These are commercially available, for example, from Nagase ChemteX Corporation under the trade name Denacol EX series, and polyglycidyl ethers whose low molecular weight aliphatic polyols are sorbitol, glycerol, polyglycerol, pentaerythritol, trimethylolpropane, etc. It is available. Among them, the water solubility is preferably 20% or more, more preferably 40% or more, still more preferably 80% or more, and bifunctional or more polyglycidyl ether is particularly preferable. Specific examples corresponding to this include, for example, Denacol EX-614B, Denacol EX-512, Denacol EX521, Denacol EX-313, Denacol EX810, and commercial products from other companies corresponding thereto. Moreover, as a commercial item of an isocyanate type crosslinking agent, self-emulsification type polyisocyanate (Aquanate 100, Nippon Polyurethane Industry Co., Ltd. product) etc. are mentioned, for example.

  The amount of the cross-linking agent varies depending on the type of the cross-linking agent, and may be adjusted as appropriate, and is not particularly limited. For example, when an epoxy-based cross-linking agent is used, amino acids in the polyalkyleneimine are used. Converted to the functional group ratio of the epoxy group to the group, the molar ratio is preferably 0.05 to 2.0, more preferably 0.3 to 1.0. When the functional group ratio of the epoxy group to the amino group is less than 0.05, the adhesive strength between the thermoplastic resin layer and the substrate may not be improved. Conversely, when the functional group ratio exceeds 2.0, the water resistance of the adhesive layer may be deteriorated. Moreover, when an isocyanate type crosslinking agent is used, it is preferably 0.5 to 2.0, more preferably 0 in terms of molar ratio in terms of the functional group ratio of the isocyanate group to the amino group in the polyalkyleneimine. .5 to 1.0. When the functional group ratio of the isocyanate group to the amino group is less than 0.5, the adhesive strength between the thermoplastic resin layer and the substrate may not be improved. Conversely, when the functional group ratio exceeds 2.0, the water resistance of the adhesive layer may be deteriorated.

<Polyvinyl alcohol resin>
The adhesive of the present invention contains a polyalkyleneimine and a crosslinking agent as essential components, and a polyvinyl alcohol-based resin can be further added. By adding the polyvinyl alcohol-based resin, the adhesive strength between the layer containing the thermoplastic resin mainly composed of the lactone ring-containing polymer and the substrate is improved.

  For example, the polyvinyl alcohol-based resin is obtained by polymerizing a vinyl monomer mainly composed of a vinyl ester monomer by a conventionally known method to obtain a vinyl ester polymer (that is, a vinyl ester monomer homopolymer, two kinds). A copolymer of the above vinyl ester monomer, and a copolymer of the vinyl ester monomer and another copolymerizable monomer (for example, an ethylenically unsaturated monomer), It can be obtained by saponifying this vinyl ester polymer by a conventional method.

  The vinyl ester monomer is not particularly limited as long as it can be radically polymerized. Specifically, for example, vinyl formate, vinyl acetate, vinyl propionate, isopropenyl acetate, vinyl valerate, Examples include vinyl caprate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl versatate, and vinyl pivalate. These vinyl ester monomers may be used alone or in combination of two or more. Of these vinyl ester monomers, vinyl acetate is particularly preferred because it is produced industrially and is inexpensive.

  Examples of monomers copolymerizable with vinyl ester monomers include olefins such as ethylene, propylene, 1-butene, and isobutene; acrylic acid, methacrylic acid, fumaric acid, maleic acid, crotonic acid, and itacone. Unsaturated carboxylic acids such as acids, maleic anhydride, phthalic anhydride, trimellitic anhydride, itaconic anhydride and their anhydrides; methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, acrylic acid n -Acrylic esters such as butyl, t-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, octadecyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n methacrylate -Butyl, t-butyl methacrylate , Methacrylates such as 2-ethylhexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate; unsaturated carboxylic esters such as dimethyl fumarate, diethyl maleate, diisopropyl itaconate; methyl vinyl ether, n-propyl vinyl ether, isopropyl Vinyl ethers such as vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, t-butyl vinyl ether, dodecyl vinyl ether, stearyl vinyl ether; nitriles such as acrylonitrile and methacrylonitrile; vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, etc. Vinyl halides; allyl compounds such as allyl acetate and allyl chloride; ethylene sulfonic acid, allyl sulfonic acid, methallyl sulfate Sulfonic acid group-containing compounds such as acid and 2-acrylamido-2-methylpropanesulfonic acid; vinylsilane compounds such as vinyltrimethoxysilane; fourth compounds such as 3-acrylamidopropyltrimethylammonium chloride and 3-methacrylamidopropyltrimethylammonium chloride A monomer having a secondary ammonium base; These copolymerizable monomers may be used alone or in combination of two or more.

  The vinyl ester polymer obtained by the above method can be saponified at a predetermined ratio to obtain a polyvinyl alcohol resin to be blended in the adhesive of the present invention. The saponification degree of the polyvinyl alcohol resin can be adjusted by a conventionally known method. The saponification degree of the polyvinyl alcohol resin blended in the adhesive of the present invention is preferably 70 mol% or more, more preferably 80 mol% or more, and further preferably 90 mol% or more. The average degree of polymerization of the polyvinyl alcohol-based resin is preferably 200 to 4,000, more preferably 250 to 3,000. The average degree of polymerization of the polyvinyl alcohol-based resin is substantially the same as the average degree of polymerization of the vinyl ester polymer before saponification. That is, the average degree of polymerization does not substantially change due to saponification. Therefore, in order to obtain a polyvinyl alcohol resin to be blended in the adhesive of the present invention, a vinyl ester polymer having an average polymerization degree of preferably 200 to 4,000, more preferably 250 to 3,000 may be used. . The average degree of polymerization of the vinyl ester polymer can be adjusted by a conventionally known method.

  The polyvinyl alcohol resin may be modified by graft addition of a compound having an alkyl group, an epoxy group, a carbonyl group, a silanol group, a thiol group, or the like.

  The blending amount of the polyvinyl alcohol-based resin in the adhesive of the present invention is preferably 5 to 500 parts by mass, more preferably 10 to 400 parts by mass with respect to 100 parts by mass of the polyalkylenimine. When the blending amount of the polyvinyl alcohol-based resin is less than 5% by mass, the effect of improving the adhesive strength between the layer containing the thermoplastic resin mainly containing the lactone ring-containing polymer and the substrate may not be observed. . On the contrary, if the blending amount of the polyvinyl alcohol-based resin exceeds 500% by mass, the water resistance of the adhesive layer may be lowered.

<Others>
Other additives that can be incorporated into the adhesive include, for example, coupling agents such as silane coupling agents and titanium coupling agents; UV absorbers, antioxidants, heat stabilizers, hydrolysis stabilizers, and other stable agents. Agent; polyethyleneimine yellowing inhibitor; and the like.

  The adhesive is usually used as an adhesive made of an aqueous solution, but an alcohol solvent may be used as a solvent other than water, or a mixed solvent of water and alcohol may be used. Examples of the alcohol used as the solvent include methanol, ethanol, isopropyl alcohol, and the like.

≪Lactone ring-containing polymer≫
The adhesive of this invention is used in order to adhere | attach the layer containing the thermoplastic resin which has a lactone ring containing polymer as a main component to a base material. The lactone ring-containing polymer that is the main component of the layer containing the thermoplastic resin is preferably the following formula (1):

[Wherein, R ^1, R ² and R ³ are, independently of one another, represents a hydrogen atom or an organic residue having 1 to 20 carbon atoms; The organic residue may contain an oxygen atom
Having a lactone ring structure.

  The content of the lactone ring structure represented by the above formula (1) in the structure of the lactone ring-containing polymer is preferably 5 to 90% by mass, more preferably 10 to 70% by mass, and still more preferably 10 to 60% by mass. Especially preferably, it is 10-50 mass%. When the content of the lactone ring structure is less than 5% by mass, the heat resistance, solvent resistance, and surface hardness of the obtained polymer may be lowered. On the contrary, when the content of the lactone ring structure exceeds 90% by mass, the moldability of the obtained polymer may be deteriorated.

  The lactone ring-containing polymer may have a structure other than the lactone ring structure represented by the above formula (1). The structure other than the lactone ring structure represented by the above formula (1) is not particularly limited. For example, a (meth) acrylic acid ester, which will be described later as a method for producing a lactone ring-containing polymer, Hydroxyl group-containing monomer, unsaturated carboxylic acid, and the following formula (2):

[Wherein, R ⁴ represents a hydrogen atom or a methyl group, and X represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, an —OAc group, a —CN group, a —CO—R ⁵ group, or —CO —O—R ⁶ group, Ac represents an acetyl group, R ⁵ and R ⁶ represent a hydrogen atom or an organic residue having 1 to 20 carbon atoms]
A polymer structural unit (repeating structural unit) formed by polymerizing at least one monomer selected from the group consisting of monomers represented by formula (1) is preferred.

  The content ratio of the structure other than the lactone ring structure represented by the above formula (1) in the structure of the lactone ring-containing polymer is a polymer structural unit (repeated structural unit) formed by polymerizing (meth) acrylic acid ester. In this case, it is preferably 10 to 95% by mass, more preferably 10 to 90% by mass, further preferably 40 to 90% by mass, and particularly preferably 50 to 90% by mass, and is formed by polymerizing a hydroxyl group-containing monomer. In the case of a polymer structural unit (repeating structural unit), preferably 0 to 30% by mass, more preferably 0 to 20% by mass, still more preferably 0 to 15% by mass, particularly preferably 0 to 10% by mass. . In the case of a polymer structural unit (repeating structural unit) formed by polymerizing an unsaturated carboxylic acid, it is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, and still more preferably 0 to 15% by mass. Especially preferably, it is 0-10 mass%. Furthermore, in the case of a polymer structural unit (repeating structural unit) formed by polymerizing the monomer represented by the above formula (2), preferably 0 to 30% by mass, more preferably 0 to 20% by mass, Preferably it is 0-15 mass%, Most preferably, it is 0-10 mass%.

  The method for producing the lactone ring-containing polymer is not particularly limited. For example, the polymer obtained after obtaining the polymer (a) having a hydroxyl group and an ester group in the molecular chain by a polymerization step. It is obtained by carrying out a lactone cyclization condensation step for introducing a lactone ring structure into the polymer by heat-treating (a).

  In the polymerization step, for example, the following formula (3):

[Wherein, R ⁷ and R ⁸ each independently represent a hydrogen atom or an organic residue having 1 to 20 carbon atoms]
The polymer which has a hydroxyl group and an ester group in a molecular chain is obtained by performing the polymerization reaction of the monomer component which mix | blended the monomer shown by.

  Examples of the monomer represented by the above formula (3) include methyl 2- (hydroxymethyl) acrylate, ethyl 2- (hydroxymethyl) acrylate, isopropyl 2- (hydroxymethyl) acrylate, and 2- (hydroxy Examples include methyl) n-butyl acrylate, t-butyl 2- (hydroxymethyl) acrylate, and the like. These monomers may be used alone or in combination of two or more. Among these monomers, 2- (hydroxymethyl) methyl acrylate and 2- (hydroxymethyl) ethyl acrylate are preferable, and since the effect of improving heat resistance is high, methyl 2- (hydroxymethyl) acrylate Is particularly preferred.

  The content ratio of the monomer represented by the formula (3) in the monomer component to be subjected to the polymerization step is preferably 5 to 90% by mass, more preferably 10 to 70% by mass, and still more preferably 10 to 60% by mass. %, Particularly preferably 10 to 50% by mass. When the content ratio of the monomer represented by the above formula (3) is less than 5% by mass, the heat resistance, solvent resistance and surface hardness of the obtained polymer may be lowered. On the contrary, when the content ratio of the monomer represented by the above formula (3) exceeds 90% by mass, gelation may occur in the polymerization step or the lactone cyclization condensation step, and the moldability of the obtained polymer may be increased. May decrease.

  You may mix | blend monomers other than the monomer shown by the said Formula (3) with the monomer component with which it uses for a superposition | polymerization process. Such a monomer is not particularly limited. For example, (meth) acrylic acid ester, hydroxyl group-containing monomer, unsaturated carboxylic acid, and the following formula (2):

[Wherein, R ⁴ represents a hydrogen atom or a methyl group, and X represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, an —OAc group, a —CN group, a —CO—R ⁵ group, or —CO —O—R ⁶ group, Ac represents an acetyl group, R ⁵ and R ⁶ represent a hydrogen atom or an organic residue having 1 to 20 carbon atoms]
And the like. These monomers may be used alone or in combination of two or more.

  The (meth) acrylic acid ester is not particularly limited as long as it is a (meth) acrylic acid ester other than the monomer represented by the above formula (3). For example, methyl acrylate, ethyl acrylate Acrylates such as n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, cyclohexyl acrylate, and benzyl acrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, methacrylic acid And methacrylic acid esters such as isobutyl, t-butyl methacrylate, cyclohexyl methacrylate, and benzyl methacrylate. These (meth) acrylic acid esters may be used alone or in combination of two or more. Among these (meth) acrylic acid esters, methyl methacrylate is particularly preferable because the obtained polymer has excellent heat resistance and transparency.

  When using a (meth) acrylic acid ester other than the monomer represented by the above formula (3), the content ratio in the monomer component to be subjected to the polymerization step is sufficient to exert the effect of the present invention. Preferably it is 10-95 mass%, More preferably, it is 10-90 mass%, More preferably, it is 40-90 mass%, Most preferably, it is 50-90 mass%.

  The hydroxyl group-containing monomer is not particularly limited as long as it is a hydroxyl group-containing monomer other than the monomer represented by the above formula (3). For example, α-hydroxymethylstyrene, α-hydroxy And 2- (hydroxyalkyl) acrylic acid esters such as ethyl styrene and methyl 2- (hydroxyethyl) acrylate; 2- (hydroxyalkyl) acrylic acids such as 2- (hydroxyethyl) acrylic acid; and the like. These hydroxyl group-containing monomers may be used alone or in combination of two or more.

  When a hydroxyl group-containing monomer other than the monomer represented by the above formula (3) is used, the content ratio in the monomer component to be subjected to the polymerization step is preferable in order to sufficiently exhibit the effects of the present invention. Is 0 to 30% by mass, more preferably 0 to 20% by mass, still more preferably 0 to 15% by mass, and particularly preferably 0 to 10% by mass.

  Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-substituted acrylic acid, α-substituted methacrylic acid and the like. These unsaturated carboxylic acids may be used alone or in combination of two or more. Among these unsaturated carboxylic acids, acrylic acid and methacrylic acid are particularly preferable because the effects of the present invention are sufficiently exhibited.

  When using an unsaturated carboxylic acid, the content ratio in the monomer component to be subjected to the polymerization step is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, in order to sufficiently exhibit the effects of the present invention. %, More preferably 0 to 15% by mass, particularly preferably 0 to 10% by mass.

  Examples of the monomer represented by the formula (2) include styrene, α-methylstyrene, vinyl toluene, acrylonitrile, methyl vinyl ketone, ethylene, propylene, and vinyl acetate. These monomers may be used alone or in combination of two or more. Of these monomers, styrene and α-methylstyrene are particularly preferable because the effects of the present invention are sufficiently exhibited.

  When the monomer represented by the above formula (2) is used, the content ratio in the monomer component to be subjected to the polymerization step is preferably 0 to 30% by mass in order to sufficiently exhibit the effects of the present invention. More preferably, it is 0-20 mass%, More preferably, it is 0-15 mass%, Most preferably, it is 0-10 mass%.

  The form of the polymerization reaction for polymerizing the monomer components to obtain a polymer having a hydroxyl group and an ester group in the molecular chain is preferably a polymerization form using a solvent, and solution polymerization is particularly preferred.

  The polymerization temperature and the polymerization time vary depending on the type and ratio of the monomer used. For example, the polymerization temperature is preferably 0 to 150 ° C., the polymerization time is 0.5 to 20 hours, and more Preferably, the polymerization temperature is 80 to 140 ° C. and the polymerization time is 1 to 10 hours.

  In the case of a polymerization form using a solvent, the polymerization solvent is not particularly limited. For example, aromatic hydrocarbon solvents such as toluene, xylene, and ethylbenzene; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; tetrahydrofuran And ether solvents such as These solvents may be used alone or in combination of two or more. Moreover, since the residual volatile matter of the lactone ring containing polymer finally obtained will increase when the boiling point of a solvent is too high, the solvent whose boiling point is 50-200 degreeC is preferable.

  During the polymerization reaction, a polymerization initiator may be added as necessary. The polymerization initiator is not particularly limited. For example, cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butylperoxyisopropyl Organic peroxides such as carbonate and t-amylperoxy-2-ethylhexanoate; 2,2′-azobis (isobutyronitrile), 1,1′-azobis (cyclohexanecarbonitrile), 2,2 ′ -Azo compounds such as azobis (2,4-dimethylvaleronitrile); These polymerization initiators may be used alone or in combination of two or more. The amount of the polymerization initiator used is not particularly limited as long as it is appropriately set according to the combination of monomers and reaction conditions.

  When performing the polymerization, it is preferable to control the concentration of the polymer produced in the polymerization reaction mixture to be 50% by mass or less in order to suppress gelation of the reaction solution. Specifically, when the concentration of the polymer formed in the polymerization reaction mixture exceeds 50% by mass, it is preferable that the polymerization solvent is appropriately added to the polymerization reaction mixture and controlled to be 50% by mass or less. . The concentration of the polymer formed in the polymerization reaction mixture is more preferably 45% by mass or less, and further preferably 40% by mass or less. In addition, since productivity will fall when the density | concentration of the polymer produced | generated in the polymerization reaction mixture is too low, the density | concentration of the polymer produced | generated in the polymerization reaction mixture becomes like this. Preferably it is 10 mass% or more, More preferably, it is 20 mass%. That's it.

  The form in which the polymerization solvent is appropriately added to the polymerization reaction mixture is not particularly limited, and for example, the polymerization solvent may be added continuously or the polymerization solvent may be added intermittently. By controlling the concentration of the polymer formed in the polymerization reaction mixture in this way, the gelation of the reaction solution can be more sufficiently suppressed, and in particular, to increase the lactone ring content and improve the heat resistance. Even when the ratio between the hydroxyl group and the ester group in the molecular chain is increased, gelation can be sufficiently suppressed. The polymerization solvent to be added may be, for example, the same type of solvent used during the initial charging of the polymerization reaction or a different type of solvent, but the solvent used during the initial charging of the polymerization reaction. It is preferable to use the same type of solvent. Moreover, the polymerization solvent to be added may be only one kind of single solvent or two or more kinds of mixed solvents.

  The polymerization reaction mixture obtained when the above polymerization step is completed usually contains a solvent in addition to the obtained polymer, but it is necessary to completely remove the solvent and take out the polymer in a solid state. Rather, it is preferably introduced into the subsequent lactone cyclization condensation step in a state containing a solvent. If necessary, after taking out in a solid state, a solvent suitable for the subsequent lactone cyclization condensation step may be added again.

  The polymer obtained in the polymerization step is a polymer (a) having a hydroxyl group and an ester group in the molecular chain, and the weight average molecular weight of the polymer (a) is preferably 1,000 to 2,000,000. 000, more preferably 5,000 to 1,000,000, still more preferably 10,000 to 500,000, particularly preferably 50,000 to 500,000. The polymer (a) obtained in the polymerization step is subjected to heat treatment in the subsequent lactone cyclization condensation step, whereby a lactone ring structure is introduced into the polymer to become a lactone ring-containing polymer.

  The reaction for introducing a lactone ring structure into the polymer (a) is a reaction in which a hydroxyl group and an ester group present in the molecular chain of the polymer (a) are cyclized and condensed to form a lactone ring structure by heating. Yes, by the cyclocondensation, alcohol is by-produced. By forming the lactone ring structure in the molecular chain of the polymer (in the main skeleton of the polymer), high heat resistance is imparted. If the reaction rate of the cyclization condensation reaction leading to the lactone ring structure is insufficient, the heat resistance will not be improved sufficiently, or a condensation reaction will occur during the molding due to the heat treatment during molding, and the resulting alcohol will be contained in the molded product. May exist as bubbles or silver streaks.

  The lactone ring-containing polymer obtained in the lactone cyclization condensation step is preferably the following formula (1):

[Wherein, R ^1, R ² and R ³ are, independently of one another, represents a hydrogen atom or an organic residue having 1 to 20 carbon atoms; The organic residue may contain an oxygen atom
Having a lactone ring structure.

  The method for heat-treating the polymer (a) is not particularly limited, and a conventionally known method may be used. For example, you may heat-process the polymerization reaction mixture containing the solvent obtained by the superposition | polymerization process as it is. Or you may heat-process using a ring-closure catalyst as needed in presence of a solvent. Or heat processing can also be performed using the heating furnace and reaction apparatus provided with the vacuum apparatus or devolatilization apparatus for removing a volatile component, the extruder provided with the devolatilization apparatus, etc.

  In carrying out the cyclization condensation reaction, in addition to the polymer (a), another thermoplastic resin may coexist. When performing the cyclization condensation reaction, if necessary, an esterification catalyst or a transesterification catalyst such as p-toluenesulfonic acid generally used as a catalyst for the cyclization condensation reaction may be used. Organic carboxylic acids such as propionic acid, benzoic acid, acrylic acid, and methacrylic acid may be used as a catalyst. Furthermore, as disclosed in, for example, Japanese Patent Application Laid-Open Nos. 61-254608 and 61-261303, basic compounds, organic carboxylates, carbonates, and the like may be used.

  Alternatively, an organophosphorus compound may be used as a catalyst for the cyclization condensation reaction. Examples of the organic phosphoric acid compounds that can be used include alkyl (aryl) phosphonous acids such as methyl phosphonous acid, ethyl phosphonous acid, and phenyl phosphonous acid (however, these are alkyl (aryl) which are tautomers. ) Which may be phosphinic acid) and their monoesters or diesters; dialkyl (aryl) phosphinic acids such as dimethylphosphinic acid, diethylphosphinic acid, diphenylphosphinic acid, phenylmethylphosphinic acid, phenylethylphosphinic acid and their Esters; alkyl (aryl) phosphonic acids such as methylphosphonic acid, ethylphosphonic acid, trifluoromethylphosphonic acid, phenylphosphonic acid and their monoesters or diesters; methylphosphinic acid, ethylphosphinic acid Alkyl (aryl) phosphinic acids such as phenylphosphinic acid and esters thereof; methyl phosphite, ethyl phosphite, phenyl phosphite, dimethyl phosphite, diethyl phosphite, diphenyl phosphite, phosphorus phosphite Phosphorous acid monoester, diester or triester such as trimethyl phosphate, triethyl phosphite, triphenyl phosphite; methyl phosphate, ethyl phosphate, 2-ethylhexyl phosphate, octyl phosphate, isodecyl phosphate, phosphoric acid Lauryl, stearyl phosphate, isostearyl phosphate, phenyl phosphate, dimethyl phosphate, diethyl phosphate, di-2-ethylhexyl phosphate, diisodecyl phosphate, dilauryl phosphate, distearyl phosphate, diisostearyl phosphate, Diphenyl phosphate, trimethyl phosphate, triethyl phosphate Phosphoric acid monoesters, diesters or triesters such as triisodecyl phosphate, trilauryl phosphate, tristearyl phosphate, triisostearyl phosphate, triphenyl phosphate; methylphosphine, ethylphosphine, phenylphosphine, dimethylphosphine, diethylphosphine , Diphenylphosphine, trimethylphosphine, triethylphosphine, triphenylphosphine, etc. mono-, di- or tri-alkyl (aryl) phosphine; methyldichlorophosphine, ethyldichlorophosphine, phenyldichlorophosphine, dimethylchlorophosphine, diethylchlorophosphine, diphenyl Alkyl (aryl) halogen phosphines such as chlorophosphine; methylphosphine oxide, ethylphosphine oxide, oxide Mono-, di- or tri-alkyl (aryl) phosphines such as phenyl phosphine, dimethyl phosphine oxide, diethyl phosphine oxide, diphenyl phosphine oxide, trimethyl phosphine oxide, triethyl phosphine oxide, triphenyl phosphine oxide; tetramethylphosphonium chloride, chloride And halogenated tetraalkyl (aryl) phosphoniums such as tetraethylphosphonium and tetraphenylphosphonium chloride. These organic phosphorus compounds may be used alone or in combination of two or more. Among these organophosphorus compounds, since the catalytic activity is high and the colorability is low, alkyl (aryl) phosphonous acid, phosphorous acid monoester or diester, phosphoric acid monoester or diester, and alkyl (aryl) phosphonic acid Preferably, alkyl (aryl) phosphonous acid, phosphorous acid monoester or diester, phosphoric acid monoester or diester is more preferable, and alkyl (aryl) phosphonous acid, phosphoric acid monoester or diester is particularly preferable.

  Although the usage-amount of the catalyst used in the case of a cyclization condensation reaction is not specifically limited, For example, Preferably it is 0.001-5 mass% with respect to a polymer (a), More preferably, it is 0.01. -2.5 mass%, More preferably, it is 0.01-1 mass%, Most preferably, it is 0.05-0.5 mass%. When the amount of the catalyst used is less than 0.001% by mass, the reaction rate of the cyclization condensation reaction may not be sufficiently improved. On the other hand, when the amount of the catalyst used exceeds 5% by mass, the obtained polymer may be colored or the polymer may be cross-linked to make melt molding difficult.

  The addition timing of the catalyst is not particularly limited. For example, the catalyst may be added at the beginning of the reaction, may be added during the reaction, or may be added in both of them.

  It is preferable to carry out the cyclization condensation reaction in the presence of a solvent and to use a devolatilization step in combination with the cyclization condensation reaction. In this case, a mode in which the devolatilization step is used throughout the cyclization condensation reaction and a mode in which the devolatilization step is not used over the entire cyclization condensation reaction but only in a part of the process. In the method using the devolatilization step in combination, the alcohol produced as a by-product in the condensation cyclization reaction is forcibly devolatilized and removed, so that the equilibrium of the reaction is advantageous for the production side.

  The devolatilization process means a process of removing volatile components such as solvents and residual monomers and alcohol by-produced by a cyclization condensation reaction leading to a lactone ring structure under reduced pressure heating conditions as necessary. To do. If this removal treatment is insufficient, residual volatile components in the obtained polymer increase, and coloring may occur due to deterioration during molding, and molding defects such as bubbles and silver streaks may occur.

  In the case of using a devolatilization step throughout the cyclization condensation reaction, the apparatus to be used is not particularly limited. It is preferable to use a devolatilizing device or vented extruder consisting of a tank, or a devolatilizing device and an extruder arranged in series, and a devolatilizing device or vented extruder consisting of a heat exchanger and a devolatilizing tank More preferably, it is used.

  The reaction treatment temperature in the case of using a devolatilizer comprising a heat exchanger and a devolatilization tank is preferably 150 to 350 ° C, more preferably 200 to 300 ° C. If the reaction treatment temperature is less than 150 ° C., the cyclization condensation reaction may be insufficient and the residual volatile matter may increase. Conversely, when the reaction treatment temperature exceeds 350 ° C., the obtained polymer may be colored or decomposed.

  The reaction treatment pressure in the case of using a devolatilizer comprising a heat exchanger and a devolatilization tank is preferably 931 to 1.33 hPa (700 to 1 mmHg), more preferably 798 to 66.5 hPa (600 to 50 mmHg). When the reaction treatment pressure exceeds 931 hPa (700 mmHg), volatile components including alcohol may easily remain. Conversely, if the reaction treatment pressure is less than 1.33 hPa (1 mmHg), industrial implementation may be difficult.

  When using an extruder with a vent, one or a plurality of vents may be used, but it is preferable to have a plurality of vents.

  The reaction treatment temperature when using an extruder with a vent is preferably 150 to 350 ° C, more preferably 200 to 300 ° C. If the reaction treatment temperature is less than 150 ° C., the cyclization condensation reaction may be insufficient and the residual volatile matter may increase. Conversely, when the reaction treatment temperature exceeds 350 ° C., the obtained polymer may be colored or decomposed.

  The reaction processing pressure when using an extruder with a vent is preferably 931 to 1.33 hPa (700 to 1 mmHg), more preferably 798 to 13.3 hPa (600 to 10 mmHg). When the reaction treatment pressure exceeds 931 hPa (700 mmHg), volatile components including alcohol may easily remain. Conversely, if the reaction treatment pressure is less than 1.33 hPa (1 mmHg), industrial implementation may be difficult.

  In the case of a form in which a devolatilization step is used throughout the cyclization condensation reaction, the physical properties of the lactone ring-containing polymer obtained may deteriorate under severe heat treatment conditions, as will be described later. It is preferable to carry out by using an extruder with a vent etc. on the conditions as mild as possible.

  In the case where the devolatilization step is used in combination throughout the cyclization condensation reaction, the polymer (a) obtained in the polymerization step is preferably introduced into the cyclization condensation reaction device together with a solvent. Depending on the situation, it may be passed once again through a cyclocondensation reaction apparatus such as a vented extruder.

  You may perform the form used together only in a part of process, without using a devolatilization process over the whole process of cyclization condensation reaction. For example, the apparatus for producing the polymer (a) is further heated, and if necessary, a part of the devolatilization step is used together to advance the cyclization condensation reaction to some extent in advance, followed by the devolatilization step. Is a form in which a cyclization condensation reaction is simultaneously used to complete the reaction.

  In the form of using the devolatilization step throughout the cyclization condensation reaction described above, for example, when the polymer (a) is heat-treated at a high temperature of about 250 ° C. or higher using a twin-screw extruder. Depending on the thermal history, partial decomposition or the like may occur before the cyclization condensation reaction occurs, and the physical properties of the resulting lactone ring-containing polymer may deteriorate. Therefore, if the cyclization condensation reaction is allowed to proceed to some extent before the cyclization condensation reaction using the devolatilization process at the same time, the latter reaction conditions can be relaxed, and the physical properties of the resulting lactone ring-containing polymer deteriorated. Is preferable. As a particularly preferred form, for example, a form in which the devolatilization step is started after a lapse of time from the start of the cyclization condensation reaction, that is, a hydroxyl group and an ester present in the molecular chain of the polymer (a) obtained in the polymerization step A mode in which a group is preliminarily subjected to a cyclization condensation reaction to increase the cyclization condensation reaction rate to some extent and then a cyclization condensation reaction using a devolatilization step simultaneously is performed. Specifically, for example, a cyclization condensation reaction is allowed to proceed to a certain reaction rate in the presence of a solvent in advance using a kettle reactor, and then a reactor equipped with a devolatilizer, for example, heat exchange Preferred is a mode in which the cyclization condensation reaction is completed with a devolatilizer comprising a vessel and a devolatilization tank, an extruder with a vent, or the like. In particular, in the case of this form, it is more preferable that a catalyst for the cyclization condensation reaction is present.

  As described above, the hydroxyl group and ester group present in the molecular chain of the polymer (a) obtained in the polymerization step are preliminarily subjected to a cyclization condensation reaction to increase the cyclization condensation reaction rate to some extent. The method of carrying out the cyclization condensation reaction simultaneously using the volatilization process is a preferred form in obtaining the lactone ring-containing polymer in the present invention. With this form, a lactone ring-containing polymer having a higher glass transition temperature, a higher cyclization condensation reaction rate, and excellent heat resistance can be obtained. In this case, as a measure of the cyclization condensation reaction rate, for example, the mass reduction rate in the range of 150 to 300 ° C. in the dynamic TG measurement shown in the examples is preferably 2% or less, more preferably 1.5% or less. More preferably, it is 1% or less.

  The reactor that can be employed in the cyclization condensation reaction performed in advance before the cyclization condensation reaction using the devolatilization process at the same time is not particularly limited. For example, an autoclave, a kettle reactor, a heat exchanger And a devolatilizer comprising a devolatilization tank, and a vented extruder suitable for a cyclization condensation reaction using a devolatilization step at the same time can also be used. Of these reactors, an autoclave and a kettle reactor are particularly preferable. However, even when a reactor such as an extruder with a vent is used, the autoclave or kettle can be adjusted by adjusting the temperature conditions, barrel conditions, screw shape, screw operating conditions, etc. It is possible to carry out the cyclization condensation reaction in the same state as the reaction state in the type reactor.

  In the case of the cyclization condensation reaction carried out in advance before the cyclization condensation reaction using the devolatilization step at the same time, for example, a mixture containing the polymer (a) and the solvent obtained in the polymerization step is used as (i) a catalyst. And (ii) a method of performing a heat reaction without a catalyst, a method of performing the above (i) or (ii) under pressure, and the like.

  The “mixture containing the polymer (a) and the solvent” introduced into the cyclization condensation reaction in the lactone cyclization condensation step refers to the polymerization reaction mixture obtained in the polymerization step itself or once the solvent is removed. It means a mixture obtained by re-adding a solvent suitable for the cyclization condensation reaction later.

  The solvent that can be re-added in the cyclization condensation reaction that is carried out in advance before the cyclization condensation reaction using the devolatilization step at the same time is not particularly limited. For example, aromatic carbonization such as toluene, xylene, ethylbenzene, etc. Hydrogens; ketones such as methyl ethyl ketone and methyl isobutyl ketone; chloroform, DMSO, tetrahydrofuran; and the like. These solvents may be used alone or in combination of two or more. It is preferable to use the same type of solvent as that used in the polymerization step.

  Examples of the catalyst to be added in the method (i) include commonly used esterification catalysts such as p-toluenesulfonic acid or transesterification catalysts, basic compounds, organic carboxylates, and carbonates. In the invention, it is preferable to use the aforementioned organophosphorus compound. The addition timing of the catalyst is not particularly limited. For example, the catalyst may be added at the beginning of the reaction, may be added during the reaction, or may be added in both of them. The addition amount of the catalyst is not particularly limited, but for example, is preferably 0.001 to 5% by mass, more preferably 0.01 to 2.5% by mass with respect to the mass of the polymer (a). More preferably, it is 0.01-1 mass%, Most preferably, it is 0.05-0.5 mass%. Although the heating temperature and heating time of method (i) are not particularly limited, for example, the heating temperature is preferably room temperature to 180 ° C., more preferably 50 to 150 ° C., and the heating time is preferably 1 to 20 hours, more preferably 2 to 10 hours. If the heating temperature is less than room temperature or the heating time is less than 1 hour, the cyclization condensation reaction rate may be lowered. Conversely, if the heating temperature exceeds 180 ° C. or the heating time exceeds 20 hours, the resin may be colored or decomposed.

  In the method (ii), for example, the polymerization reaction mixture obtained in the polymerization step may be heated as it is using a pressure-resistant kettle reactor or the like. Although the heating temperature and heating time of method (ii) are not particularly limited, for example, the heating temperature is preferably 100 to 180 ° C, more preferably 100 to 150 ° C, and the heating time is preferably 1 to 20 hours, more preferably 2 to 10 hours. When the heating temperature is less than 100 ° C. or the heating time is less than 1 hour, the cyclization condensation reaction rate may be lowered. Conversely, if the heating temperature exceeds 180 ° C. or the heating time exceeds 20 hours, the resin may be colored or decomposed.

  In any method, there is no problem even under pressure depending on conditions.

  In the case of the cyclization condensation reaction performed in advance before the cyclization condensation reaction using the devolatilization step at the same time, there is no problem even if part of the solvent volatilizes spontaneously during the reaction.

  The mass reduction rate within the range of 150 to 300 ° C. in the dynamic TG measurement at the end of the cyclization condensation reaction performed in advance before the cyclization condensation reaction simultaneously used in combination with the devolatilization step, ie, immediately before the start of the devolatilization step is Preferably it is 2% or less, More preferably, it is 1.5% or less, More preferably, it is 1% or less. When the mass reduction rate exceeds 2%, the cyclization condensation reaction rate does not rise to a sufficiently high level even if the cyclization condensation reaction is performed simultaneously with the devolatilization step, and the physical properties of the resulting lactone ring-containing polymer. May deteriorate. In addition, when performing said cyclization condensation reaction, in addition to a polymer (a), you may coexist other thermoplastic resins.

  The hydroxyl group and ester group present in the molecular chain of the polymer (a) obtained in the polymerization step are preliminarily subjected to a cyclization condensation reaction to increase the cyclization condensation reaction rate to some extent. In the case of the form in which the cyclized condensation reaction is performed, the polymer obtained by the cyclized condensation reaction performed in advance (the polymer in which at least a part of the hydroxyl group and the ester group present in the molecular chain is subjected to the cyclized condensation reaction) and the solvent May be introduced into the cyclization condensation reaction using the devolatilization step at the same time, and if necessary, the polymer (at least a part of the hydroxyl group and ester group present in the molecular chain is cyclized and condensed). You may introduce | transduce into the cyclocondensation reaction which used the devolatilization process together, after passing through other processes, such as adding a solvent again after isolating the polymer which reacted.

  The devolatilization step is not limited to being completed at the same time as the cyclization condensation reaction, and may be completed after a lapse of time from the completion of the cyclization condensation reaction.

  The weight average molecular weight of the lactone ring-containing polymer is preferably 1,000 to 2,000,000, more preferably 5,000 to 1,000,000, still more preferably 10,000 to 500,000, particularly preferably. 50,000 to 500,000.

  The lactone ring-containing polymer preferably has a mass reduction rate in the range of 150 to 300 ° C. in dynamic TG measurement of 1% or less, more preferably 0.5% or less, and still more preferably 0.3% or less.

  Since the lactone ring-containing polymer has a high cyclization condensation reaction rate, it is possible to avoid the disadvantage that bubbles and silver streaks enter the molded product after molding. Furthermore, since the lactone ring structure is sufficiently introduced into the polymer due to the high cyclization condensation reaction rate, the obtained lactone ring-containing polymer has sufficiently high heat resistance.

  The lactone ring-containing polymer has a coloring degree (YI) of preferably 6 or less, more preferably 3 or less, still more preferably 2 or less, and particularly preferably 1 or less when a chloroform solution having a concentration of 15% by mass is used. . When the coloring degree (YI) exceeds 6, transparency may be impaired due to coloring, and may not be used for the intended purpose.

  The lactone ring-containing polymer has a 5% mass reduction temperature in thermal mass spectrometry (TG) of preferably 330 ° C. or higher, more preferably 350 ° C. or higher, and still more preferably 360 ° C. or higher. The 5% mass reduction temperature in thermal mass spectrometry (TG) is an index of thermal stability, and if it is less than 330 ° C., sufficient thermal stability may not be exhibited.

  The lactone ring-containing polymer has a glass transition temperature (Tg) of preferably 115 ° C. or higher, more preferably 125 ° C. or higher, still more preferably 130 ° C. or higher, and particularly preferably 140 ° C. or higher.

  The total amount of residual volatile components contained in the lactone ring-containing polymer is preferably 1,500 ppm or less, more preferably 1,000 ppm or less. If the total amount of residual volatile components exceeds 1,500 ppm, it may be colored due to alteration during molding, foaming, or molding defects such as silver streak.

  In applications requiring transparency, the lactone ring-containing polymer has a total light transmittance of preferably 85% or more measured by a method based on ASTM-D-1003 for a molded product obtained by injection molding. Preferably it is 88% or more, More preferably, it is 90% or more. The total light transmittance is an index of transparency, and if it is less than 85%, the transparency may be lowered and may not be used for applications requiring transparency.

≪Thermoplastic resin layer≫
The content ratio of the lactone ring-containing polymer in the thermoplastic resin layer is at least 50% by mass, preferably 60 to 100% by mass, more preferably 70 to 100% by mass, and further preferably 80 to 100% by mass. When the content of the lactone ring-containing polymer in the thermoplastic resin layer is less than 50% by mass, the effects of the present invention may not be sufficiently exhibited.

  The thermoplastic resin layer may contain a polymer other than the lactone ring-containing polymer (hereinafter sometimes referred to as “other polymer”) as another component. Examples of other polymers include olefin polymers such as polyethylene, polypropylene, ethylene-propylene copolymer, poly (4-methyl-1-pentene); halogens such as vinyl chloride, vinylidene chloride, and chlorinated vinyl resins. Acrylic polymer such as polymethyl methacrylate; Styrene polymer such as polystyrene, styrene-methyl methacrylate copolymer, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene block copolymer Polyesters such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate; polyamides such as nylon 6, nylon 66 and nylon 610; polyacetal; polycarbonate; polyphenylene oxide; Sulfides; polyetheretherketone; polysulfones; polyethersulfones; polyoxyethylene benzylidene alkylene; polyamideimide; polybutadiene rubber, rubber-like polymer such as ABS resin or ASA resin containing an acrylic rubber; and the like.

  The content of other polymers in the thermoplastic resin layer is preferably 0 to 50% by mass, more preferably 0 to 40% by mass, further preferably 0 to 30% by mass, and particularly preferably 0 to 20% by mass. .

  The thermoplastic resin layer may contain various additives. Examples of additives include antioxidants such as hindered phenols, phosphorus, and sulfur; stabilizers such as light stabilizers, weather stabilizers, and heat stabilizers; reinforcing materials such as glass fibers and carbon fibers; phenyls UV absorbers such as salicylate, (2,2′-hydroxy-5-methylphenyl) benzotriazole, 2-hydroxybenzophenone; near infrared absorbers; tris (dibromopropyl) phosphate, triallyl phosphate, antimony oxide, etc. Flame retardants; Antistatic agents such as anionic, cationic and nonionic surfactants; Colorants such as inorganic pigments, organic pigments and dyes; Organic fillers and inorganic fillers; Resin modifiers; Organic fillers and inorganic fillers Agents, plasticizers, lubricants, antistatic agents, flame retardants, and the like.

  The content of the additive in the thermoplastic resin layer is preferably 0 to 5% by mass, more preferably 0 to 2% by mass, and still more preferably 0 to 0.5% by mass.

  The thermoplastic resin layer is preferably used after being formed into a form such as a film or a sheet. The method for forming the thermoplastic resin layer is not particularly limited. For example, the lactone ring-containing polymer and other polymers and additives are sufficiently mixed by a conventionally known mixing method. From the thermoplastic resin composition, it can be formed into a film or sheet. Alternatively, the lactone ring-containing polymer and other polymers, additives, and the like may be made into separate solutions and then mixed to form a uniform mixed solution, and then formed into a film or sheet form.

  First, in order to produce a thermoplastic resin composition, for example, the above raw materials are pre-blended with a conventionally known mixer such as an omni mixer, and then the obtained mixture is extrusion kneaded. In this case, the mixer used for extrusion kneading is not particularly limited. For example, a conventionally known mixer such as an extruder such as a single screw extruder or a twin screw extruder or a pressure kneader can be used. .

  Examples of the molding method include conventionally known molding methods such as a solution casting method (solution casting method), a melt extrusion method, a calendar method, and a compression molding method. Among these molding methods, the solution casting method (solution casting method) and the melt extrusion method are preferable.

  Examples of the solvent used in the solution casting method (solution casting method) include aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as cyclohexane and decalin; esters such as ethyl acetate and butyl acetate Ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; alcohols such as methanol, ethanol, isopropanol, butanol, isobutanol, methyl cellosolve, ethyl cellosolve, and butyl cellosolve; ethers such as tetrahydrofuran and dioxane; dichloromethane, chloroform, and four Halogenated hydrocarbons such as carbon chloride; dimethylformamide; dimethyl sulfoxide; These solvents may be used alone or in combination of two or more.

  Examples of the apparatus for performing the solution casting method (solution casting method) include a drum casting machine, a band casting machine, and a spin coater.

  Examples of the melt extrusion method include a T-die method and an inflation method, and the molding temperature at that time is preferably 150 to 350 ° C., more preferably 200 to 300 ° C.

  When forming by the T-die method, a T-die is attached to the tip of a known single-screw extruder or twin-screw extruder, the film or sheet extruded into a film or sheet is wound up, and a roll film And get a sheet. At this time, it is possible to perform uniaxial stretching by appropriately adjusting the temperature of the winding roll and adding stretching in the extrusion direction. Also, simultaneous biaxial stretching, sequential biaxial stretching, and the like can be performed by stretching a film or sheet in a direction perpendicular to the extrusion direction.

  The thermoplastic resin layer may be an unstretched film or sheet or a stretched film or sheet. When it is a stretched film or sheet, it may be either a uniaxially stretched film or sheet or a biaxially stretched film or sheet. In the case of a biaxially stretched film or sheet, either a simultaneous biaxially stretched film or sheet or a sequential biaxially stretched film or sheet may be used. In the case of biaxial stretching, the mechanical strength is improved and the performance of the film or sheet is improved. The film or sheet constituting the thermoplastic resin layer can suppress the increase in retardation even when stretched by mixing other thermoplastic resins, and can maintain optical isotropy.

  The stretching temperature is preferably in the vicinity of the glass transition temperature of the thermoplastic resin composition as a raw material, and specifically, preferably (glass transition temperature-30 ° C.) to (glass transition temperature + 100 ° C.), more preferably It is within the range of (glass transition temperature−20 ° C.) to (glass transition temperature + 80 ° C.). If the stretching temperature is less than (glass transition temperature-30 ° C.), a sufficient stretching ratio may not be obtained. Conversely, when the stretching temperature exceeds (glass transition temperature + 100 ° C.), the resin composition may flow, and stable stretching may not be performed.

  The draw ratio defined by the area ratio is preferably in the range of 1.1 to 25 times, more preferably 1.3 to 10 times. If the draw ratio is less than 1.1 times, the toughness accompanying the drawing may not be improved. On the other hand, when the draw ratio exceeds 25 times, the effect of increasing the draw ratio may not be recognized.

  The stretching speed is unidirectional, preferably 10 to 20,000% / min, more preferably 100 to 10,000% / min. When the stretching speed is less than 10% / min, it takes time to obtain a sufficient stretching ratio, and the production cost may increase. On the other hand, when the stretching speed exceeds 20,000% / min, the stretched film or sheet may break.

  The film or sheet constituting the thermoplastic resin layer can be subjected to a heat treatment (annealing) after the stretching treatment in order to stabilize its optical isotropy and mechanical properties. The conditions for the heat treatment may be appropriately selected similarly to the conditions for the heat treatment performed on a conventionally known stretched film or sheet, and are not particularly limited.

  The thickness of the thermoplastic resin layer is preferably 5 μm to 5 mm. In the present invention, a thermoplastic resin layer having a thickness of 5 to 200 μm is distinguished as a film, and a thermoplastic resin layer having a thickness exceeding 200 μm and 5 mm or less is distinguished as a sheet. When a thermoplastic resin layer is a film, the thickness becomes like this. Preferably it is 5-200 micrometers, More preferably, it is 10-100 micrometers. When the thermoplastic resin layer is a sheet, the thickness is preferably more than 200 μm and 5 mm or less, more preferably 500 μm to 2 mm.

  The surface of the thermoplastic resin layer has a wet tension of preferably 40 mN / m or more, more preferably 50 mN / m or more, and even more preferably 55 mN / m or more. When the surface wetting tension is at least 40 mN / m or more, the adhesive strength between the thermoplastic resin layer and the substrate is further improved. In order to adjust the surface wetting tension, for example, corona discharge treatment, ozone spraying, ultraviolet irradiation, flame treatment, chemical treatment, and other conventionally known surface treatments can be performed.

≪Base material≫
The adhesive of this invention is used in order to adhere | attach a thermoplastic resin layer to a base material. The substrate is not particularly limited as long as high adhesiveness with the adhesive layer is obtained. For example, styrene resin, vinyl chloride resin, polycarbonate resin, polyester resin, (meth) acrylic Thermoplastic resins such as polyolefin resins, polyolefin resins, and polyamide resins; phenol resins, urea resins, melamine resins, unsaturated polyester resins, epoxy resins, silicone resins, polyurethane resins, polyimide resins, etc. Thermosetting resin: Tin-plated steel sheet, galvanized steel sheet, zinc-aluminum alloy-plated steel sheet, aluminum-plated steel sheet, aluminum plate, stainless steel plate, cold-rolled steel plate, titanium plate, copper plate, brass plate, phosphor bronze plate, etc .; , Maple, pine, cedar, hiba, spruce and other conifers, beech, oak, sen Hardwood such as china, hoo, wig, etc., wood such as plywood, lauan, laminated wood; paper such as fine paper, coated paper, art paper, recycled paper; soda glass, lead glass, borosilicate glass, quartz glass, etc. Glass; ceramics such as alumina, silica, titania, zirconia, ceria, silicon carbide, silicon nitride, and composites thereof; and the like. These base materials may be used independently or may use 2 or more types together.

≪Laminated body≫
The laminate of the present invention is characterized in that a layer containing a thermoplastic resin containing a lactone ring-containing polymer as a main component and a substrate are bonded with an adhesive for a lactone ring-containing polymer. The structure of the laminate may be at least two layers or three layers, or may be a multilayer having more than that. In any case, at least the thermoplastic resin layer is bonded to one surface of the base material, or is bonded to both surfaces of the base material. What is necessary is just to adjust suitably the dimension and thickness of a laminated body according to the use, and it is not specifically limited.

  The method of adhering the thermoplastic resin layer and the base material may be appropriately selected and used according to the type of the base material, and is not particularly limited. For example, in the case of two layers, Apply heat to at least one or both surfaces in advance, dry the adhesive as necessary, and then heat and pressure-bond the other to the adhesive layer or the other adhesive layer Adhesive method: Preliminary adhesive is applied to at least one or both surfaces, and the other adhesive is layered on the adhesive layer or the other adhesive layer before the adhesive is dried. A wet lamination method in which pressure is applied with a roller or the like while extruding.

  In the case of a normal thermoplastic resin, it is possible to bond by a hot pressing method such as pressing at a high temperature, but in that case, depending on the combination of thermoplastic resins, there are problems such as warping of the laminate. May occur. On the other hand, when the adhesive of the present invention is used, it is possible to adhere by laminating at a temperature of about 100 to 150 ° C. after applying the adhesive to the substrate in advance and drying it. In addition, defects such as warpage are unlikely to occur in the laminate.

  The method for applying the adhesive to the thermoplastic resin layer and / or the substrate and the method for drying the adhesive as necessary may be any conventionally known method and is not particularly limited. Moreover, the heating temperature and pressure bonding pressure in the thermal bonding method, and the pressure bonding pressure and drying conditions in the wet lamination method may be appropriately adjusted according to the type of the base material and the number of layers, and are particularly limited. is not.

≪Use of laminates≫
The laminate of the present invention is not only excellent in transparency and heat resistance of the lactone ring-containing polymer, but also has desired properties such as surface gloss and mechanical strength. If vinyl chloride resin, polycarbonate resin, polyester resin, (meth) acrylic resin, polyolefin resin, polyamide resin, etc. are used, the resulting laminate will be a transparent optical lens, optical element, OA equipment, automobile, etc. It can be applied to various uses such as transparent parts, optical film materials, and optical laminate materials. Alternatively, if a thermosetting resin, metal, wood, paper, glass, ceramics, or the like is used as the base material, the resulting laminate will be centered on carports, signboards / displays, light electrical / industrial parts, and automobiles. It is suitable for vehicle parts, vehicle interior materials, soundproof walls, building materials / store accessories, coating materials, protective films for depainting, thermoforming sheets for depainting, lighting equipment, furniture, door materials and the like.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the following examples, but may be appropriately modified within a range that can meet the purpose described above and below. It is also possible to implement, and they are all included in the technical scope of the present invention. Hereinafter, for convenience, “parts by mass” may be represented by “parts” and “mass%” may be represented by “wt%”.

  First, a method for evaluating a lactone ring-containing polymer, a thermoplastic resin layer, and a laminate will be described.

<Polymerization reaction rate, polymer composition analysis>
For the reaction rate during the polymerization reaction and the content of the specific monomer unit in the polymer, the amount of unreacted monomer in the obtained polymerization reaction mixture was measured using a gas chromatograph (GC17A, manufactured by Shimadzu Corporation). It was obtained by measuring using.

<Dynamic TG>
The polymer (or polymer solution or pellet) is once dissolved or diluted in tetrahydrofuran, poured into excess hexane or methanol for reprecipitation, and the taken out precipitate is vacuum dried (1 mmHg (1.33 hPa), 80 ° C. Volatile components and the like were removed by conducting the reaction for 3 hours or more, and the obtained white solid resin was analyzed by the following method (dynamic TG method).
Measuring apparatus: differential type differential thermal balance (Thermo Plus 2 TG-8120 Dynamic TG, manufactured by Rigaku Corporation)
Measurement conditions: Sample amount 5-10 mg
Temperature increase rate: 10 ° C / min
Atmosphere: Nitrogen flow 200 mL / min
Method: Step-like isothermal control method (controlled to a mass reduction rate value of 0.005% / s or less in the range from 60 ° C to 500 ° C)

<Containing ratio of lactone ring structure>
First, based on the amount of mass reduction that occurs when all hydroxyl groups are dealcoholated as methanol from the obtained polymer composition, 300 before the start of decomposition of the polymer from 150 ° C. before the mass reduction starts in dynamic TG measurement. The dealcoholization reaction rate was determined from the mass reduction due to the dealcoholization reaction up to ° C.

That is, in the dynamic TG measurement of the polymer having a lactone ring structure, the mass reduction rate between 150 ° C. and 300 ° C. is measured, and the obtained actual measurement value is defined as the actual mass reduction rate (X). On the other hand, from the composition of the polymer, the mass reduction rate when assuming that all the hydroxyl groups contained in the polymer composition become alcohol and dealcoholate because they are involved in the formation of the lactone ring (that is, 100 in the composition) % Mass reduction rate calculated assuming that the dealcoholization reaction occurred) is defined as the theoretical mass reduction rate (Y). The theoretical mass reduction rate (Y) is more specifically the molar ratio of raw material monomers having a structure (hydroxyl group) involved in the dealcoholization reaction in the polymer, that is, the raw material single amount in the polymer composition. It can be calculated from the body content. These values are calculated for the dealcoholization:
1- (actual mass reduction rate (X) / theoretical mass reduction rate (Y))
Substituting for, the value is obtained and expressed in percentage (%), the dealcoholization reaction rate is obtained. Then, the content (mass ratio) in the polymer composition of the raw material monomer having a structure (hydroxyl group) involved in lactone cyclization, assuming that the predetermined lactone cyclization has been performed by the dealcoholization reaction rate. The content ratio of the lactone ring structure in the polymer can be calculated by multiplying the reaction rate by the dealcoholization reaction rate.

  As an example, the content rate of the lactone ring structure in the pellet obtained in the production example of the thermoplastic resin layer described later is calculated. When the theoretical mass reduction rate (Y) of this polymer was determined, the molecular weight of methanol was 32, the molecular weight of methyl 2- (hydroxymethyl) acrylate was 116, and methyl 2- (hydroxymethyl) acrylate. Since the content (mass ratio) in the polymer is 20.0% by mass in terms of composition, (32/116) × 20.0≈5.52% by mass. On the other hand, the actual mass reduction rate (X) by dynamic TG measurement was 0.17% by mass. When these values are applied to the above-described dealcoholization calculation formula, 1− (0.17 / 5.52) ≈0.969, and the dealcoholization reaction rate is 96.9%. In the polymer, the content (20.0% by mass) of methyl 2- (hydroxymethyl) acrylate in the polymer is determined as having been subjected to predetermined lactone cyclization corresponding to the dealcoholization reaction rate. Is multiplied by the dealcoholization reaction rate (96.9% = 0.969), the content of the lactone ring structure in the polymer is 19.4 (20.0 × 0.969) mass%.

<Weight average molecular weight>
The weight average molecular weight of the polymer was determined in terms of polystyrene using a gel permeation chromatograph (GPC system, manufactured by Tosoh Corporation).

<Melt flow rate>
The melt flow rate was measured at a test temperature of 240 ° C. and a load of 10 kg in accordance with JIS-K6874.

<Thermal analysis of polymer>
The thermal analysis of the polymer was performed using a differential scanning calorimeter (DSC-8230, manufactured by Rigaku Corporation) under the conditions of about 10 mg of sample, a heating rate of 10 ° C./min, and a nitrogen flow of 50 mL / min. In addition, the glass transition temperature (Tg) was calculated | required by the midpoint method based on ASTM-D-3418.

<Peel strength>
Each sample of the laminate was cut into a width of 25 mm to obtain a test piece. Using a tensile tester, the peel strength was evaluated by measuring the force required to peel the thermoplastic resin layer from the substrate of this test piece in the direction of 180 ° at a tensile speed of 50 mm / min. The peel strength is expressed in kg / 25 mm.

  Next, production examples of the thermoplastic resin layer and the adhesive will be described.

<Thermoplastic resin layer>
In a 30 L capacity reactor equipped with a stirrer, temperature sensor, cooling pipe, and nitrogen introduction pipe, 8,000 g of methyl methacrylate (MMA) and 2,000 g of methyl 2- (hydroxymethyl) methyl acrylate (MHMA) were added. ) 10,000 g of 4-methyl-2-pentanone (methyl isobutyl ketone, MIBK), 5 g of n-dodecyl mercaptan were charged, and the temperature was raised to 105 ° C. while passing nitrogen, and when the mixture was refluxed, the polymerization initiator At the same time as adding 5.0 g of t-butylperoxyisopropyl carbonate (Kaya-Carbon BIC-75, manufactured by Kayaku Akzo Co., Ltd.), a solution comprising 10.0 g of t-butylperoxyisopropyl carbonate and 230 g of MIBK While dropping over 4 hours, solution polymerization is performed at about 105 to 120 ° C. under reflux, Aging was carried out over a period of 4 hours in La.

  To the obtained polymer solution, 30 g of stearyl phosphate / distearyl phosphate mixture (Phoslex A-18, manufactured by Sakai Chemical Industry Co., Ltd.) was added and cyclized at about 90-120 ° C. for 5 hours under reflux. A condensation reaction was performed. Next, the obtained polymer solution was a vent type screw twin screw extruder having a barrel temperature of 260 ° C., a rotation speed of 100 rpm, a degree of vacuum of 13.3 to 400 hPa (10 to 300 mmHg), a rear vent number of 1, and a forevent number of 4. (Φ = 29.75 mm, L / D = 30) is introduced at a processing rate of 2.0 kg / h in terms of resin amount, and is further subjected to cyclization condensation reaction and devolatilization in this extruder and extruded. As a result, transparent pellets of the lactone ring-containing polymer were obtained.

  The obtained lactone ring-containing polymer was measured for dynamic TG, and a mass loss of 0.17% by mass was detected. The lactone ring-containing polymer had a weight average molecular weight of 133,000, a melt flow rate of 6.5 g / 10 min, and a glass transition temperature of 131 ° C.

  This lactone ring-containing polymer pellet was melt-extruded from a coat hanger type T die having a width of 400 mm using a 50 mmφ single-screw extruder, and the thickness was determined as a layer containing a thermoplastic resin mainly composed of a lactone ring-containing polymer. About 100 μm of film A was obtained.

<Adhesive>
First, in a reactor equipped with a stirrer, a reflux condenser and a thermometer, 700 parts of water and 10 parts of 1,2-dichloroethane were charged and heated. After the temperature increase, 300 parts of ethyleneimine was added at 80 ° C. over 4 hours. After completion of the addition, the mixture was aged at 80 ° C. for 3 hours to complete the reaction to obtain a polyethyleneimine aqueous solution. After cooling, the viscosity of the obtained aqueous solution was measured with a B-type viscometer and found to be 275 mPa · s (25 ° C.). Moreover, when 5 wt% aqueous solution was prepared and pH was measured using the pH meter, it was pH10.8. Furthermore, when a predetermined amount of the aqueous solution was dried with a hot air dryer at 150 ° C. for 1 hour, the residue (nonvolatile content) was 30 wt%. The weight average molecular weight of polyethyleneimine was 70,000 as measured by gel permeation chromatography using pullulan as a standard substance. The amine value of polyethyleneimine was 18 mmol / g (solid content).

Adhesive 1
The polyethyleneimine aqueous solution (non-volatile content 30 wt%) synthesized above was diluted to 10 wt% with pure water. 100 parts of this 10 wt% polyethyleneimine aqueous solution is blended with 60 parts of a 10 wt% aqueous solution of a water-soluble polyepoxy compound (Denacol EX-810, manufactured by Nagase Chemitex Co., Ltd.) as a cross-linking agent. An aqueous solution was obtained. The functional group ratio of the epoxy group to the amino group in this adhesive was 0.3 in terms of molar ratio.

Adhesive 2
Similarly, the polyethyleneimine aqueous solution (non-volatile content 30 wt%) synthesized above was diluted to 10 wt% with pure water. To 100 parts of this 10 wt% polyethyleneimine aqueous solution, 60 parts of a 10 wt% aqueous solution of a water-soluble polyepoxy compound (Denacol EX-810, manufactured by Nagase Chemitex Co., Ltd.) was blended as a crosslinking agent. Furthermore, 25 parts of a 10 wt% aqueous solution of polyvinyl alcohol (Kuraray Poval PVA-110, manufactured by Kuraray Co., Ltd.) was blended to obtain a 10 wt% aqueous adhesive solution. The functional group ratio of the epoxy group to the amino group in this adhesive was 0.3 in terms of molar ratio.

  Next, production examples and evaluation results of the laminate will be described.

<Laminated body>
Laminate 1
Adhesive 1 with a bar coater so that the thickness of the adhesive layer when dried is 4 μm on one side of a polymethyl methacrylate (PMMA) film (“SUMIPEX TECHNOROY”, manufactured by Sumitomo Chemical Co., Ltd .; thickness 125 μm). Was applied. Subsequently, the film is dried in an oven at 150 ° C. for 1 minute, and immediately before the heating step is completed, the film A is superimposed on the adhesive layer, and laminating is performed with a laminator having a roll temperature of 100 ° C. The laminate 1 was obtained. The peel strength of the obtained laminate 1 was measured, and the appearance was visually observed. The results are shown in Table 1.

Laminate 2
Adhesive 2 with a bar coater so that the thickness of the adhesive layer when dried is 4 μm on one side of a polymethyl methacrylate (PMMA) film (“SUMIPEX TECHNOROY”, manufactured by Sumitomo Chemical Co., Ltd .; thickness 125 μm) Was applied. Subsequently, the film is dried in an oven at 150 ° C. for 1 minute, and immediately before the heating step is completed, the film A is superimposed on the adhesive layer, and laminating is performed with a laminator having a roll temperature of 100 ° C. The laminate 2 was obtained. The peel strength of the obtained laminate 2 was measured, and the appearance was visually observed. The results are shown in Table 1.

Laminate 3
Adhesive 1 was applied to one side of a galvanized steel sheet (thickness 0.5 mm) with a bar coater such that the thickness of the adhesive layer when dried was 4 μm. Subsequently, the film is dried in an oven at 150 ° C. for 1 minute, and immediately before the heating step is completed, the film A is superimposed on the adhesive layer, and laminating is performed with a laminator having a roll temperature of 100 ° C. The laminate 3 was obtained. The peel strength of the obtained laminate 3 was measured, and the appearance was visually observed. The results are shown in Table 1.

Laminate 4
Film A and polymethylmethacrylate (PMMA) film (“SUMIPEX TECHNOROY”, manufactured by Sumitomo Chemical Co., Ltd .; thickness: 125 μm) are superposed on each other for 5 minutes at a pressure of 50 kg / cm ² using a 220 ° C. hot press machine. The laminated body 4 of the film A and the polymethylmethacrylate film was obtained by hold | maintaining. The peel strength of the obtained laminate 4 was measured and the appearance was visually observed. The results are shown in Table 1.

  As is clear from Table 1, Examples 1, 2, and 3 are PMMA films and galvanized plates in which the film A used as a layer containing a thermoplastic resin containing a lactone ring-containing polymer as a main component is used as a base material. Since the steel sheet is bonded with adhesives 1 and 2 in which polyethyleneimine and an epoxy crosslinking agent are blended, the peel strength is high, there is no warp, and the appearance is good. Moreover, since Example 2 uses the adhesive 2 in which the polyvinyl alcohol-based resin is blended, the peel strength is higher than that in Example 1 in which the adhesive 1 without the polyvinyl alcohol-based resin is blended. .

  On the other hand, the comparative example is not bonded with an adhesive containing polyethyleneimine and an epoxy-based crosslinking agent, but is manufactured by a hot press method, so that the peel strength is low, the warp is large, and the appearance is poor. It is.

  Thus, a polyalkyleneimine and a crosslinking agent (for example, an epoxy-based crosslinking agent and / or an isocyanate-based crosslinking agent) are blended in adhering a layer containing a thermoplastic resin containing a lactone ring-containing polymer as a main component to a substrate. It can be seen that a laminated body having a good appearance without warping or the like having high adhesive strength between the thermoplastic resin layer and the substrate can be obtained by using an adhesive. It can also be seen that the peel strength of the laminate is improved by using an adhesive containing a polyvinyl alcohol resin.

  Since the adhesive of the present invention has very high adhesive strength with a lactone ring-containing polymer, the field of application of the lactone ring-containing polymer can be expanded. In addition, the laminate of the present invention exhibits not only transparency and heat resistance but also excellent properties of the lactone ring-containing polymer such as surface gloss and mechanical strength. As an excellent thermoplastic resin, for example, polycarbonate resin, methacrylic resin, styrenic resin, etc. have greatly contributed to the field.

Claims (11)

  Lactone ring-containing adhesive for adhering a layer containing a thermoplastic resin containing a lactone ring-containing polymer as a main component to a substrate, comprising a polyalkyleneimine and a crosslinking agent Polymer adhesive. The lactone ring-containing polymer has the following formula (1):

[Wherein, R ^1, R ² and R ³ are, independently of one another, represents a hydrogen atom or an organic residue having 1 to 20 carbon atoms; The organic residue may contain an oxygen atom
The adhesive of Claim 1 which has a lactone ring structure shown by these.   The adhesive according to claim 1 or 2, wherein the polyalkyleneimine is polyethyleneimine or a derivative thereof.   The adhesive according to any one of claims 1 to 3, wherein the polyalkyleneimine has a weight average molecular weight of 100 to 100,000.   The adhesive according to any one of claims 1 to 4, wherein the crosslinking agent is an epoxy crosslinking agent and / or an isocyanate crosslinking agent.   The adhesive according to claim 5, wherein the functional group ratio of the epoxy group in the epoxy-based crosslinking agent to the amino group in the polyalkyleneimine is 0.05 to 2.0 in terms of molar ratio.   The adhesive according to claim 5, wherein the functional group ratio of the isocyanate group in the isocyanate-based crosslinking agent to the amino group in the polyalkyleneimine is 0.5 to 2.0 in terms of molar ratio.   Furthermore, the polyvinyl alcohol resin is mix | blended, The adhesive agent of any one of Claims 1-7.   A layered product comprising a layer containing a thermoplastic resin containing a lactone ring-containing polymer as a main component and a substrate bonded with the adhesive according to any one of claims 1 to 8.   The base material contains at least one thermoplastic resin selected from the group consisting of styrene resin, vinyl chloride resin, polycarbonate resin, polyester resin, (meth) acrylic resin, polyolefin resin, and polyamide resin. The laminate according to claim 9.   The laminate according to claim 9, wherein the base material contains at least one material selected from the group consisting of thermosetting resin, metal, wood, paper, glass, and ceramics.