TWI665521B - Ultraviolet ray-curable resin composition, and laminate using the same - Google Patents

Abstract

The present invention provides an ultraviolet-curable resin composition excellent in transparency and a laminate using the same. The ultraviolet curable resin composition contains (A) at least one polymer selected from the group consisting of a hydrocarbon-based polymer, a polyoxyalkylene group, and a polyurethane modified with (meth) acrylate, and (B) a photopolymerization initiator, (C) a naphthaleneimine-based compound having a naphthaleneimine skeleton and / or a benzooxazoline-based compound having a benzooxazoline skeleton, and (D) 1 molecule A (meth) acryloxy group-containing monomer and / or a plasticizer having at least one (meth) acryloxy group in the polymer; the polymer and the photopolymerization initiator and the (meth) group The total of 100 parts by mass of the propylene fluorenyl monomer and / or the plasticizer is 0.001 to 5 parts by mass of the naphthaleneimine-based compound and / or the benzoxazoline-based compound.

Description

Ultraviolet curable resin composition and laminate using the same

The present invention relates to an ultraviolet curable resin composition and a laminate using the same.

Conventionally, it has been proposed that a functional film or the like constituting an electronic device part for a display, such as a touch panel, be bonded with a light-curable adhesive composition (for example, Patent Document 1).

[Prior technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2012-46658

When coating a hard coating material that can exert anti-blue light function on the surface or back of a functional film, if the functional film is provided with a layer with anti-blue light function and an adhesive layer, the productivity is poor. In addition, the inventor It was found that if the adhesive layer is provided with an anti-blue light function, the transparency becomes low.

The present invention has been developed in view of the above problems, and an object thereof is to provide an ultraviolet curable resin composition excellent in transparency and a laminated body using the same.

In order to solve the above-mentioned problems, the present inventors have worked hard to find out that the above-mentioned problems can be solved by the following configuration.

An ultraviolet curable resin composition comprising: (A) at least one selected from the group consisting of a hydrocarbon polymer, a polyoxyalkylene group, and a polyurethane (A) modified with a (meth) acrylate; A polymer, (B) a photopolymerization initiator, (C) a naphthaleneimine-based compound having a naphthaleneimine skeleton, and / or a benzooxazoline-based compound having a benzooxazoline skeleton, and ( D) A (meth) acryloxy group-containing monomer and / or a plasticizer having at least one (meth) acryloxy group in one molecule, with respect to the polymer and the photopolymerization initiator and the foregoing A total of 100 parts by mass containing a (meth) acrylic fluorenyloxy monomer and / or the plasticizer, and an amount of the naphthylimide-based compound and / or the benzoxazoline-based compound is 0.001 to 5 parts by mass .

2. The ultraviolet curable resin composition according to the above 1, wherein the (meth) acrylate-modified hydrocarbon polymer has a material selected from the group consisting of polyisobutylene, polyolefin, polyisoprene, polybutadiene, and At least one hydrocarbon polymer in the group consisting of hydrogenated polybutadiene as main chain, terminal and / or The side chain has a (meth) acrylfluorenyl group or a group having a (meth) acrylfluorenyl group.

3. The ultraviolet curable resin composition according to the above 1 or 2, wherein the (meth) acrylate-modified polyoxyalkylene group has polyoxypropylene as a main chain, and the terminal and / or side chain has (A (Meth) acryloxy or a group having a (meth) acryloxy.

4. The ultraviolet-curable resin composition according to any one of the above 1 to 3, wherein the weight average molecular weight of the polymer is 1,000 to 100,000.

5. The ultraviolet-curable resin composition according to any one of the above 1 to 4, wherein the naphthaleneimine-based compound is a compound represented by formula (1) described later.

6. The ultraviolet curable resin composition according to any one of 1 to 5 above, which is used for bonding an optical display panel and a touch panel, bonding an optical display panel and a protective panel, and bonding a touch panel and a protective panel. , Bonding of optical display panel and optical display panel, or bonding of optical film and parallax barrier.

7. A laminated body borrowing an adhesive layer formed of the ultraviolet curable resin composition according to any one of 1 to 6 above, followed by an optical display panel and a touch panel, an optical display panel and a protective panel, a touch panel and a protection Panel, optical display panel and optical display panel, or optical film and parallax barrier.

The ultraviolet curable resin composition of the present invention and the laminated body of the present invention have excellent transparency.

100‧‧‧ laminated

102‧‧‧components

104‧‧‧ Adhesive layer

106‧‧‧components

FIG. 1 is a cross-sectional view schematically showing an example of the laminate of the present invention.

[UV-curable resin composition]

The present invention is explained in detail below.

First, the ultraviolet curable resin composition of the present invention will be described below.

The ultraviolet-curable resin composition of the present invention (the composition of the present invention) contains (A) a (meth) acrylic acid modified group selected from the group consisting of a hydrocarbon polymer, polyoxyalkylene, and polyurethane. At least one polymer, (B) a photopolymerization initiator, (C) a naphthaleneimine-based compound having a naphthaleneimine skeleton, and (D) at least one (meth) propylene in one molecule The (meth) acrylic methoxy group-containing monomer and / or plasticizer of the methoxy group is different from the polymer, the photopolymerization initiator, the (meth) acrylic oxy group-containing monomer, and / or the plasticizer. The total amount of the plasticizer is 100 parts by mass, and the amount of the aforementioned naphthaleneimine-based compound is 0.001 to 5 parts by mass.

In this specification, the (A) polymer may be referred to as a polymer, (A), or (A) component. The components described in (B) to (E) are also the same.

The excellent transparency may be referred to as the excellent effect of the present invention.

<(A) polymer>

The (A) polymer is explained below.

(A) The polymer is at least one selected from the group consisting of a hydrocarbon polymer, a polyoxyalkylene group, and a polyurethane modified with a (meth) acrylate.

(A) The polymer is not particularly limited as long as it has a (meth) acrylate-modified group and at least one selected from the group consisting of a hydrocarbon polymer, polyoxyalkylene, and polyurethane. limit.

As a (meth) acrylate modification group, a (meth) acryl methoxy group and the group which has a (meth) acryl methoxy group are mentioned as one of the preferable aspects.

In addition, "(meth) acryloxy" shall mean acryloxy (CH ₂ = CHCOO-) or methacryloxy (CH ₂ = C (CH ₃ ) COO-), and "(methyl "Acrylate" shall mean acrylate or methacrylate.

(A) The number of (meth) acrylate-modified groups per polymer is 1 or more. Considering that the effect of the present invention is more excellent, and the blue light resistance, appearance when hardened, and adhesive properties are excellent, the number of (meth) acrylate modified groups is preferably 2 in each molecule of the (A) polymer. To 8, more preferably 2 to 4.

The (meth) acrylate-modified group may be bonded to the end of the main chain and / or the side chain directly or through an organic group. The organic group is not particularly limited. The organic group may have, for example, a urethane bond.

Considering that the effect of the present invention is more excellent, and the blue light resistance, appearance when cured, and adhesive properties are excellent, the weight average molecular weight of the (A) polymer is preferably 1,000 to 100,000, and more preferably 5,000 to 50,000. In the present invention, the weight average molecular weight is a value obtained by converting a standard polystyrene with a gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent.

In view of the fact that the effect of the present invention is more excellent, and the blue light resistance, appearance when hardened, and adhesive properties are excellent, the hydrocarbon polymer modified with (meth) acrylate is preferably selected from polyisobutylene, polyolefin, poly At least one hydrocarbon polymer in the group consisting of isoprene, polybutadiene, and hydrogenated polybutadiene is used as the main chain.

The (meth) acrylate-modified polyoxyalkylene has a polyoxyalkylene skeleton as a main chain. Considering the viewpoint that the effect of the present invention is more excellent, blue light resistance, appearance when hardened, and adhesive properties are excellent, the poly (meth) acrylate modified by (meth) acrylate preferably has polyoxyethylene and polyoxypropylene as the Main chain.

The (meth) acrylate-modified polyurethane has a polyurethane skeleton as a main chain.

There are no particular restrictions on the production of (A) polymer. For example, conventionally well-known methods are mentioned.

<(B) Photopolymerization initiator>

The photopolymerization initiator will be described below.

As long as the photopolymerization initiator contained in the composition of the present invention The ethylenic functional group (for example, (meth) acryl fluorenyloxy) may be polymerized, and it is not particularly limited.

Examples of the photopolymerization initiator include an acetophenone-based compound, a benzoin ether-based compound, a benzophenone-based compound, a sulfur compound, an azo compound, a peroxide compound, and a phosphine oxide-based compound. Specifically, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, acetoin, butyridine, toluidine, benzoin, benzophenone, p-methoxybenzophenone , Diethoxyacetophenone, α, α-dimethoxy-α-phenylacetophenone, methylphenylglyoxylate, ethylphenylglyoxylate, 4,4'-bis (Dimethylaminobenzophenone), 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 2,2-dimethoxy-1,2-diphenylethane- Carbonyl compounds such as 1-ketone, 1-hydroxycyclohexylphenyl ketone; sulfur compounds such as tetramethylthiuram monosulfide, tetramethylthiuram disulfide; azobisisobutyronitrile, azo-2, Azo compounds such as 4-dimethylvaleronitrile; peroxide compounds such as benzamidine peroxide and bis-third butyl peroxide.

Among these, from the viewpoints of photostability, photolytic efficiency, surface hardening, compatibility, low volatility, and low odor, 1-hydroxycyclohexylphenyl ketone and 2-hydroxy-2-methyl-1 are preferred. -Phenyl-propane-1-one, and 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one.

The photopolymerization initiators can be used alone or in combination of two or more kinds.

The amount of the photopolymerization initiator is preferably 1 to 10 parts by mass based on 100 parts by mass of the (A) polymer.

<(C) Naphthylimine-based compound and / or benzoxazoline-based compound> (Napthalene imine-based compound)

The naphthalene imine-based compound will be described below.

The naphthaleneimine-based compound contained in the composition of the present invention is a compound having a naphthaleneimine skeleton.

Since the composition of the present invention contains a naphthylimine-based compound, it has excellent blue light resistance.

In view of the fact that the effect of the present invention is more excellent and that it has a high blue light resistance ratio, the naphthaleneimine-based compound is preferably a compound represented by the following formula (1).

(In formula (1), R ¹ represents a hydrogen atom or a hydrocarbon group which may have a hetero atom, R ² represents a hydrogen atom or an organic group, and a plurality of R ² may be the same or different from each other)

Examples of the hydrocarbon group which may have a hetero atom represented by R ¹ in the formula (1) include, for example, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and combinations thereof. The hydrocarbon group may have an unsaturated bond.

The hydrocarbon group represented by R ¹ is preferably a linear or branched alkyl group, and the number of carbon atoms is preferably 1 to 12.

As the organic group represented by R ² in the formula (1), functional groups such as an amine group, a hydroxyl group, and the like; a hydrocarbon group such as an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group; and a hydrocarbon group of the combination, etc. . The hydrocarbon group may have a hetero atom or an unsaturated bond.

The hydrocarbon group in the organic group represented by R ² is preferably an alkoxy group, and more preferably a methoxy group or an ethoxy group.

The naphthalene imine-based compound can reduce the transmittance of at least a part of the light in the wavelength range of 385 to 495 nm.

As a commercially available product of such a naphthaleneimine-based compound, for example, Lumogen F Violet 570 (manufactured by BASF) can be appropriately cited.

(Benzoxazoline compound)

The benzoxazoline-based compound will be described below.

The benzoxazoline-based compound contained in the composition of the present invention is a compound having a benzoxazoline skeleton.

Since the composition of the present invention contains a benzoxazoline-based compound, it has excellent blue light resistance.

The compound having a benzoxazoline skeleton is not particularly limited as long as it is a compound having a benzoxazole ring, but considering the reason that the overall blue light resistance is better, it is preferably represented by the following formula (I) Among these compounds, a compound represented by the following formula (Ia) is more preferred.

[Chemical 2]

(In formula (I), R ^a represents a hydrogen atom or an organic group, and a plurality of R ^a may be the same or different from each other)

Examples of the organic group represented by R ^a in the formula (I) include a hydrocarbon group which may have a hetero atom, and specific examples thereof include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and combinations thereof. , May also have unsaturated bonds.

The hydrocarbon group represented by R ^a is preferably a linear or branched alkyl group, and more preferably a branched alkyl group.

In addition, the number of carbon atoms of the hydrocarbon group represented by ^Ra is preferably from 1 to 12, more preferably from 3 to 6.

Examples of commercially available products of such benzoxazoline-based compounds include Tinopal OB CO (manufactured by BASF), Nikkafluor OB (manufactured by Japan Chemical Industry Co., Ltd.), and the like.

Based on the total of (A) polymer and (B) photopolymerization initiator and (D) (meth) acrylic fluorenyl monomer and / or plasticizer In the case of polymer and plasticizer, it refers to the total of (A) polymer and (B) photopolymerization initiator and (meth) acrylic fluorenyl monomer and plasticizer. The same applies below) 100 parts by mass of naphthalene Amine compounds and / or benzene The amount of the oxazoline-based compound is 0.001 to 5 parts by mass, and considering the point that the effect of the present invention is more excellent, it is preferably 0.001 to 2.0 parts by mass, and more preferably 0.001 to 0.5 parts by mass.

(Actinide)

The composition of the present invention may further contain a compound (fluorene-based compound) having a fluorene skeleton. The compound having a fluorene skeleton is not particularly limited. The fluorene skeleton may have a substituent. The osmium skeleton is represented by the following formula (2).

Examples of commercially available compounds having a fluorene skeleton include Lumogen F Yellow 083 (manufactured by BASF).

The compound having a fluorene skeleton can absorb a region (420 to 495 nm) of a long wavelength end in blue light than a compound having a naphthalene imine skeleton.

(Benzotriazole compound)

The composition of the present invention may further contain a compound (benzotriazole-based compound) having a benzotriazole skeleton. Compounds with a benzotriazole skeleton No special restrictions. The benzotriazole skeleton may have a substituent. The benzotriazole skeleton is represented by the following formula (3).

(In formula (3), R ³ represents a hydrogen atom or a hydrocarbon group which may have a hetero atom)

Examples of the hydrocarbon group which may have a hetero atom represented by R ³ in the formula (3) include, for example, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a combination thereof, and may have an unsaturated bond.

The hydrocarbon group represented by R ³ is preferably a linear or branched alkyl group, and the number of carbon atoms is preferably 1 to 12.

Examples of commercially available compounds having such a benzotriazole skeleton include Tinuvin Carbo protect (manufactured by BASF), Tinuvin 384-2 (manufactured by BASF), and the like.

The compound having a benzotriazole skeleton can absorb light having a wavelength of 220 to 430 nm.

(Stilbyl biphenyl derivative)

The composition of the present invention may further contain a distyrylbiphenyl derivative as a fluorescent whitening agent. A distyryl biphenyl derivative is a derivative of a compound in which two styryl groups are bonded to biphenyl, and specific examples thereof include A compound represented by the following formula (II) and the like. The compound represented by the following formula (II) can be obtained in the form of Tinopal NFW LIQ (manufactured by BASF).

(Hydroxyphenyltriazine-based compound)

The composition of the present invention may further contain a compound having a hydroxyphenyltriazine skeleton (a hydroxyphenyltriazine-based compound) as an ultraviolet absorber. The hydroxyphenyltriazine-based compound is not particularly limited as long as it is a compound having a hydroxyphenyl group and a triazine ring, both of which are bonded by a single bond.

Examples of commercially available products of hydroxyphenyltriazine-based compounds include Tinuvin 400 (manufactured by BASF), Tinuvin 405 (manufactured by BASF), Tinuvin 460 (manufactured by BASF), Tinuvin 477 (manufactured by BASF), and Tinuvin 479. (Manufactured by BASF).

The amounts of the fluorene-based compound, benzotriazole-based compound, distyrylbiphenyl derivative, and hydroxyphenyltriazine-based compound are not particularly limited, and are relative to (A) the polymer and (B) the photopolymerization initiator. A total of 100 parts by mass with (D) the (meth) acryl-containing methoxy monomer and / or plasticizer is, for example, 0.001 to 5 parts by mass, preferably 0.001 to 2.0 parts by mass, More preferably, it is 0.001 to 0.5 parts by mass.

<(D) Containing (meth) acrylic fluorenyl monomer and / or plasticizer> (Contains (meth) acrylic fluorenyl monomer)

Hereinafter, the (meth) acrylic fluorenyl monomer is demonstrated.

The (meth) acryloxy group-containing monomer which can be contained in the composition of the present invention is not particularly limited as long as it is a monomer having at least one (meth) acryloxy group in one molecule.

The (meth) acrylfluorenyl group may be bonded to an organic group. The organic group is not particularly limited. For example, a hydrocarbon group which may have a hetero atom, such as an oxygen atom, a nitrogen atom, and a sulfur atom, is mentioned. Examples of the hydrocarbon group include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a combination thereof. At least one of the carbon atom or hydrogen atom which the hydrocarbon group has may be substituted with a substituent.

Examples of the substituent include monovalent substituents such as a hydroxyl group, an amino group, a mercapto group, and a halogen group; an ether bond, an imine bond, a thioether bond, a polythioether bond, a urethane bond, a urea bond, and an ester bond , Diamine bond, and other divalent substituents.

Examples of the (meth) acryloxy-containing monomer include (meth) acrylates of polyhydric alcohols.

Examples of the (meth) acrylate of a polyol include bifunctional compounds such as neopentyl glycol diacrylate; trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and Trifunctional compounds such as pentaerythritol tri (meth) acrylate; pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, tripentaerythritol tetra 4-functional compounds such as (meth) acrylates; dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylic acid Esters, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate and the like having more than 5 functions.

Among these, in consideration of the point that the effect of the present invention is more excellent, and the blue light resistance, hardenability, and adhesion are excellent, a bifunctional compound and a trifunctional compound are preferred, and neopentyl glycol diacrylate is more preferred.

The (meth) acrylic fluorenyloxy-containing monomers can be used alone or in combination of two or more kinds.

In consideration of the point that the effect of the present invention is more excellent, and the blue light resistance, hardenability, and viscosity are excellent, the amount of the (meth) acrylic fluorenyl monomer is preferably 10 to 100 parts by mass of the (A) polymer. 60 parts by mass, more preferably 10 to 50 parts by mass.

(Plasticizer)

The plasticizer is described below.

The plasticizer that can be contained in the composition of the present invention is not particularly limited.

Examples include phthalates such as diisononyl phthalate (DINP), dioctyl phthalate, dibutyl phthalate, and benzyl phthalate; adipic acid Aliphatic dibasic esters such as dioctyl ester, isodecyl succinate, dibutyl sebacate, etc .; alcohol esters such as diethylene glycol dibenzoate, pentaerythritol ester; butyl oleate, ethyl之 Fatty esters such as ricinoleic acid methyl ester; tricresyl phosphate, trioctyl phosphate, octyl diphenyl phosphate, etc. Phosphate esters; propylene glycol adipic acid polyester, butylene glycol adipic acid polyester; epoxy plasticizers such as epoxidized soybean oil, epoxidized linseed oil, epoxy benzyl stearate; polyester ; Polyethers such as polypropylene glycol or its derivatives; polystyrenes such as poly-α-methylstyrene and polystyrene; polybutadiene, butadiene-acrylonitrile copolymer, polychloroprene Ene, polyisoprene, polybutene; paraffin-based oil, naphthenic oil, aromatic oil, etc.

Among them, considering the viewpoint that the effect of the present invention is more excellent, and the anti-blue light performance, compatibility of other components, viscosity, and adhesion are excellent, dioctyl phthalate and liquid polybutadiene are preferred.

The plasticizers can be used alone or in combination of two or more kinds.

Considering the viewpoint that the effect of the present invention is more excellent, and the blue light resistance, hardenability, and viscosity are excellent, the amount of the plasticizer is preferably 10 to 60 parts by mass, and more preferably 10 relative to 100 parts by mass of the (A) polymer. To 50 parts by mass.

In the present invention, when a (meth) acryloxyl-containing monomer and a plasticizer are used in combination, considering that the effect of the present invention is more excellent, and the viewpoint of excellent blue light resistance, hardenability, and viscosity is superior to (A) polymerization 100 parts by mass, and the total amount of the two is preferably 10 to 60 parts by mass, and more preferably 10 to 50 parts by mass.

<(E) Epoxy polymer, fluorine polymer, polysiloxane>

In consideration of the point that the effect of the present invention is more excellent, and the blue light resistance and adhesiveness are excellent, the composition of the present invention preferably further contains (E) selected from the group consisting of epoxy polymers, fluorine polymers, polysiloxanes, and Group of modified substances At least one of the groups.

The epoxy-based polymer is not particularly limited as long as it is a polymer having one or more epoxy groups in one molecule.

The fluorine-based polymer is not particularly limited as long as it is a polymer having one or more fluorine atoms in one molecule.

The polysiloxane is not particularly limited as long as it is a polymer having a polysiloxane in the main chain.

In consideration of the point that the effect of the present invention is more excellent, and the blue light resistance and adhesion are excellent, the weight average molecular weight of (E) is preferably 1,000 to 100,000, and more preferably 5,000 to 50,000.

Considering that the effect of the present invention is more excellent, and the blue light resistance and adhesiveness are excellent, compared with (A) the polymer and (B) the photopolymerization initiator and (D) the (meth) acrylic fluorenyloxy monomer and The total amount of the plasticizer is 100 parts by mass, and the amount of (E) (the total amount of these when two or more kinds are used) is preferably 0.1 to 3 parts by mass, and more preferably 0.1 to 1 part by mass.

<Other additives>

The composition of the present invention may further contain additives as long as the object of the present invention is not impaired. Examples of the additives include blue light absorbers other than (C), monomers other than (meth) acryloxy-containing monomers, ultraviolet absorbers, fillers, anti-aging agents, antistatic agents, flame retardants, Tackifier, dispersant, antioxidant, defoamer, leveling agent, matting agent, light stabilizer, dye, pigment.

<Manufacturing method>

The production of the composition of the present invention is not particularly limited. For example, the above-mentioned (A) to (D), (E), and additives that can be used when necessary may be uniformly mixed to produce the composition of the present invention.

<Use etc.>

The composition of the present invention can form a transparent coating film with blue light resistance. In addition, the composition of the present invention can form an adhesive coating film.

The composition of the present invention can be used, for example, as a composition for forming a coating film having an anti-blue light function, a composition for forming an adhesive layer, a plastic surface protective agent, a hard coating material, a hard coating agent, and ultraviolet curing Paint, primer composition, etc.

The member to which the composition of the present invention can be applied is not particularly limited. Examples include optical display panels, touch panels, protective panels, optical films, and parallax barriers. The above-mentioned members are not particularly limited. For example, conventionally well-known members are mentioned.

The material of the member to which the composition of the present invention can be applied is not particularly limited. Examples include plastic, rubber, glass, metal, and ceramic. The form of the member may be, for example, a thin film.

The plastic using the composition of the present invention may be any of a thermosetting resin and a thermoplastic resin. Examples of the plastic include polyethylene terephthalate (PET), cycloolefin-based polymers (including homopolymers, copolymers, and hydrogen additives), polymethyl methacrylate resin (PMMA resin), Polycarbonate resin, polystyrene resin, acrylonitrile -Hard-to-stick resins such as styrene copolymer resin, polyvinyl chloride resin, acetate resin, ABS resin, polyester resin, and polyamide resin.

The member may be subjected to a surface treatment such as a corona treatment.

The method (use method) of applying the composition of the present invention to a member is not particularly limited, and for example, a well-known coating method such as brush coating, flow coating, dip coating, spray coating, and spin coating can be used.

Examples of the method for curing the composition of the present invention include a method using ultraviolet rays. When the composition of the present invention is hardened by ultraviolet irradiation, the amount of ultraviolet radiation (cumulative light amount) used when the composition of the present invention is hardened is preferably 50 to 3,000 mJ / from the viewpoints of rapid curing and workability. cm ² . The device for irradiating ultraviolet rays is not particularly limited. For example, a conventionally well-known apparatus can be mentioned. When curing, heating can be used together.

The composition of the present invention can be used in, for example, bonding of an optical display panel and a touch panel, bonding of an optical display panel and a protective panel, bonding of a touch panel and a protective panel, bonding of an optical display panel and an optical display panel, or optical Lamination of film and parallax barrier.

[Laminate]

The laminated body of the present invention will be described below.

The laminated system of the present invention borrows an adhesive layer formed of the ultraviolet curable resin composition of the present invention, and then the optical display panel and the touch panel, the optical display panel and the protection panel. A laminated body formed of a protective panel, a touch panel and a protective panel, an optical display panel and an optical display panel, or an optical film and a parallax barrier.

Since the laminated body of this invention has the adhesive layer formed using the composition of this invention, it is excellent in at least one of blue light resistance and transparency.

The composition used in the laminate of the present invention is not particularly limited as long as it is the composition of the present invention.

In addition, as a member used in the laminated body of the present invention, the optical display panel, touch panel, protective panel, optical film, and parallax barrier are not particularly limited. For example, a conventionally well-known thing can be mentioned.

Hereinafter, the structure of the laminated body of this invention is demonstrated using drawing. However, the present invention is not limited to the drawings.

FIG. 1 is a cross-sectional view schematically showing an example of the laminate of the present invention.

In FIG. 1, the laminated body 100 includes a member 102 as a first member, a member 106 as a second member, and an adhesive layer 104 formed using the composition of the present invention. The component 102 and the component 106 are connected by an adhesive layer 104.

The thickness of the component and the adhesive layer is not particularly limited. The thickness of each member is preferably about 50 to 300 μm. The thickness of the adhesive layer is preferably about 0.05 to 2,000 μm.

<Manufacturing method>

As for the manufacturing method of the laminated body of this invention, the composition which coat | coated the composition of this invention on the 1st member, dried, and superimposed on it is mentioned, for example. A method of manufacturing the second member and irradiating it with ultraviolet rays.

Here, the method of applying the composition of the present invention is not particularly limited, and for example, a well-known coating method such as brush coating, flow coating, dip coating, spray coating, and spin coating can be used.

In addition, the temperature for drying after coating is preferably 20 to 110 ° C.

In addition, from the viewpoints of rapid hardening property and workability, as the irradiation amount (cumulative light amount) of ultraviolet rays used when curing the composition of the present invention, the ultraviolet irradiation after drying is preferably 50 to 3,000 mJ / cm ² . The device for irradiating ultraviolet rays is not particularly limited. For example, a conventionally well-known apparatus can be mentioned. When curing, heating can be used together.

[Example]

Examples are shown below to specifically explain the present invention. The invention is not limited to these examples.

<Manufacture of composition>

Using a blender, each component of the following Table 1 was mixed according to the composition (parts by mass) shown in the table to produce a composition.

<Evaluation of subsequent strength>

A test piece for adhesion strength measurement was prepared as follows.

First, each composition manufactured as described above was applied to a circular glass having a diameter of 5 mm, and this glass was bonded to other glasses in a cross shape so as to have a thickness of 0.3 mm, followed by UV curing. The UV irradiation conditions were an illuminance of 300 mW / cm ² and a cumulative light amount of 300 mJ / cm ^{2. The} UV irradiation device was a high-pressure mercury lamp.

The adhesion strength was measured in the following manner. One of the cross-shaped glass was fixed, and the other glass was stretched at a tensile speed of 5 mm / min, and the maximum value when the cross-shaped glass was peeled was measured as the bonding strength. The results are shown in Table 1.

<Manufacturing of Laminates>

Using a coating bar, each composition produced as described above was applied to a polyethylene terephthalate film (PET texture: trade name A-4300, manufactured by Toyobo Co., Ltd., thickness 125 μm) at 80 ° C. This was dried for 1 minute, and then irradiated with ultraviolet rays (UV) using a GS UV SYSTEM manufactured by Kawaguchi Spring Manufacturing Co., Ltd. (UV irradiation conditions: illuminance 300 mW / cm ² , cumulative light amount 300 mJ / cm ² , UV irradiation device is a high-pressure mercury lamp), The composition hardens, forms an adhesive layer, and forms a laminate. The film thickness of the adhesive layer was 0.1 μm.

<Evaluation of average blue light resistance ratio, total light transmittance, and haze>

Using the laminates prepared as described above, the following evaluations were performed. The results are shown in Table 1.

(Average anti-blue light ratio)

Using a Hitachi spectrophotometer 3900H as a device, the laminated body manufactured as described above was irradiated with light having a wavelength in the range of 800 to 300 nm, and measured at 385. Average transmission (%) in the nm to 495nm range. The measurement result was substituted into the following formula, and the average blue light resistance ratio of the laminated body was calculated.

Average anti-blue light ratio of adhesive layer (%) = 100- (average transmittance in the range of 385 to 495nm)

(Full light transmittance)

The haze meter (HM-150, manufactured by Murakami Color Technology Research Institute) was used to measure the total light transmittance of the laminated body prepared as described above in accordance with JIS K 7361. Results are shown as the average of the number of samples n = 3.

The total light transmittance is preferably 90% or more.

(Haze)

The haze of the laminated body prepared as described above was measured using a haze meter (HM-150, manufactured by Murakami Color Technology Research Institute) in accordance with JIS K 7105. Results are shown as the average of the number of samples n = 3.

In the present invention, when the haze is 1.0 or less, the transparency is excellent.

The mixtures 1 to 4 shown in Table 1 are as follows.

The components (parts by mass) shown in the following Table 2 were used as the mixtures 1 to 4.

Each component shown in Table 2 is as follows.

‧ (Meth) acrylate modified polyisoprene: trade name UC-1, manufactured by Kuraray. It has a weight average molecular weight of 25,000 and has 3 (meth) acrylate groups per molecule.

‧ (Meth) acrylate modified polyurethane: trade name UA-1, manufactured by Light Chemical. The weight average molecular weight is 2,400, and it has 2 (meth) acrylate groups per molecule.

‧ (Meth) acrylate modified polybutadiene: trade name TE-2000, manufactured by Soda Japan. It has a weight average molecular weight of 2,000 and has 2 (meth) acrylate groups per molecule.

‧ (Meth) acrylate modified hydrogenated polybutadiene: trade name TEAI-1000, manufactured by Soda Japan. It has a weight average molecular weight of 1,000 and has two (meth) acrylate groups per molecule.

‧ (Meth) acrylate modified polypropylene glycol: (meth) acrylate modified polyoxypropylene, trade name FA-P270A, manufactured by Hitachi Chemical Co., Ltd. The weight average molecular weight is 823, and it has 2 (meth) acrylate groups per molecule.

‧Photopolymerization initiator: Irgacure 184 (manufactured by BASF)

‧ Contains (meth) acrylic alkoxy monomer 1: Trimethylolpropane triacrylate, trade name TMPTA, manufactured by Daicel Allnex

‧Contains (meth) acrylic alkoxy monomer 2: neopentyl glycol diacrylate, trade name FA-125M, manufactured by Hitachi Chemical Co., Ltd.

‧Plasticizer 1: Liquid polybutadiene, trade name L-LIR, manufactured by Kuraray

The components other than the mixtures 1 to 4 shown in Table 1 are as follows.

‧Napthalene imine-based compound 1: Lumogen F Violet 570 (manufactured by BASF)

‧Benzoxazoline compound 1: Tinopal OB CO (manufactured by BASF)

‧Sulfur Compound 1: Lumogen F Yellow 083 (manufactured by BASF)

‧Benzotriazole-based compound 1: Tinuvin Carbo protect (manufactured by BASF)

‧Stilbyl biphenyl derivative 1: Tinopal NFW LIQ (manufactured by BASF)

‧Hydroxyphenyltriazine compound 1: Tinuvin 479 (manufactured by BASF)

As can be seen from the results shown in Table 1, Comparative Examples 1 to 3 in which the naphthaleneimine-based compound exceeded a predetermined amount had high haze and low transparency.

In contrast, Examples 1 to 16 are excellent in transparency. In addition, Examples 1 to 16 have high bonding strength, excellent adhesion, and high blue light resistance.

Further, after comparing Example 5 and Example 8, it was found that Example 8 containing a (meth) acrylate-modified polyurethane was more excellent in adhesion than Example 5 containing no (meth) acrylate-modified polyurethane.

Claims (5)

An ultraviolet curable resin composition comprising: (A) a polymer of a hydrocarbon-based polymer modified with (meth)acrylate, and (B) a photopolymerization initiator, and (C) having a naphthalimide The naphthaleneimide-based compound of the skeleton, and the (meth)acryloyloxy group-containing monomer and/or plasticizer having at least one (meth)acryloyloxy group in one molecule of (D), relative to A total of 100 parts by mass of the polymer, the photopolymerization initiator, the (meth)acryloyl group-containing monomer and/or the plasticizer, and the amount of the naphthalimide-based compound is 0.001 to 5 parts by mass Parts; the aforementioned (meth)acrylate modified hydrocarbon polymer has at least one selected from the group consisting of polyisobutylene, polyolefin, polyisoprene, polybutadiene, and hydrogenated polybutadiene One type of hydrocarbon polymer is the main chain, and the terminal and/or side chain has a (meth)acryloyloxy group or a (meth)acryloyloxy group; the naphthaleneimide-based compound is represented by the following formula (1 ) Compounds shown:

In formula (1), R ¹ represents a hydrogen atom or a hydrocarbon group which may have a hetero atom, R ² represents a hydrogen atom or an organic group, and plural R ² may be the same or different. An ultraviolet curable resin composition comprising: (A) a polymer of a hydrocarbon-based polymer modified with (meth)acrylate, and (B) a photopolymerization initiator, and (C) having a naphthalimide The naphthaleneimide-based compound of the skeleton, and the (meth)acryloyloxy group-containing monomer and/or plasticizer having at least one (meth)acryloyloxy group in one molecule of (D), relative to A total of 100 parts by mass of the polymer, the photopolymerization initiator, the (meth)acryloyl group-containing monomer and/or the plasticizer, and the amount of the naphthalimide-based compound is 0.001 to 5 parts by mass Parts; the aforementioned (meth)acrylate-modified polyoxyalkylene has polyoxypropylene as the main chain, and the terminal and/or side chains have (meth)acryloyloxy or (meth)acryloyloxy The base of the group; the aforementioned naphthalamide compound is a compound represented by the following formula (1):

In formula (1), R ¹ represents a hydrogen atom or a hydrocarbon group which may have a hetero atom, R ² represents a hydrogen atom or an organic group, and plural R ² may be the same or different. The ultraviolet curable resin composition according to claim 1 or 2, wherein the weight average molecular weight of the aforementioned polymer is 1,000 to 100,000. The ultraviolet curable resin composition according to claim 1 or 2, which is used for bonding of an optical display panel and a touch panel, bonding of an optical display panel and a protective panel, bonding of a touch panel and a protective panel, and optical display panel and The bonding of the optical display panel, or the bonding of the optical film and the parallax barrier. A laminate using an adhesive layer formed from the ultraviolet curable resin composition of any one of claims 1 to 4, followed by an optical display panel and a touch panel, an optical display panel and a protection panel, a touch panel and a protection panel , Optical display panel and optical display panel, or optical film and parallax barrier.