TW201505825A - Laminate - Google Patents

Abstract

An object of the invention is to provide a laminate superior in adhesion between a transparent resin film and a curable resin layer and to provide the transparent resin. The laminate of the invention has a transparent resin film which comprises one or more thermoplastic resin layers, and a curable resin layer which is laminated on at least one surface of the transparent resin film, wherein, the curable resin layer is obtained by curing a curable resin composition comprising a cage-type silsesquioxane resin, a thermoplastic resin composing the thermoplastic resin layer contacting with the curable resin layer is a copolymer of an alkyl methacrylate with an alkyl acrylate and has a deflection temperature under load of from 20 to 80 DEG C.

Description

Laminated body

The present invention relates to a laminate comprising a transparent resin film and a curable resin layer laminated on at least one surface of the transparent resin film, and a transparent resin film used in the laminate.

Since the transparent resin film made of an acrylic resin is excellent in transparency, it has been used as an optical film in various applications such as a display panel such as a liquid crystal display.

However, the surface hardness of the transparent resin film made of the acrylic resin is insufficient, and there is still room for improvement.

In the surface area of the acrylic resin film, a layered body in which the surface of the acrylic resin film is cured by photocuring a curable resin composition containing a cage-type sesquioxane resin, and having a surface hardness is disclosed.

However, the curable resin composition is applied onto the acrylic resin film and the obtained laminate is cured, and the adhesion between the acrylic resin film and the curable resin layer is insufficient. Therefore, the laminate disclosed in Patent Document 1 is subjected to a layer of C before the layer of the curable resin is laminated on the acrylic resin film. The surface of the layer of the curable resin layer of the olefinic resin film is subjected to a plasma discharge treatment in advance.

[Previous Technical Literature] [Patent Document]

Patent Document 1: Japanese Patent Laid-Open Publication No. 2009-221321

An object of the present invention is to provide a laminate and a transparent resin film which are excellent in adhesion between a transparent resin film and a curable resin layer.

The present inventors have conducted active research to solve the above problems, and have completed the present invention. That is, the present invention is constituted by the following constitution.

(1) A laminate comprising a transparent resin film made of one or more thermoplastic resin layers and a laminate of a curable resin layer laminated on at least one surface of the transparent resin film. The curable resin layer is characterized in that the curable resin composition containing the cage sesquioxane resin is cured, and the thermoplastic resin-based methacrylic acid constituting the thermoplastic resin layer in contact with the curable resin layer is characterized. A copolymer of an alkyl ester and an alkyl acrylate, and having a load deformation temperature of 20 to 80 ° C.

(2) The laminate according to the above (1), wherein the weight ratio of the alkyl methacrylate to the alkyl acrylate in the copolymer is methyl propyl The alkyl methacrylate is 40% by weight to 90% by weight based on 100% by weight of the total of the alkylate and the alkyl acrylate, and the alkyl acrylate is 60% by weight to 10% by weight.

(3) The laminate according to the above (1) or (2), wherein the alkyl methacrylate is methyl methacrylate, and the alkyl acrylate is n-butyl acrylate.

(4) A transparent resin film which is characterized by using the laminate according to any one of the above (1) to (3).

The transparent resin film of the laminate of the present invention is excellent in adhesion to the curable resin layer.

<Layered body>

The laminate of the present invention comprises a specific transparent resin film and a curable resin layer laminated on at least one side of the transparent resin film. In other words, the laminated system of the present invention comprises a transparent resin film, a laminate having a curable resin layer on both surfaces of the curable resin layer laminated on both surfaces of the transparent resin film, or a transparent resin film and a laminate in the transparent layer. A laminate of a single-sided curable resin layer on one side of the resin film.

The thickness of the laminate is usually 0.1 to 5.0 mm, preferably 0.2 to 3.0 mm, more preferably 0.3 to 2.0 mm.

Further, the ratio of the thickness of the transparent resin film to the curable resin layer (the thickness of the transparent resin film / the thickness of the curable resin layer) is preferably from 0.2 to 500, more preferably from 0.7 to 150, still more preferably from 1.5 to 40.

The thickness of the curable resin layer is preferably from 10 to 500 μm, more preferably from 20 to 300 μm, still more preferably from 50 to 200 μm.

[The thermoplastic resin layer]

The transparent resin film is composed of one or more thermoplastic resin layers, and the thermoplastic resin layer constituting the thermoplastic resin layer in contact with the curable resin layer is a specific methacrylic resin (hereinafter referred to as It is a methacrylic resin (a)). In other words, when the transparent resin film is formed of a plurality of layers of the thermoplastic resin layer, the two surface layers of the transparent resin film used in the laminate of the two layers of the curable resin layer are made of the methacrylic resin (a); At least one surface of the transparent resin film used in the laminate of the single-sided curable resin layer is made of a methacrylic resin (a).

(The thermoplastic resin layer made of methacrylic resin (a))

The methacrylic resin (a) constituting the thermoplastic resin layer in contact with the curable resin layer is a copolymer of an alkyl methacrylate and an alkyl acrylate, and has a load deformation temperature of 20 to 80 ° C, preferably 25 °. 75 ° C. The load deformation temperature was measured by setting the bending stress to 1.80 MPa in accordance with JIS K 7191-2.

The deformation temperature of the methacrylic resin (a) is in the above range In the case where the surface of the layer of the curable resin layer of the transparent resin film is not subjected to the plasma discharge treatment before the layer of the curable resin is laminated on the transparent resin film, the transparent resin film and the curable resin layer may be densely formed. A laminate with excellent properties.

In the above range, the load-deformation temperature of the methacrylic resin (a) is, for example, a method of preparing a monomer composition of the methacrylic resin (a) as described later; in the methacrylic resin (a) A method containing an additive, and the like.

The methacrylic resin (a) is a copolymer of an alkyl methacrylate and an alkyl acrylate, and is a copolymer having a load deformation temperature within the above range (hereinafter sometimes referred to as a copolymer (a)). The copolymer may contain, as a monomer, an alkyl methacrylate and an alkyl acrylate, and may contain other monomers copolymerizable with an alkyl methacrylate or an alkyl acrylate.

The weight ratio of the alkyl methacrylate to the alkyl acrylate in the copolymer (a) is preferably 100% by weight based on 100% by weight based on the total of the alkyl methacrylate and the alkyl acrylate. The weight %, the alkyl acrylate is 60% by weight to 10% by weight, more preferably 40% by weight to 80% by weight of the alkyl methacrylate, and 60% by weight to 20% by weight of the alkyl acrylate. However, the total of the monomers does not exceed 100% by weight.

The alkyl methacrylate is exemplified by, for example, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, and the like. The alkyl group of the alkyl methacrylate is usually from 1 to 8, more preferably from 1 to 4. Among them, methyl methacrylate is preferred.

As the alkyl acrylate, for example, methyl acrylate, C Ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and the like. The alkyl group of the alkyl acrylate is usually 1 to 8, preferably 1 to 4. Among them, n-butyl acrylate is preferred.

As the methacrylic resin (a), one type of copolymer (a) may be used, or two or more types of copolymer (a) may be used in combination. When two or more types of copolymers (a) are used as the methacrylic resin (a), the combination of the copolymer (a) is not particularly limited. For example, when the two copolymers (a) are mixed, the two copolymers (a) are preferably a copolymer of methyl methacrylate and n-butyl acrylate and a copolymer of methyl methacrylate and methyl acrylate. . The weight ratio of the copolymer of methyl methacrylate and n-butyl acrylate and the copolymer of methyl methacrylate and methyl acrylate is preferably methyl methacrylate based on 100% by weight of the total of the copolymers. The copolymer with n-butyl acrylate is 50-90% by weight, and the copolymer of methyl methacrylate and methyl acrylate is 50-10% by weight. More preferably, the copolymer of methyl methacrylate and n-butyl acrylate is 70 to 90% by weight, the copolymer of methyl methacrylate and methyl acrylate is 30 to 10% by weight.

The methacrylic resin (a) may optionally contain, for example, rubber particles; an alkyl sulfonate, a sodium alkyl sulfate, a stearic acid monoglycidyl ester, a polyether ester decylamine or the like; an antistatic agent; Antioxidant; flame retardant such as phosphate; slipper such as palmitic acid, stearyl alcohol; light stabilizer for hindered amine; benzotriazole ultraviolet absorber, benzophenone ultraviolet absorber, cyano Ultraviolet absorber such as acrylate-based ultraviolet absorber, malonate-based ultraviolet absorber, oxalic acid-based ultraviolet absorber, acetate ultraviolet absorber; light diffusing agent; dye; fluorescent whitening agent In addition, these additives may contain two or more of these types as needed.

For the rubber particles, for example, acrylic rubber particles, butadiene rubber particles, styrene-butadiene rubber particles, or the like can be used. Among them, acrylic rubber particles are preferable in terms of weather resistance and durability.

The acrylic rubber particles can be the same as those of the acrylic rubber particles described in JP-A-2013-022822.

The content of the rubber particles in the methacrylic resin (a) is 0 to 70% by weight, preferably 0 to 60% by weight based on 100% by weight based on the total of the methacrylic resin (a) and the rubber particles. More preferably 0 to 50% by weight.

(Synthesis method of methacrylic resin (a))

The method for synthesizing the methacrylic resin (a) is, for example, a method in which the monomer, the radical polymerization initiator, water, and a dispersant are fed into a reactor and heated to perform suspension polymerization while stirring.

The radical polymerization initiator is exemplified by, for example, lauryl peroxide, benzhydryl peroxide, di-tert-butyl peroxide, t-butylperoxy-2-ethylhexanoate, Tert-butylperoxy isobutyrate, tert-butylperoxypivalate, tert-butylperoxybenzoate, tert-butylperoxyacetate, diisopropyl a peroxide-based initiator such as a hydroxycarbonate, a di-t-butylperoxycarbonate or the like; 2,2'-azobisisobutyronitrile, 2,2'-azobis (2) An azo initiator such as 4-dimethylvaleronitrile or the like.

Suspension stabilizers can also be used, and suspension stabilizers are listed, for example, as polymethyl groups. Alkali metal acrylate (sodium salt, potassium salt, etc.), sodium dodecyl benzene sulfonate, sodium lauryl sulfate, sodium alkylnaphthalene sulfonate, sodium dialkyl sulfosuccinate, boric acid, sodium carbonate, hydrogen phosphate A conventional suspension stabilizer such as disodium, sodium dihydrogen phosphate or sodium sulfate.

In addition, chain transfer agents for adjusting the molecular weight of the polymer may also be used. The chain transfer agents are exemplified by, for example, alkyl mercaptans, alkyl sulfides, alkyl disulfides, thioglycolate, α-methylstyrene. A conventional chain transfer agent such as a dimer.

The amount of the radical polymerization initiator to be added is preferably 0.02 to 2 parts by weight, more preferably 0.05 to 1 part by weight, per 100 parts by weight of the total of the alkyl methacrylate and the alkyl acrylate.

The amount of the suspension stabilizer to be added is preferably 0.001 to 2 parts by weight, more preferably 0.01 to 0.5 parts by weight, per 100 parts by weight based on the total of the alkyl methacrylate and the alkyl acrylate.

The amount of the chain transfer agent is preferably from 0.01 to 3 parts by weight, more preferably from 0.05 to 1 part by weight, per 100 parts by weight of the total of the alkyl methacrylate and the alkyl acrylate.

The polymerization is preferably carried out at a relatively low temperature in such a manner that no monomer remains, and is usually heated at 60 to 80 ° C for 30 minutes to 3 hours with stirring, and the temperature is raised at 80 to 130 ° C for 10 minutes to 2 hours. Thereby the polymerization reaction is completed.

As the methacrylic resin (a), copolymer particles having an average particle diameter of about 100 to 800 μm are usually obtained.

(other thermoplastic resin layer)

When the transparent resin film is formed of two or more thermoplastic resin layers, it is different from the thermoplastic resin layer (hereinafter sometimes referred to as a thermoplastic resin layer (a)) made of the methacrylic resin (a). The resin of the thermoplastic resin layer is exemplified by, for example, a polycarbonate resin, a polyvinyl chloride resin, an acrylonitrile-butadiene-styrene resin, a low-density polyethylene resin, a high-density polyethylene resin, a linear low-density polyethylene resin, Polystyrene resin, polypropylene resin, acrylonitrile-styrene resin, cellulose acetate resin, ethylene-vinyl acetate resin, acrylic acid-acrylonitrile-styrene resin, acrylic acid-chlorinated polyethylene resin, ethylene-ethylene Alcohol resin, fluororesin, methyl methacrylate-styrene resin, polyacetal resin, polyamide resin, polyethylene terephthalate resin, polyfluorene resin, polyether oxime resin, methyl pentene Resin, polyarylate resin, polybutylene terephthalate resin, resin containing ethylenically unsaturated monomer unit containing an alicyclic structure, polyphenylene sulfide resin, polyphenylene ether resin, polyetheretherketone resin Extensive use Engineering plastics, as well as polyvinyl chloride elastomers, chlorinated polyethylene, ethylene-ethyl acrylate resin, thermoplastic polyurethane elastomers, thermoplastic polyester elastomers, ionic polymer resins, styrene One type of these may be used for the diene block polymer, the ethylene-propylene rubber, the polybutadiene resin, or the like, or two or more types may be used in combination.

When the transparent resin film is formed of two or more thermoplastic resin layers, the layer constitution of the transparent resin film is not particularly limited. For example, a polycarbonate resin layer and a laminated film having a three-layer structure of a thermoplastic resin layer (a) laminated on both surfaces of the resin layer (hereinafter sometimes referred to simply as a laminate) membrane).

In this case, the thickness of the polycarbonate resin layer is preferably from 0.1 to 5.0 mm, more preferably from 0.2 to 20 mm, and the thickness of the single layer of the thermoplastic resin layer (a) is preferably from 0.01 to 0.5 mm, more preferably from 0.02 to 0.02. 0.3mm. The thermoplastic resin layer (a) laminated on one surface of the polycarbonate resin layer and the thermoplastic resin layer (a) laminated on the other surface of the polycarbonate resin layer may have the same thickness or different thicknesses.

The polycarbonate resin of the material of the polycarbonate resin layer is exemplified by, for example, reacting a dihydric phenol with a carbonylating agent by an interfacial polycondensation method or a melt transesterification method, and prepolymerizing a carbonate by a solid phase transesterification method. The polymer obtained by polymerization is obtained by polymerizing a cyclic carbonate compound by a ring-opening polymerization method.

The dihydric phenol which is a raw material of the polycarbonate resin is exemplified by, for example, hydroquinone, resorcin, 4,4'-dihydroxybiphenyl, bis(4-hydroxyphenyl)methane, bis{(4-hydroxy-3). ,5-dimethyl)phenyl}methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2 - bis(4-hydroxyphenyl)propane (commonly known as bisphenol A), 2,2-bis{(4-hydroxy-3-methyl)phenyl}propane, 2,2-bis{(4-hydroxy-) 3,5-Dimethyl)phenyl}propane, 2,2-bis{(4-hydroxy-3,5-dibromo)phenyl}propane, 2,2-bis{(3-isopropyl-4) -hydroxy)phenyl}propane, 2,2-bis{(4-hydroxy-3-phenyl)phenyl}propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-dual ( 4-hydroxyphenyl)-3-methylbutane, 2,2-bis(4-hydroxyphenyl)-3,3-dimethylbutane, 2,4-bis(4-hydroxyphenyl)- 2-methylbutane, 2,2-bis(4-hydroxyphenyl)pentane, 2,2-bis(4-hydroxyphenyl)-4-methylpentyl Alkane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-4-isopropylcyclohexane, 1,1-bis(4-hydroxybenzene -3,3,5-trimethylcyclohexane, 9,9-bis(4-hydroxyphenyl)anthracene, 9,9-bis{(4-hydroxy-3-methyl)phenyl}anthracene , α,α'-bis(4-hydroxyphenyl)-o-diisopropylbenzene, α,α'-bis(4-hydroxyphenyl)-m-diisopropylbenzene, α,α'- Bis(4-hydroxyphenyl)-p-diisopropylbenzene, 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane, 4,4'-dihydroxydiphenyl Bismuth, 4,4'-dihydroxydiphenylarylene, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenyl Ether, 4,4'-dihydroxydiphenyl ester, etc., or two or more of these may be used as needed.

Among them, bisphenol A, 2,2-bis{(4-hydroxy-3-methyl)phenyl}propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2- are preferably used. Bis(4-hydroxyphenyl)-3-methylbutane, 2,2-bis(4-hydroxyphenyl)-3,3-dimethylbutane, 2,2-bis(4-hydroxyphenyl) -4-methylpentane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane and α,α'-bis(4-hydroxyphenyl)-inter - 2 or more of dihydric phenols selected from diisopropylbenzene, more preferably bisphenol A alone, or 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethyl Cyclohexane and selected from bisphenol A, 2,2-bis{(4-hydroxy-3-methyl)phenyl}propane and α,α'-bis(4-hydroxyphenyl)-m-isopropylene One or more kinds of dihydric phenols of benzene.

The carbonylating agent which is a raw material of a carbonate resin is, for example, a carbonium halide such as carbonium chloride; a carbonate such as diphenyl carbonate; a halogenated acid ester such as a dihaloformate of a dihydric phenol, etc., which may be used as needed. Two or more of these.

The other thermoplastic resin layer may optionally contain, for example, the above rubber particles; an alkyl sulfonate, a sodium alkyl sulfate, a stearic acid monoglycidyl ester, a polyether ester decylamine or the like; an antioxidant such as a hindered phenol; a flame retardant such as a phosphate ester; a slip agent such as palmitic acid or stearyl alcohol; a light stabilizer for a hindered amine; a benzotriazole ultraviolet absorber, a benzophenone ultraviolet absorber, and a cyanoacrylate; An ultraviolet absorber such as a UV absorber, a malonate-based ultraviolet absorber, a grassy anilide-based ultraviolet absorber, or an acetate ultraviolet absorber; a light diffusing agent; a dye; a fluorescent whitening agent; The additive may contain two or more of these as needed.

[curable resin layer]

The curable resin layer is obtained by curing a curable resin composition containing a cage type sesquiterpene oxide resin.

The curable resin composition contains a cage sesquioxane resin, and may contain an acrylic monomer, an acrylic resin, or the like as necessary. The curable resin composition has thermosetting property or photocurability, and has fluidity or plasticity. Further, the curable resin composition can be cured by heat treatment or active energy ray irradiation or the like.

The content of the cage sesquioxane resin in the curable resin composition is preferably 100% by weight or more, more preferably 5% by weight to 30% by weight, more preferably 5 to 30% by weight, based on the curable resin composition. 10~25% by weight. When the content ratio of the cage sesquioxane is within the above range, it can be a laminate having excellent surface hardness and heat resistance and good appearance.

Moreover, by adjusting the content ratio of the cage sesquioxane resin, it is adjustable When the glass transition temperature of the sclerosing resin layer is the same as the glass transition temperature of the other resin used in combination with the cage sesquioxane resin, the glass transition temperature is the same as that of the cage sesquioxane resin. The glass transition temperature of the curable resin layer can be adjusted by appropriately adjusting the content ratio of the cage sesquioxane resin.

The content ratio of the acrylic monomer is preferably 97% by weight or less, more preferably 70 to 95% by weight, still more preferably 75 to 90% by weight, based on the curable resin composition. When the content ratio of the acrylic monomer is within the above range, it can be a laminate having excellent surface hardness.

(Cage sesquioxane resin)

As the cage type sesquioxane resin, a curable cage type sesquiterpene resin having thermosetting property or photocurability is preferably used. The caged sesquiterpene oxide resin is exemplified by, for example, hydrolyzing and partially condensing the hydrazine compound represented by the following formula (1) in the presence of an organic polar solvent and a basic catalyst, followed by a non-polar solvent and a basic contact. A resin obtained by recondensing the obtained hydrolyzate in the presence of a medium.

General formula (1): RSiX ₃ ... (1)

(In the formula (1), R represents an organic functional group having a group of a (meth)acryl fluorenyl group, a glycidyl group, and a vinyl group, and X represents a hydrolyzable group).

In the present invention, the resin is preferably a resin represented by the following formula (2).

General formula (2): [RSiO _3/2 ] _n ... (2)

(In the formula (2), R represents an organic functional group having any one of a (meth) acryloyl group, a glycidyl group, and a vinyl group, and n represents 8, 10, 12 or 14).

When the cage type sesquiterpene oxide resin is contained in the curable resin composition, the surface hardness is improved.

R in the general formulae (1) and (2) is preferably represented by the following general formula (3), (4) or (5). Further, in the formula (3), R ¹ represents a hydrogen atom or a methyl group. Further, in the general formulae (3) and (4), m represents an integer of 1 to 3.

[Chemical 3] CH ₂ =CH-...(5)

The cage sesquioxane resin preferably has a reactive functional group formed by an organic functional group having a (meth) acryl fluorenyl group, a glycidyl group or a vinyl group in all of the ruthenium atoms in the resin, and has a molecular weight distribution and A curable cage type sesquiterpene oxide resin whose molecular structure is controlled, but a part of the organic functional group may be substituted by an alkyl group, a phenyl group or the like.

Further, the molecular structure of the cage sesquioxane resin may not be a fully closed polyhedral structure, but may be, for example, a partially cracked structure. Further, the average molecular weight of the cage sesquioxane resin is not particularly limited, and the cage sesquioxane resin may also be an oligomer.

(acrylic monomer)

The acrylic single system means a (meth) acrylate monomer having one or more (meth) propylene fluorenyloxy groups in the molecule (hereinafter referred to as a (meth) acrylate monomer), and has 2 in the molecule. At least one (meth) acrylate oxy group (meth) acrylate oligomer (hereinafter referred to as (meth) acrylate oligomer) or the like containing at least (meth) propylene oxime compound 1 species.

Further, the following (meth) propylene fluorenyloxy group means an acryloxy group and a methacryloxy group, and the (meth) acrylate monomer and the (meth) acrylate oligomer are also the same.

<(Meth)acrylate monomer class>

The (meth) acrylate monomer is exemplified by a monofunctional (meth) acrylate monomer having one (meth) propylene fluorenyloxy group in the molecule (hereinafter referred to as a monofunctional (meth) acrylate monomer). a bifunctional (meth) acrylate monomer having two (meth) acryloxy groups in the molecule (hereinafter referred to as a bifunctional (meth) acrylate monomer) and having at least three or more molecules in the molecule A polyfunctional (meth) acrylate monomer (hereinafter referred to as a polyfunctional (meth) acrylate monomer) of (meth) acryloxy group. One type or two or more types may be used for the (meth) acrylate monomers.

The monofunctional (meth) acrylate monomer as an example of the (meth) acrylate monomer is exemplified by, for example, tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) Hydroxypropyl acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate Ester, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentenyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate , phenoxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, ethyl carbitol (meth)acrylate, Trimethylolpropane mono (meth) acrylate, pentaerythritol mono (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, in addition, as a carboxyl group-containing (meth) acrylate monomer For example, 2-(meth)acryloxyethyl phthalate, 2-(meth) propylene oxiranyl ethyl hexahydroortylene Dicarboxylate, carboxyethyl (meth)acrylate, 2-(meth)acryloxyethyl succinic acid, N-(methyl) propylene oxime-N', N'-dicarboxy-pair - phenylenediamine, 4-(meth)acryloxyethyltrimellitic acid, and the like.

Further, the monofunctional (meth) acrylate monomer contains a vinyl group-containing monomer such as N-vinylpyrrolidone and a content of 4-(meth)acryloylamino-1-carboxymethylpiperidine or the like. A monomer of (meth)acrylonitrile-based amine group.

Examples of the bifunctional (meth) acrylate monomer which is one example of the (meth) acrylate monomer are, for example, an alkanediol di(meth)acrylate or a polyoxyalkylene glycol di(meth)acrylate. , halogen-substituted alkanediol di(meth)acrylates, di(meth)acrylates of fatty acid polyols, di(meth)acrylates of bisphenol A or bisphenol F alkylene oxide adducts The epoxy group of the bisphenol A or the bisphenol F is not limited to these, and various types can be used. Specifically, it is exemplified by ethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6 -Hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolpropane di(meth)acrylic acid Ester, pentaerythritol di(meth)acrylate, di-trimethylolpropane di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, Dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol II (Meth) acrylate, in addition, examples are hydroxypivalate neopentyl glycol di(meth) acrylate, 2,2-bis[4-(methyl) propyl Iridyloxyethoxyethoxyphenyl]propane, 2,2-bis[4-(methyl)propenyloxyethoxyethoxycyclohexyl]propane, 2,2-bis[4- (Meth) propylene methoxy ethoxy ethoxy phenyl] methane, hydrogenated dicyclopentadienyl di (meth) acrylate, cis (hydroxyethyl) isocyanurate di (methyl) Acrylates.

Examples of the polyfunctional (meth) acrylate monomer which is one example of the (meth) acrylate monomer are glycerol tri(meth) acrylate, trimethylolpropane tri (meth) acrylate, and the like. - Trimethylolpropane tri(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, di-pentaerythritol Poly(meth)acrylate of a trihydric or higher aliphatic polyol such as tetrakis(meth)acrylate, dipentaerythritol penta(meth)acrylate or dipentaerythritol hexa(meth)acrylate; or a trivalent or higher halogen Poly(meth) acrylate of substituted polyol, tri(meth) acrylate of alkylene oxide adduct of glycerol, tris(methyl) of alkylene oxide adduct of trimethylolpropane Acrylate, 1,1,1-para[(methyl)acryloxyethoxyethoxyethoxy]propane, hydroxy(hydroxyethyl)isocyanurate tri(meth)acrylate, and the like.

<(Meth)acrylate oligomer>

The (meth) acrylate oligomer is exemplified by a polyfunctional urethane (meth) acrylate oligomer having two or more functional groups (hereinafter referred to as polyfunctional urethane (meth) acrylate oligomerization) Polyfunctional polyester (meth) acrylate oligomer (hereinafter referred to as polyfunctional polyester) (Meth) acrylate oligomer), a bifunctional or higher polyfunctional epoxy (meth) acrylate oligomer (hereinafter referred to as a polyfunctional epoxy (meth) acrylate oligomer), or the like. One type or two or more types may be used for the (meth) acrylate oligomer.

The polyfunctional urethane (meth) acrylate oligomer of one example of the (meth) acrylate oligomer is exemplified by having at least one (meth) acryloxy group and a hydroxyl group in one molecule (A) a urethane reaction product of a acrylate monomer and a polyisocyanate; a (meth) acrylate monomer having at least one (meth) propylene oxime group and a hydroxyl group in one molecule, and a polyol The urethanation reaction product of an isocyanate compound obtained by reacting with a polyisocyanate or the like.

The (meth) acrylate monomer having at least one (meth) acryloxy group and a hydroxyl group in one molecule used for the urethanation reaction is exemplified by, for example, 2-hydroxyethyl (meth) acrylate, ( 2-hydroxypropyl methacrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerol di(meth) acrylate, three Hydroxymethylpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and the like.

The polyisocyanate used in the urethanation reaction is exemplified by, for example, hexamethylene diisocyanate, quaternary acid diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, toluene diisocyanate, xylene diisocyanate, a diisocyanate obtained by hydrogenating an aromatic isocyanate in the diisocyanate (for example, hydrogenated toluene diisocyanate, diisocyanate such as xylene diisocyanate), triphenylmethane triisocyanate A polyisocyanate of two or three of an acid ester, dimethylene triphenyl triisocyanate, or a polyisocyanate obtained by multimerizing a diisocyanate.

The polyols used in the urethanation reaction are generally selected from the group consisting of polyester polyols, polyether polyols, and the like, in addition to aromatic, aliphatic, and alicyclic aliphatic polyols. The aliphatic and alicyclic polyols are exemplified by, for example, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, ethylene glycol, propylene glycol, trimethylolethane, trimethylolpropane. , dimethylol heptane, dimethylolpropionic acid, dimethylolbutanoic acid, glycerol, hydrogenated bisphenol A, and the like.

The polyether polyol which is one example of the polyol used for the urethanation reaction is exemplified by, for example, a dehydration condensation reaction of the above polyol with a polybasic carboxylic acid (anhydride). The compound of the polybasic carboxylic acid is exemplified by, for example, succinic acid (anhydride), adipic acid, maleic acid (anhydride), trimellitic acid (anhydride), hexahydrophthalic acid (anhydride), phthalic acid ( Anhydride), isophthalic acid, terephthalic acid, and the like.

The polyether polyol of one example of the polyol used in the urethanation reaction is exemplified by, for example, a polyalkylene glycol; a polyoxyalkylene group obtained by reacting the above polyol or a phenol with an alkylene oxide Alcohol, etc.

A polyfunctional polyester (meth) acrylate oligomer which is an example of a (meth) acrylate oligomer is a dehydration condensation reaction of (meth)acrylic acid, a polybasic carboxylic acid (anhydride), and a polyhydric alcohol. Got it. The polybasic carboxylic acid (anhydride) used in the dehydration condensation reaction is exemplified by, for example, succinic acid (anhydride), adipic acid, maleic acid (anhydride), itaconic acid (anhydride), trimellitic acid (anhydride), and benzene. Tetraacid (anhydride), hexahydrophthalic acid (anhydride), phthalic acid (anhydride), isophthalic acid, terephthalic acid, and the like.

The polyol used in the dehydration condensation reaction is exemplified by, for example, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, dimethylol heptane, Dimethylolpropionic acid, dimethylolbutanoic acid, trimethylolpropane, di-trimethylolpropane, pentaerythritol, dipentaerythritol, and the like.

A polyfunctional epoxy (meth) acrylate oligomer which is an example of a (meth) acrylate oligomer is obtained by an addition reaction of a polyglycidyl ether and (meth)acrylic acid.

The polyglycidyl ether used in the addition reaction is exemplified by, for example, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, bisphenol A condensed water. Glycerol ether, etc.

(acrylic resin)

The acrylic resin is, for example, 50 to 100% by weight of an alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms, and 0 to 50% by weight of an acrylate, based on the total amount of all the monomers. A thermoplastic polymer obtained by polymerization of a monomer obtained by copolymerizing other ethylene monomers in an amount of from 0 to 49% by weight. Here, the acrylate is preferably in the range of 0.1 to 50% by weight, more preferably 0.5 to 50% by weight. Therefore, a more preferable copolymerization ratio of the alkyl methacrylate is in the range of 50 to 99.9% by weight, and a more preferable copolymerization ratio is in the range of 50 to 99.5% by weight.

In addition, in the present specification, the term "monomer" is not limited to a single monomer, but also includes a state in which a plurality of monomers are mixed.

The alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms used for constituting the thermoplastic polymer is exemplified by, for example, methyl methacrylate, Ethyl acrylate, butyl methacrylate or the like, especially methyl methacrylate, can be preferably used.

The acrylate used to form the thermoplastic polymer as needed is usually an alkyl acrylate, and the alkyl group is preferably a carbon number of about 1 to 8. Specifically, it is exemplified by methyl acrylate, ethyl acrylate, butyl acrylate, and the like.

Further, other vinyl monomers copolymerizable with at least one selected from the group consisting of alkyl methacrylate and alkyl acrylate, which are used to form the thermoplastic polymer, may be used in various conventionally known in the art. Examples of the compound include an aromatic vinyl compound such as styrene, an ethylene cyanide compound such as acrylonitrile, and the like.

The glass transition temperature of the acrylic resin is preferably 40 ° C or higher, more preferably 60 ° C or higher.

The glass transition temperature can be appropriately set by changing the kind and amount of other ethylene monomer copolymerizable with the alkyl methacrylate. Further, since the glass transition temperature of the homopolymer of methyl methacrylate is about 106 ° C, when methyl methacrylate is used as the alkyl methacrylate, the glass transition temperature of the obtained acrylic resin is usually 106 ° C or lower.

The polymerization method of the acrylic resin is not particularly limited, and it can be carried out by a general suspension polymerization, emulsion polymerization, or bulk polymerization. Further, in order to obtain an appropriate glass transition temperature or to obtain a viscosity indicating a formability to a film, a chain transfer agent is preferably used in the polymerization. The amount of the chain transfer agent may be appropriately determined depending on the type and composition of the monomer.

(additive)

The curable resin composition may optionally contain a filler-based additive, a photopolymerization initiator, a diluent, or the like, as long as it does not inhibit the curability.

The photopolymerization initiator can be appropriately selected from commercially available ones, and examples thereof include photopolymerization initiators such as phenylalkanone type, mercapto phosphine oxide type, and titanocene type.

The diluent is exemplified by a solvent such as a conventional one used for adjusting the viscosity and the like. The content of the solvent is preferably 5% by weight or less based on the curable resin composition, and preferably contains no solvent. When the content of the solvent is more than 5% by weight, it takes time to reduce the production efficiency in consideration of the volatilization removal step of the solvent, and there is a possibility that the properties of the formed film are lowered by the presence of a residual solvent or the like inside the cured film. Further, the curable resin composition is preferably one which does not generate volatiles upon curing.

[Method for Producing Transparent Resin Film]

In the method for producing a transparent resin film, when the transparent resin film is formed only of the methacrylic resin (a), for example, the thermoplastic resin constituting the transparent resin film is melt-extruded by using an extruder, and the self-molding is performed. a melt extrusion method in which at least one surface of the film obtained by spraying the nozzle is brought into contact with a roll or a conveyor belt to form a film; and the thermoplastic resin constituting the transparent resin film is formed into a film-like pressure forming by using a heating and pressing device. Wait.

When the transparent resin film is a laminated film, for example, a uniaxial or biaxial extruder is used, and the methacrylic resin (a) and the resin constituting the other thermoplastic resin layer are separately melted and kneaded, and then passed through the feeding tube. A method of laminating a die mouth or a branch die.

<Manufacturing method of laminated body>

The method for producing the laminate is, for example, a method in which the curable resin composition is applied to the surface of the transparent resin film and cured, and the like.

The method of applying the curable resin composition to the transparent resin film is not particularly limited, and examples thereof include a coating method using a conventional coating device. Further, the coating method may be any coating method which is excellent in uniformity and coating shape, and examples thereof include die coating, lip coating, gravure coating, roll coating, reverse coating, and blade coating. Conventional coating methods such as blade coating, extrusion coating, slit coating, wire bar coating, and extrusion coating.

The coating thickness (wet thickness) of the curable resin composition may be applied so as to be the thickness of the curable resin layer, and is preferably 0.01 to 0.8 mm, more preferably 0.03 to 0.4 mm. The coating thickness in the above range is preferably applied uniformly and from the viewpoint of poor deformation due to curing and shrinkage of the curable resin composition.

The method of curing the curable resin layer to form a curable resin layer is, for example, a heat curing method in which a heat-curable resin composition is subjected to heat treatment, and a photo-curing method in which an energy line such as ultraviolet rays is applied to the curable resin composition.

The heat curing method is exemplified by a method of using a heat treatment apparatus such as a heat treatment furnace and holding it at a temperature of 70 to 150 ° C for 5 to 60 minutes.

Photohardening is exemplified by, for example, using an ultraviolet lamp to illuminate violet The method of the outside line, etc.

The ultraviolet lamp is exemplified by, for example, a metal halide lamp, a high pressure mercury lamp, a low pressure mercury lamp, a pulse type xenon lamp, a xenon/mercury hybrid lamp, a low pressure germicidal lamp, an electrodeless lamp, etc., among which a metal halide lamp or a high pressure mercury lamp is preferable.

The irradiation conditions may be appropriately adjusted depending on the ultraviolet lamp to be used. For example, the exposure amount of the ultraviolet light is preferably from 20 to 10,000 mJ/cm ² , more preferably from 100 to 10,000 mJ/cm ² .

When the curable resin composition is cured by a photo-curing method, the curable resin composition is preferably applied onto the transparent resin film, and then the surface of the curable resin composition is coated with a transparent protective film before the energy ray is irradiated. Thereby, when the curable resin composition is irradiated with an energy ray to perform a photohardening reaction, the reaction inhibition by oxygen can be suppressed.

Further, a transparent protective film having a small oxygen permeability is preferably used as the transparent protective film. Thereby, the oxygen concentration on the surface of the curable resin composition can be made 1% or less, and further 0.1% or less.

The material of the transparent protective film is exemplified by, for example, PET (polyethylene terephthalate), PEN (polyethylene naphthalate), PBT (polybutylene terephthalate), PC (polycarbonate), Plastics such as polypropylene, polyethylene, acetate resin, acrylic resin, fluorinated vinyl resin, polyamide, polyacrylate, cellophane, polyether oxime, norbornene resin. These plastics may be used alone or in combination of two or more. Further, since the transparent protective film is required to be peeled off from the curable resin composition (curable resin layer) after curing, it is preferably transparent. The surface of the film is subjected to an easy peeling treatment such as polyoxymethylene coating or fluorine coating.

Since the laminated body of the present invention is excellent in adhesion between the transparent resin film and the curable resin layer, it is suitable for display devices such as optical displays, protective glass, building materials, window glass, and window materials for vehicles, and various industrial applications. .

[Examples]

Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited by the following examples. In the following examples, the parts indicating the content ratio and the amount used are based on weight unless otherwise specified.

(copolymer)

The copolymers used in the following examples and comparative examples are as follows.

Copolymer 1: A copolymer of methyl methacrylate/n-butyl acrylate = 60/40 (weight ratio) synthesized as follows (load deformation temperature: 39 ° C).

Copolymer 2: a copolymer of methyl methacrylate/n-butyl acrylate = 80/20 (weight ratio) synthesized as follows (load deformation temperature: 63 ° C).

Copolymer 3: a copolymer of methyl methacrylate/methyl acrylate = 90/10 (weight ratio) synthesized as follows.

Copolymer 4: a copolymer of methyl methacrylate/methyl acrylate = 97.5 / 2.5 (weight ratio) synthesized as follows (load deformation temperature: 101 ° C).

In addition, the load deformation temperature is a measured value measured by using a bending stress of 1.80 MPa based on JIS K 7191-2.

[Synthesis Example of Copolymer 1]

60 parts by weight of methyl methacrylate, 40 parts by weight of n-butyl acrylate, 0.45 parts by weight of lauryl peroxide, 0.11 parts by weight of dodecyl mercaptan, 120 parts by weight of ion-exchanged water, 1.2% polymethacrylic acid 0.03 parts by weight of a sodium aqueous solution, 0.24 parts by weight of disodium hydrogen phosphate heptahydrate salt, and 0.21 parts by weight of monosodium hydrogen phosphate were heated and heated to obtain a copolymer 1 in the form of particles.

In the obtained copolymer 1, the content of n-butyl acrylate was 40% by weight based on 100% by weight based on the total of methyl methacrylate and n-butyl acrylate. Here, the content of n-butyl acrylate is measured by a thermal decomposition gas chromatograph.

[Synthesis Example of Copolymer 2]

The mixing amount of methyl methacrylate was changed to 80 parts by weight, the mixing amount of n-butyl acrylate was changed to 20 parts by weight, the mixing amount of dodecyl mercaptan was changed to 0.14 parts by weight, and the mixture of monosodium hydrogen phosphate was mixed. The amount of the copolymer 2 was obtained in the same manner as in the above [Synthesis Example of Copolymer 1], except that the amount was changed to 0.28 parts by weight. In the obtained copolymer 2, the content of n-butyl acrylate was measured in the same manner as in [Synthesis Example of Copolymer 1], and was 20% by weight based on 100% by weight based on the total of methyl methacrylate and n-butyl acrylate.

[Synthesis Example of Copolymer 3]

90 parts by weight of methyl methacrylate, 10 parts by weight of methyl acrylate, 0.2 parts by weight of lauryl peroxide, 0.38 parts by weight of dodecyl mercaptan, 300 parts by weight of ion-exchanged water, 1.2% sodium polymethacrylate 0.06 parts by weight of an aqueous solution, 0.6 parts by weight of polyoxylated propyl ether, 0.3 parts by weight of disodium hydrogen phosphate heptahydrate salt, and 0.3 parts by weight of monosodium hydrogen phosphate were heated and heated to obtain a copolymer 3 in the form of particles.

In the obtained copolymer 3, the content of methyl acrylate was 10% by weight based on 100% by weight based on the total of methyl methacrylate and methyl acrylate. Here, the content of methyl acrylate is measured by a thermal decomposition gas chromatograph.

[Synthesis Example of Copolymer 4]

The copolymer 4 was obtained in the same manner as in the above [Synthesis Example of Copolymer 3] except that the methyl methacrylate was changed to 97.5 parts by weight and the methyl acrylate was changed to 2.5 parts by weight. In the obtained copolymer 4, the content of methyl acrylate was measured in the same manner as in [Synthesis Example of Copolymer 3], and was 2.5% by weight based on 100% by weight based on the total of methyl methacrylate and methyl acrylate.

(curable resin composition) [Synthesis Example 1]

Into a reaction vessel equipped with a stirrer, a dropping funnel, and a thermometer, 400 ml of 2-propanol (IPA) as a solvent and a 5% aqueous solution of tetramethylammonium hydroxide (TMAH aqueous solution) as a basic catalyst were charged. IPA 150ml with 3-methacryloxypropyltrimethoxydecane (MTMS: 126.9 g of "SZ-6300" manufactured by TORAY‧DOW CORNING‧SILICONE Co., Ltd. was fed into a dropping funnel, and the IPMS solution of MTMS was added dropwise at room temperature for 30 minutes while stirring the reaction vessel. After the completion of the dropwise addition of MTMS, stirring was carried out for 2 hours without heating. After stirring for 2 hours, the solvent was removed under reduced pressure and dissolved in 500 ml of toluene. The reaction solution was washed with saturated brine until neutral, and then dried over anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered and concentrated to obtain 86 g of a hydrolyzate (sesquioxane). The sesquiterpene oxide is a colorless viscous liquid which is soluble in various organic solvents.

Next, 20.65 g of sesquiterpene oxide and 82 ml of toluene and 3.0 g of 10% TMAH aqueous solution were fed into a reaction vessel equipped with a stirrer, a Dean-Stark trap, and a cooling tube, and slowly distilled off. water. Subsequently, the mixture was heated to 130 ° C and subjected to a recondensation reaction at a temperature at which toluene was refluxed. At this time, the temperature of the reaction solution was 108 °C. After the toluene was refluxed and stirred for 2 hours, the reaction was terminated. The reaction solution was washed with saturated brine until neutral, and then dried over anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered and concentrated to obtain 18.77 g of the desired caged sesquioxane resin. The obtained cage sesquioxane resin is a colorless viscous liquid which is soluble in various organic solvents.

The cage type sesquiterpene oxide resin obtained in the above Synthesis Example 1 was mixed: 25 parts by weight, dipentaerythritol hexaacrylate: 40 parts by weight, dicyclopentenyl diacrylate: 30 parts by weight, urethane acrylate Oligomer (UF-503, manufactured by Kyoeisha Chemical Co., Ltd.: number average molecular weight: about 3,800): 5 parts by weight, 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator: 2.5 parts by weight, obtained transparent A curable resin composition.

[acrylic rubber particles]

A particle having a spherical three-layer structure is used, and the innermost layer of the particle is obtained by polymerizing a monomer composed of 93.8% of methyl methacrylate with 6% of methyl acrylate and 0.2% of allyl methacrylate. The hard polymer, the intermediate layer is an elastic polymer obtained by polymerizing a monomer composed of 81% butyl acrylate and 17% styrene and 2% methacrylic acid ester, and the outermost layer is made by The hard polymer obtained by polymerization of a monomer composed of methyl methacrylate 94% and 6% methyl acrylate has a polymerization ratio of the innermost layer/intermediate layer/outermost layer of 35/45/20, and the elasticity of the intermediate layer. The average particle diameter of the polymer layer was 220 nm, which was obtained by an emulsion polymerization method.

Further, the average particle diameter of the elastic polymer layer of the intermediate layer of the above acrylic rubber particles was measured by the following method.

(Measurement of average particle size of layer of elastic polymer)

The acrylic rubber particles were mixed with a methacrylic resin to form a film, and the obtained film was cut into an appropriate size, and the chips were immersed in a 0.5% osmium tetroxide aqueous solution at room temperature for 15 hours to form an elastic polymer layer in the rubber particles. dyeing. Further, the sample was cut into a thickness of about 80 mm using MICROTOME, and then photographed by a transmission electron microscope. From the photograph, 100 layers of the dyed elastic polymer were randomly selected, and the respective diameters thereof were calculated, and the average value thereof was obtained.

<Example 1>

The copolymer 1 was subjected to press molding at 170 ° C to obtain a methacrylic resin film having a thickness of 0.5 mm. The curable resin composition was applied to one surface of the methacrylic resin film obtained above so that the thickness of the curable resin layer after curing was 100 μm. Next, a transparent protective film (polyethylene terephthalate having a thickness of 100 μm and a light transmittance of 90% or more at a wavelength of 550 nm) was applied and pressed against a curable resin composition, and then irradiated with a high-pressure mercury lamp at 6400 mJ/cm. The irradiation exposure amount of ² is such that the curable resin composition is photocured to form a curable resin layer. Subsequently, the transparent protective film is peeled off from the surface of the curable resin layer to obtain a laminate having a curable resin layer on one surface of the methacrylic resin film.

With respect to the obtained laminate, the adhesion after the initial stage and the endurance test was evaluated by the method shown below. The durability test was carried out under the conditions of 85 ° C to 85% (3 days) and 85 ° C - dry (5 days) to evaluate the adhesion.

<Adhesion test (initial adhesion)>

On the surface of the laminate, a 100-square checkerboard cut of 1 mm square was cut into a film by a cutter, and a glass tape [NICHIBAN (width) of 24 mm] was attached thereto, and then peeled off in a vertical direction. The number of grids remaining without peeling off every 100 checkerboards was evaluated. The results are shown in Table 1.

<Adhesion test (85 ° C - dry (5 days))

In addition to using a 210mm × 300mm laminate at 85 ° C 0% RH In the same manner as in the <adhesion test (initial adhesion), the number of cells remaining without peeling off the 100 checkerboards was evaluated in the same manner as in the case of the adhesion test (initial adhesion). . The results are shown in Table 1.

<Adhesion test (85 ° C - 85% (3 days)) >

The laminate was heat-treated with a laminate of 210 mm × 300 mm in an oven at 85 ° C and 85% RH for 3 days, and the laminate was the same as the "adhesion test (initial adhesion)". Evaluate the number of undivided bars per 100 checkerboards. The results are shown in Table 1.

<Example 2>

A laminate was obtained in the same manner as in Example 1 except that the copolymer 2 was used instead of the copolymer 1, and the adhesion was evaluated in the same manner as in Example 1 with respect to the obtained laminate. The results are shown in Table 1.

<Example 3>

Each of the copolymer 2 and the polycarbonate resin is melt-kneaded in an extruder, and each is supplied to a feeding tube, and extruded from a nozzle to form a layer composed of a copolymer 2 on both sides of a layer made of a polycarbonate resin. A film-like molten resin of the layer. The film-shaped molten resin extruded from the die is sandwiched between the first and second cooling rolls, wound around the third cooling roll, and formed and cooled to obtain a layer made of a polycarbonate resin. 3 layers of the layer formed by the copolymer 2 on both sides Laminated film of layer structure. The thickness of the laminated film was 0.5 mm, the thickness of the polycarbonate resin layer was 0.3 mm, and the thickness of the methacrylic resin layer was 0.1 mm and 0.1 mm, respectively.

A laminate was obtained in the same manner as in Example 1 except that a laminate film was used instead of the methacrylic resin film, and the adhesion was evaluated in the same manner as in Example 1 with respect to the obtained laminate. The results are shown in Table 1.

<Example 4>

The mixture was mixed by an ultra-kneading machine at a ratio of 33.5 wt% of acrylic rubber particles, 50% by weight of copolymer 2, and 16.5% by weight of copolymer 3, and melt-kneaded by a two-axis extruder to obtain copolymerization of rubber-containing particles. The particles formed by the object. Based on JIS K 7191-2, the bending stress was set to 1.80 MPa, and the measurement result of the load deformation temperature of the copolymer was 71 °C.

A laminate was obtained in the same manner as in Example 1 except that the obtained pellets were subjected to press molding at 230 ° C, and the obtained laminate was evaluated for adhesion in the same manner as in Example 1. The results are shown in Table 1.

<Comparative Example 1>

A laminate was obtained in the same manner as in Example 1 except that the copolymer 4 was used instead of the copolymer 1, and the adhesion was evaluated in the same manner as in Example 1 for the obtained laminate. The results are shown in Table 1.

As can be seen from Table 1, the laminate obtained in Examples 1 to 4 was more excellent in adhesion to the transparent resin film and the curable resin layer than the laminate obtained in Comparative Example 1.

Claims (4)

A laminated body comprising a transparent resin film made of one or more thermoplastic resin layers and a laminate of a curable resin layer laminated on at least one surface of the transparent resin film, characterized in that The curable resin layer is obtained by curing a curable resin composition containing a cage type sesquiterpene oxide resin, and constituting a thermoplastic resin-based alkyl methacrylate of a thermoplastic resin layer in contact with the curable resin layer. A copolymer of alkyl acrylate with a load deformation temperature of 20 to 80 ° C. The laminate according to claim 1, wherein the weight ratio of the alkyl methacrylate to the alkyl acrylate in the copolymer is 100% by weight based on 100% by weight of the alkyl methacrylate and the alkyl acrylate, and the alkyl methacrylate It is 40% by weight to 90% by weight, and the alkyl acrylate is 60% by weight to 10% by weight. The laminate according to claim 1 or 2, wherein the aforementioned alkyl methacrylate is methyl methacrylate, and the alkyl acrylate is n-butyl acrylate. A transparent resin film which is characterized by being used in the laminate according to any one of claims 1 to 3.