JP2021008530A - Photocurable composition and laminate - Google Patents

Abstract

To produce a non-aqueous photocurable composition that has a high curing rate and high adhesive strength while having a viscosity suitable for coating.SOLUTION: The photocurable composition includes [a] an alicyclic epoxy compound, [b] a (meth)acrylate, [c] a photocationic polymerization initiator and [d] a radical polymerization initiator in which the (meth)acrylate [b] includes [b1] a (meth)acrylate having a Tg of -40 to 70°C.SELECTED DRAWING: None

Description

The present invention relates to photocurable compositions and laminates.

Epoxy compounds are used in a wide range of fields as the main components of coating compositions and adhesive compositions. However, depending on the epoxy compound used, the viscosity of the composition becomes extremely high, and there is room for improvement from the viewpoint of coatability. Further, depending on the base material, a primer treatment may be performed before applying the coating composition, but there is no suggestion about the adhesiveness to the primer surface.

An object of the present invention is to obtain a non-aqueous photocurable composition having a high curing rate and adhesive strength while having a viscosity suitable for coating.

As a result of diligent studies on the above problems, the present inventor blended an alicyclic epoxy compound and (meth) acrylate as curing components, and further used a photocationic polymerization initiator and a radical polymerization initiator in combination to obtain a viscosity. The present invention has been completed by finding that a good balance between curing speed and adhesiveness can be achieved.

That is, the present invention relates to:
[1]
[A] Alicyclic epoxy compound,
[B] (Meta) acrylate,
[C] Photocationic polymerization initiator and
[D] A photocurable composition containing a radical polymerization initiator.
[B] (meth) acrylate is a photocurable composition containing [b1] (meth) acrylate at Tg-40 to 70 ° C.
[2]
[B1] The photocuring of [1], wherein the (meth) acrylate has a weight average molecular weight of 100 to 300 and has at least one selected from the group consisting of an ether bond, a hydroxyl group and a heterocycle in the molecule. Sex composition;
[3]
[B1] The (meth) acrylate is hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, tetrahydrofurfuryl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, tetrahydrofur. It comprises at least one selected from the group consisting of frill methacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, benzyl acrylate, and cyclic trimethylolpropanformal acrylate [1]. Or the photocurable composition of [2];
[4]
[A] The alicyclic epoxy compound is 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, (4R) -1,2-epoxy-4- (2-methyloxylanyl) -1-. Methylcyclohexane, 3', 4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 1,2-epoxy-4-vinylcyclohexane, 4,5- (3,4-epoxycyclopentane) -1,2- The photocurable composition according to any one of [1] to [3], which comprises at least one selected from the group consisting of epoxycyclohexane and cyclohexanedimethanol diglycidyl ether;
[5]
Further, the photocurable composition according to any one of [1] to [4], which comprises [e] an aromatic epoxy compound;
[6]
[E] The aromatic epoxy compound comprises [e1] an aromatic epoxy compound having two or more epoxy groups in one molecule or [e2] an aromatic epoxy compound having one epoxy group in one molecule [5]. ] Photocurable composition;
[7]
[E] The aromatic epoxy compound comprises [e1] an aromatic epoxy compound having two or more epoxy groups in one molecule, and [e2] an aromatic epoxy compound having one epoxy group in one molecule [e2]. 5] or [6] photocurable composition;
[8]
[E1] The aromatic epoxy compound is bisphenol A type diglycidyl ether, bisphenol F type diglycidyl ether, bisphenol S type diglycidyl ether, brominated bisphenol A type diglycidyl ether, terminal carboxylic acid polybutadiene and bisphenol A type epoxy resin. Group consisting of addition reactants, phenol novolac type epoxy resin, cresol novolac type epoxy resin, novolac type epoxy resin, biphenyl type epoxy resin, hydroquinone diglycidyl ether, resorcinol diglycidyl ether, terephthalic acid diglycidyl ester and phthalic acid diglycidyl ester The photocurable compositions of [6] and [7], comprising at least one selected from the above;
[9]
[E2] The aromatic epoxy compound comprises at least one selected from the group consisting of phenylglycidyl ether, biphenylglycidyl ether, 2,3-propylphenylglycidyl ether, tertiary butylphenylglycidyl ether, and dibromophenylglycidyl ether. The photocurable composition according to any one of [6] to [8];
[10]
The photocurable composition according to any one of [7] to [9], which comprises the aromatic epoxy compound [e1] and the aromatic epoxy compound [e2] in a weight ratio of 100: 0.1 to 40:60;
[11]
Further, the photocurable composition according to any one of [1] to [10], which comprises the [f] oxetane compound;
[12]
[F] Oxetane compounds are 3-ethyl-3-hydroxymethyloxetane, 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] benzene, 3-ethyl-3- (phenoxymethyl) oxetane, di. [(3-Ethyl-3-oxetanyl) methyl] ether, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (cyclohexyloxymethyl) oxetane, phenol novolac oxetane, 1,3- The photocurable composition of [11], comprising at least one selected from the group consisting of bis [(3-ethyloxetane-3-yl) methoxy] benzene, oxetanyl silsesquioxane and oxetanyl silicate;
[13]
[A] A laminate in which the [B] functional layer is arranged on at least one surface of the base film.
[B] A laminate in which the functional layer contains a cured product of the photocurable composition according to any one of [1] to [12];
[14]
[A] The laminate of [13], wherein the base film contains an acrylic film;
[15]
Another functional layer containing at least one selected from the group consisting of [C] urethane-based resin, ester-based resin and acrylic-based resin is arranged between the [A] base film and the [B] functional layer. [13] or [14] laminate; and [16]
The laminate according to any one of [13] to [15], wherein the adhesive strength between the base film [A] and the functional layer [B] is 1 N / 50 mm or more.

According to the present invention, it is possible to obtain a non-aqueous photocurable composition having a high curing rate and adhesive strength while having a viscosity suitable for coating.

Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to the following.

<< Photo-curable composition >>
The present invention
[A] Alicyclic epoxy compound,
[B] (Meta) acrylate,
[C] Photocationic polymerization initiator and
[D] The present invention relates to a photocurable composition containing a radical polymerization initiator.

<[A] Alicyclic epoxy compound>
The alicyclic epoxy compound is not particularly limited as long as it is a compound containing at least one epoxy group and at least one alicyclic ring in one molecule. Specific examples include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, (4R) -1,2-epoxy-4- (2-methyloxylanyl) -1-methylcyclohexane, 3'. , 4'-Epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 1,2-epoxy-4-vinylcyclohexane, 4,5- (3,4-epoxycyclopentane) -1,2-epoxycyclohexane, cyclohexanedi Examples thereof include methanol diglycidyl ether. These may be used alone or in combination of two or more. Among these, those containing two or more epoxy groups are preferable from the viewpoint of coatability and curability, and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, (4R) -1,2-epoxy. -4- (2-Methyloxylanyl) -1-methylcyclohexane, 3', 4'-epoxycyclohexylmethyl, and 4,5- (3,4-epoxycyclopentane) -1,2-epoxycyclohexane preferable.

[A] The blending amount of the alicyclic epoxy compound is preferably 10 to 90 parts by weight, more preferably 30 to 70 parts by weight, out of 100 parts by weight of the total of the curable components. [A] When the blending amount of the alicyclic epoxy compound is within the above numerical range, good coatability and curability tend to be obtained.
Here, the curable component means a component that can be cured by irradiating with an active energy ray, and specific examples thereof include [a] an alicyclic epoxy compound and [b] (meth) acrylate. Further, [e] aromatic epoxy compound and [f] oxetane compound, which will be described later, can also be mentioned as curable components.

<[B] (meth) acrylate>
[B] The (meth) acrylate is not particularly limited as long as it has at least one (meth) acryloyl group in one molecule (excluding those having an epoxy group), but will be described later [A]. From the viewpoint of adhesiveness to the base film, it is preferable that the glass transition temperature (Tg) is 40 to 70 ° C. [b1] (meth) acrylate, and the Tg is -20 to 10 ° C. [b1] (meth). ) It is more preferably acrylate.
Further, among the [b1] (meth) acrylates, those having a weight average molecular weight of 100 to 300 are preferable from the viewpoint of adhesiveness to the [A] base film, and those having a weight average molecular weight of 100 to 200 are further preferable. preferable.
Further, among the [b1] (meth) acrylates, those having at least one selected from the group consisting of an ether bond, a hydroxyl group and a heterocycle in the molecule from the viewpoint of adhesiveness to the [A] base film. preferable.

[B] Examples of the (meth) acrylate include hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, tetrahydrofurfuryl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and hydroxybutyl methacrylate. , Tetrahydrofurfuryl methacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, cyclic trimethylolpropanformal acrylate and the like. These may be used alone or in combination of two or more. Among these, hydroxyethyl acrylate, hydroxypropyl acrylate, and tetrahydrofurfuryl acrylate are preferable from the viewpoint of adhesiveness to the [A] base film.

[B] The blending amount of the (meth) acrylate is preferably 10 to 90 parts by weight, more preferably 20 to 50 parts by weight, out of a total of 100 parts by weight of the curable component. When the blending amount of [b] (meth) acrylate is within the above numerical range, good adhesiveness to the [A] base film can be exhibited.

<[C] Photocationic polymerization initiator>
[C] The photocationic polymerization initiator is not particularly limited as long as it generates a cationic species or Lewis acid by irradiation with active energy rays to initiate a cationic polymerization reaction, and is, for example, hexafluoroantimonate or hexafluoro. Examples thereof include aromatic sulfonium salts with anions such as phosphate and tetrakis (pentafluorophenyl) borate, and onium salts such as aromatic iodonium salts.

Examples of the aromatic sulfonium salt include triphenylsulfonium, hexafluorophosphate, triphenylsulfonium, hexafluoroantimonate, triphenylsulfonium, tetrakis (pentafluorophenyl) borate, and 4,4'-bis (diphenylsulfonio) diphenyl. Sulfide, bishexafluorophosphate, 4,4'-bis [di (β-hydroxyethoxy) phenylsulfonio] diphenylsulfide, bishexafluoroantimonate, 4,4'-bis [di (β-hydroxyethoxy) phenylsulfonium] Nio] diphenyl sulfide, bishexafluorophosphate, 7- [di (p-toluyl) sulfonio] -2-isopropylthioxanthone, hexafluoroantimonate, 7- [di (p-toluyl) sulfonio] -2-isopropylthioxanthone, tetrakis (Pentafluorophenyl) borate, 4-phenylcarbonyl-4'-diphenylsulfonio-diphenylsulfide, hexafluorophosphate, 4- (p-tert-butylphenylcarbonyl) -4'-diphenylsulfonio-diphenylsulfide, hexafluoro Examples thereof include antimonate, 4- (p-tert-butylphenylcarbonyl) -4'-di (p-toluyl) sulfonio-diphenylsulfide, and tetrakis (pentafluorophenyl) borate.

Examples of the aromatic iodonium salt include diphenyliodonium tetrakis (pentafluorophenyl) borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, and di (4-nonylphenyl) iodonium hexafluorophosphate.

These may be used alone or in combination of two or more. Among these, from the viewpoint of curing rate, it is preferable that the anion does not contain a phosphorus atom. For example, triphenylsulfonium, hexafluoroantimonate, triphenylsulfonium, tetrakis (pentafluorophenyl) borate, diphenyliodonium hexafluoro Antimonate, diphenyliodonium tetrakis (pentafluorophenyl) borate and the like are suitable.

The blending amount of the [c] photocationic polymerization initiator is preferably 1 to 10 parts by weight with respect to 100 parts by weight of the total of the curable components having an epoxy group containing the [a] alicyclic epoxy compound. More preferably, it is ~ 5 parts by weight. [C] When the blending amount of the photocationic polymerization initiator is within the above numerical range, it is preferable from the viewpoint of cured physical properties.

<[D] Radical polymerization initiator>
[D] The radical polymerization initiator is not particularly limited as long as it can initiate a radical polymerization reaction by irradiation with active energy rays, and is, for example, acetophenone, 2,2-diethoxy-2-phenylacetophenone, p-dimethylamino. Propiophenone, dichloroacetophenone, 2-methyl-1- [4- (methylthiophenyl] -2-morpholinopropane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino- Acetophenones such as 1- (4-morpholinophenyl) -butanone-1, benzophenone, 2-chlorobenzophenone, p, p-bisdimethylaminobenzophenone, p, p-bisdiethylaminobenzophenone, 4-benzoyl-4'-methyldiphenyl Benzophenones such as sulfide, benzyl, benzoin, benzoin methyl ether, benzoin ethers such as benzoin isobutyl ether, ketals such as benzyldimethyl ketal, anthraquinones such as thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2 , 4,5-Triarylimidazole dimer, 2,4,6-tris-S-triazine, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, etc. These may be used alone or may be used alone. Two or more types may be used together.

The blending amount of the [d] radical polymerization initiator is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the [b] (meth) acrylate. preferable. [D] When the blending amount of the radical polymerization initiator is within the above numerical range, it is preferable from the viewpoint of cured physical properties.

The photocurable composition of the present invention may optionally contain other components in addition to the above-mentioned components [a] to [d]. Examples of other components include [e] aromatic epoxy compounds, [f] oxetane compounds, [g] aliphatic epoxy compounds, leveling agents, defoamers, coupling agents, photosensitizers, and the like.

<[E] Aromatic epoxy compound>
From the viewpoint of moisture resistance and heat reliability, it is preferable to contain the [e] aromatic epoxy compound. [E] The aromatic epoxy compound is not particularly limited as long as it is a compound containing at least one epoxy group and at least one aromatic ring in one molecule, but from the viewpoint of heat resistance, an epoxy group in one molecule. It is preferable to contain the [e1] aromatic epoxy compound having two or more of [e1]. Further, from the viewpoint of viscosity and coatability, it contains a [e1] aromatic epoxy compound having two or more epoxy groups in one molecule and a [e2] aromatic epoxy compound having one epoxy group in one molecule. Is preferable.

[E1] Examples of the aromatic epoxy compound include bisphenol A type diglycidyl ether, bisphenol F type diglycidyl ether, bisphenol S type diglycidyl ether, brominated bisphenol A type diglycidyl ether, polybutadiene terminal carboxylate and bisphenol A type epoxy resin. Addition reactants, phenol novolac type epoxy resin, cresol novolac type epoxy resin, novolac type epoxy resin, biphenyl type epoxy resin, hydroquinone diglycidyl ether, resorcinol diglycidyl ether, terephthalic acid diglycidyl ester, phthalic acid diglycidyl ester, etc. Can be mentioned. These may be used alone or in combination of two or more. Among these, bisphenol F type diglycidyl ether, bisphenol S type diglycidyl ether, and resorcinol diglycidyl ether are preferable from the viewpoint of viscosity and reactivity.

[E2] Examples of the aromatic epoxy compound include phenylglycidyl ether, biphenylglycidyl ether, 2,3-propylphenylglycidyl ether, tertiary butylphenylglycidyl ether, dibromophenylglycidyl ether and the like. These may be used alone or in combination of two or more. Among these, phenylglycidyl ether and tertiary butylphenylglycidyl ether are preferable from the viewpoint of reactivity and heat resistance.

Further, as the [e2] aromatic epoxy compound, an epoxy acrylate having at least one epoxy group in one molecule and at least one (meth) acryloyl group in one molecule can also be used. When epoxy acrylate is used as the [e2] aromatic epoxy compound, it can also be used in combination with the [f] oxetane compound described later.

When the [e1] aromatic epoxy compound and the [e2] aromatic epoxy compound are used in combination, the [e1] aromatic epoxy compound and the [e2] aromatic epoxy compound are contained in a weight ratio of 100: 0.1 to 40:60. Is preferable.

When the photocurable composition of the present invention contains the [e] aromatic epoxy compound, the blending amount of the [e] aromatic epoxy compound shall be 5 to 80 parts by weight out of a total of 100 parts by weight of the curable components. Is preferable, and 10 to 50 parts by weight is more preferable. [E] When the blending amount of the aromatic epoxy compound is within the above numerical range, the reactivity tends to be good and the heat resistance tends to be high.

<[F] Oxetane compound>
From the viewpoint of viscosity and reaction rate, it is preferable to contain the [f] oxetane compound. [F] The oxetane compound is not particularly limited as long as it is a compound having a 4-membered ring ether (oxetanyl group) in the molecule, but specifically, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis. [(3-Ethyl-3-oxetanyl) methoxymethyl] benzene, 3-ethyl-3- (phenoxymethyl) oxetane, di [(3-ethyl-3-oxetanyl) methyl] ether, 3-ethyl-3- (2) -Ethylhexyloxymethyl) oxetane, 3-ethyl-3- (cyclohexyloxymethyl) oxetane, phenol novolac oxetane, 1,3-bis [(3-ethyloxetane-3-yl) methoxy] benzene, oxetanyl silsesquioxane, Examples thereof include oxetane silicate.

When the photocurable composition of the present invention contains the [f] oxetane compound, the blending amount of the [f] oxetane compound is preferably 5 to 80 parts by weight out of a total of 100 parts by weight of the curable components. More preferably, it is 10 to 60 parts by weight. [F] When the blending amount of the oxetane compound is within the above numerical range, the viscosity tends to be low and the reactivity tends to be high.

[G] Examples of the aliphatic epoxy compound include monofunctional epoxy compounds such as glycidyl etherified products of aliphatic alcohols and glycidyl esters of alkylcarboxylic acids, polyglycidyl etherified products of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, and fats. Examples thereof include polyfunctional epoxy compounds such as polyglycidyl esters of long-chain polybasic acids. Typical compounds include allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, C12-13 mixed alkyl glycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and glycerin. Triglycidyl ethers of polyhydric alcohols such as triglycidyl ethers of trimethylolpropane, tetraglycidyl ethers of sorbitol, hexaglycidyl ethers of dipentaerythritol, diglycidyl ethers of polyethylene glycol, diglycidyl ethers of polypropylene glycol, and propylene. Polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as glycol, trimethylolpropane, and glycerin, and diglycidyl esters of aliphatic long-chain dibasic acids. Can be mentioned.

Examples of the leveling agent include siloxane compounds, fluorine compounds, polyether compounds, carboxylic acids, ester compounds, sulfonate compounds, phosphate compounds, amide compounds, acrylic compounds and the like.

Examples of the defoaming agent include a silicon-based defoaming agent, a fluorine-based defoaming agent, and a polymer-based defoaming agent.

Coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxy. Silane, N-phenyl-γ-aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyltrimethoxysilane, 3-amino Propyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, N- (2- (vinylbenzylamino) ethyl) 3-aminopropyltrimethoxysilane hydrochloride, 3-methacryloxypropyltrimethoxysilane, 3 −Chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane and the like can be mentioned.

Examples of the photosensitizer include acridine compounds, benzoflavins, perylenes, anthracenes, thioxanthone compounds, laser dyes and the like.

The viscosity of the photocurable composition of the present invention at 25 ° C. is preferably 200 mPa · s or less, and more preferably 100 mPa · s or less, from the viewpoint of coatability. Viscosity is measured by the method described in Examples.

From the viewpoint of curability, the photocurable composition of the present invention preferably has a water content of 1% by weight or less, more preferably 0.5% by weight or less. When the water content is 0.5% by weight or less, cationic polymerization is less likely to be inhibited, which is preferable.

From the viewpoint of heat resistance and reliability, the photocurable composition of the present invention preferably has a glass transition temperature of 40 ° C. or higher, more preferably 60 ° C. or higher. When the glass transition temperature is 60 ° C. or higher, adhesion reliability is ensured even in a moisture resistance heat test of 60 ° C. or higher, which is preferable. The glass transition temperature is measured by the method described in Examples.

<< Laminated body >>
In the laminate of the present invention, the [B] functional layer is arranged on at least one surface of the [A] base film, and the [B] functional layer contains a cured product of the photocurable composition of the present invention. It is characterized by.

<[A] Base film>
[A] The material of the base film is not particularly limited, and examples thereof include a cellulose-based film such as triacetyl cellulose, an acrylic film such as polymethyl methacrylate, a COP film, and a polyester-based film such as polyethylene terephthalate. ..

[A] The thickness of the base film is preferably 5 to 100 μm, more preferably 10 to 80 μm. [A] When the thickness of the base film is within the above numerical range, it is preferable because the light transmission is good and the strength of the film can be maintained.

The base film [A] may be subjected to surface treatment such as corona treatment, primer treatment, and plasma treatment in order to improve the adhesiveness with the [B] functional layer.

<[B] Functional layer>
The [B] functional layer contains a cured product of the photocurable composition of the present invention and is arranged on at least one surface of the [A] base film.

[B] The method for forming the functional layer is not particularly limited. For example, [A] a method in which the photocurable composition of the present invention is applied to at least one surface of a base film and cured by irradiating it with active energy rays. Can be mentioned. Further, the photocurable composition of the present invention is applied to the surface of a base material other than the [A] base film, the [A] base film is superposed on the surface, and the film is cured by irradiating with active energy rays. It can also be formed by. The active energy rays may be irradiated from any surface of the [A] base film.

The method of applying the photocurable composition is not particularly limited, and for example, curtain coater, roll coater, knife coater, die coater, lip coater, bar coater, gravure printing, offset printing, letterpress printing, screen printing, spray coating. And so on.

Visible light, ultraviolet rays, X-rays, electron beams and the like can be used as the active energy rays. The light source is not particularly limited, and may be selected depending on the [c] photocationic polymerization initiator and the [d] radical polymerization initiator. For example, high-pressure mercury lamps, ultra-high pressure mercury lamps, low-pressure mercury lamps, carbon arcs, black lights, metal halide lamps, halogen lamps, LED lamps and the like can be mentioned.

The curing conditions are not particularly limited, but for example, it is preferable to set the integrated light amount to 250 mJ / cm ² or more at about 20 to 30 ° C.

The adhesive strength between the base film [A] and the functional layer [B] is preferably 1N / 50 mm or more, and more preferably 3N / 50 mm or more. Adhesive strength is measured by the method described in Examples.

[B] The thickness of the functional layer is preferably 0.001 to 20 μm, more preferably 1 to 10 μm. [B] When the thickness of the functional layer is within the above numerical range, good adhesiveness and transparency are exhibited, which is preferable.

<[C] Other functional layers>
Another functional layer containing at least one selected from the group consisting of [C] polyurethane-based resin, polyester-based resin, and acrylic-based resin is arranged between the [A] base film and the [B] functional layer. May be. Examples of such a functional layer include a blocking prevention layer of the [A] base film.

In this case, as a method for forming the [B] functional layer, after arranging [C] another functional layer on the surface of the [A] base film, the photocurable composition of the present invention is applied to [C] other functions. A method of applying and curing on the surface of a layer, or applying the photocurable composition of the present invention to the surface of a base material other than the [A] base film, and then [C] via another functional layer. [A] Examples thereof include a method in which base films are laminated and cured by irradiating them with active energy rays.

The photocurable composition of the present invention can be used as an optical film, an adhesive for optical elements, an adhesive for antireflection, an adhesive for laminated films, an adhesive for flexible substrates, and an adhesive for display element-related members. .. Further, the photocurable composition of the present invention can be used as various coatings, for example, a surface protection coating, a hard coating, a transparent coating and the like.

The laminate of the present invention can be used as an optical film such as a polarizing plate, a surface protective film, a transparent conductive film, an antistatic film, a gas barrier film, a steam barrier film and the like.

Hereinafter, the present invention will be specifically described based on Examples and Comparative Examples, but the present invention is not limited to the following Examples.

(1) Materials used (1-1) Alicyclic epoxy compound Celoxide 2021P (3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, manufactured by Daicel)
(1-2) Aromatic epoxy compound jER828 (bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Corporation, number of functional groups: 2)
jER806 (bisphenol F type epoxy resin, manufactured by Mitsubishi Chemical Corporation, number of functional groups: 2)
Denacol EX-141 (Phenylglycidyl ether, manufactured by Nagase ChemteX, number of functional groups: 1)
UVAC1561 (bisphenol skeleton epoxy acrylate, manufactured by Daicel UCB, number of functional groups: 1)
(1-3) (Meta) Acrylate IBXA (Isobornyl Acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd., Tg: 97 ° C., Weight Average Molecular Weight: 207)
FA-511AS (dicyclopentenyl acrylate, manufactured by Hitachi Chemical Co., Ltd., Tg: 120 ° C., molecular weight: 204)
FA-513AS (dicyclopentanyl acrylate, manufactured by Hitachi Chemical Co., Ltd., Tg: 120 ° C., weight average molecular weight: 206)
Viscoat 160 (benzyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd., Tg: 6 ° C., weight average molecular weight: 162)
THF-A (Tetrahydrofurfuryl Acrylate, manufactured by Kyoeisha Chemical Co., Ltd., Tg: -12 ° C., weight average molecular weight: 156)
Viscort 190 (ethylcarbitol acrylate, Tg: -67 ° C, weight average molecular weight: 188)
Viscoat 192 (phenoxyethyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd., Tg: 2 ° C., weight average molecular weight: 192)
(1-4) Photocationic polymerization initiator CPI-101A (aromatic sulfonium salt, manufactured by San-Apro)
A2074 (4-Methylphenyl-4- (1-methylethyl) phenyliodonium-tetrakis (pentafluorophenyl) borate, manufactured by Rhodia)
(1-5) Radical Polymerization Initiator Irgacure651 (2,2-dimethoxy-2-phenylacetophenone, manufactured by IGM Resins BV)
DETX (2,4-diethylthioxanthene-9-one)
(1-6) Others OXT-221 (bifunctional oxetane compound, 3-ethyl-3 {[(3-ethyloxetane-3-yl) methoxy] methyl} oxetane, manufactured by Toagosei Corporation)
BYK-361N (Acrylic compound leveling agent, manufactured by BYK Chemie)

(2) Evaluation method (2-1) Viscosity Measured according to JISZ8803.
Those below 100 mPa · s were designated as "○", and those exceeding 100 mPa · s were designated as "x".
(2-2) Moisture content Measured according to JISK1557-2.
Measurements were made using an automatic Karl Fischer titer.
Those having a water content of 0.5% by weight or less were designated as "◯", and those having a water content of 1% by weight or more were designated as "x".
(2-3) Glass transition temperature (Tg)
Measured according to JIS K7095.
100 ° C. or higher was designated as “◯”, and less than 100 ° C. was designated as “x”.
(2-4) As the adhesive base material, a primer surface (containing a polyurethane resin) of an acrylic film (thickness 40 μm) was used. A photocurable composition was applied to the surface of the base material, the films were bonded to each other, cured with a D valve to form a laminate, and then the adhesiveness was evaluated by a tensile tester. Specifically, the composition was applied to form a coating film having a thickness of 3 μm, and the mixture was irradiated so that the integrated light intensity was 250 mJ / cm ² and cured to obtain a laminate. After leaving the film in an environment of 25 ° C. for 24 hours, the films were pulled to 180 degrees, and the adhesiveness was evaluated by a pulling tester.
"◎" indicates that the adhesive strength is 3N / 50 mm or more, "○" indicates that the adhesive strength is 1N / 50 mm or more and less than 3N / 50 mm, and "○" indicates that the adhesive strength is less than 1N / 50 mm. × ”.
(2-5) Reliability Test A laminate obtained by applying a photocurable composition to the primer surface of an acrylic film by the above method and curing it was used.
(A) Hot water immersion test The laminate was immersed in hot water at 60 ° C. for 10 hours, taken out, and then the adhesiveness was confirmed by touch as described above.
(B) Moisture and Heat Resistance Test After the laminate was left in an environment of 85 ° C. and a relative humidity of 85% for 7 days, the adhesiveness was confirmed by touch as described above.
(C) Crack resistance test The laminate was attached to the glass using a water-based adhesive (elastic modulus at 30 ° C. of 5 MPa) so that the film side was in contact with the glass. After leaving this in a cold environment (100 cycles with 40 ° C. for 30 minutes and 85 ° C. for 30 minutes as one cycle), the adhesiveness was confirmed by touch as described above.

(Examples 1 to 8, Comparative Examples 1 to 4)
Each component was mixed according to the formulation (part by weight) shown in Table 1 to produce a photocurable composition. The viscosity, reactivity and glass transition temperature of each composition were evaluated. In addition, a laminate was manufactured and the adhesiveness and reliability were evaluated. The results are shown in Table 1.

In Comparative Examples 1 to 4, the adhesiveness of the acrylic film to the primer surface was insufficient. On the other hand, in Examples 1 to 8, the results of the adhesiveness and reliability test were good while having a low viscosity and a high glass transition temperature.

Claims (16)

[A] Alicyclic epoxy compound,
[B] (Meta) acrylate,
[C] Photocationic polymerization initiator and
[D] A photocurable composition containing a radical polymerization initiator.
[B] (meth) acrylate is a photocurable composition containing [b1] (meth) acrylate at Tg-40 to 70 ° C. [B1] The first aspect of the present invention, wherein the (meth) acrylate has a weight average molecular weight of 100 to 300, and has at least one selected from the group consisting of an ether bond, a hydroxyl group and a heterocycle in the molecule. Photocurable composition. [B1] The (meth) acrylate is hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, tetrahydrofurfuryl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, tetrahydrofur. 1. Claim 1 comprising at least one selected from the group consisting of frill methacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, benzyl acrylate, and cyclic trimethylolpropanformal acrylate. Or the photocurable composition according to 2. [A] The alicyclic epoxy compound is 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, (4R) -1,2-epoxy-4- (2-methyloxylanyl) -1-. Methylcyclohexane, 3', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1,2-epoxy-4-vinylcyclohexane, 4,5- (3,4-epoxycyclopentane) -1,2 -The photocurable composition according to any one of claims 1 to 3, comprising at least one selected from the group consisting of epoxycyclohexane and cyclohexanedimethanol diglycidyl ether. The photocurable composition according to any one of claims 1 to 4, further comprising [e] an aromatic epoxy compound. [E] Aromatic epoxy compounds include [e1] aromatic epoxy compounds having two or more epoxy groups in one molecule or [e2] aromatic epoxy compounds having one epoxy group in one molecule. 5. The photocurable composition according to 5. [E] The aromatic epoxy compound comprises [e1] an aromatic epoxy compound having two or more epoxy groups in one molecule, and [e2] an aromatic epoxy compound having one epoxy group in one molecule. Item 5. The photocurable composition according to Item 5 or 6. [E1] The aromatic epoxy compound is bisphenol A type diglycidyl ether, bisphenol F type diglycidyl ether, bisphenol S type diglycidyl ether, brominated bisphenol A type diglycidyl ether, terminal carboxylic acid polybutadiene and bisphenol A type epoxy resin. Group consisting of addition reactants, phenol novolac type epoxy resin, cresol novolac type epoxy resin, novolac type epoxy resin, biphenyl type epoxy resin, hydroquinone diglycidyl ether, resorcinol diglycidyl ether, terephthalic acid diglycidyl ester and phthalic acid diglycidyl ester The photocurable composition according to claims 6 and 7, which comprises at least one selected from. [E2] The aromatic epoxy compound comprises at least one selected from the group consisting of phenylglycidyl ether, biphenylglycidyl ether, 2,3-propylphenylglycidyl ether, tertiary butylphenylglycidyl ether, and dibromophenylglycidyl ether. The photocurable composition according to any one of claims 6 to 8. The photocurable composition according to any one of claims 7 to 9, which comprises the aromatic epoxy compound [e1] and the aromatic epoxy compound [e2] in a weight ratio of 100: 0.1 to 40:60. The photocurable composition according to any one of claims 1 to 10, further comprising [f] an oxetane compound. [F] Oxetane compounds are 3-ethyl-3-hydroxymethyloxetane, 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] benzene, 3-ethyl-3- (phenoxymethyl) oxetane, di. [(3-Ethyl-3-oxetanyl) methyl] ether, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (cyclohexyloxymethyl) oxetane, phenol novolac oxetane, 1,3- The photocurable composition according to claim 11, which comprises at least one selected from the group consisting of bis [(3-ethyloxetane-3-yl) methoxy] benzene, oxetanyl silsesquioxane and oxetanyl silicate. [A] A laminate in which the [B] functional layer is arranged on at least one surface of the base film.
[B] A laminate in which the functional layer contains a cured product of the photocurable composition according to any one of claims 1 to 12. [A] The laminate according to claim 13, wherein the base film includes an acrylic film. Another functional layer containing at least one selected from the group consisting of [C] urethane-based resin, ester-based resin, and acrylic-based resin is arranged between the [A] base film and the [B] functional layer. The laminate according to claim 13 or 14. The laminate according to any one of claims 13 to 15, wherein the adhesive strength between the base film [A] and the functional layer [B] is 1 N / 50 mm or more.