TW201615725A - Ultraviolet curable resin composition and laminate using the same - Google Patents

Abstract

The purpose of the present invention is to provide: an ultraviolet light curable resin composition which has an excellent blue light-blocking function and excellent scratch resistance; and a laminate using the same. The present invention is an ultraviolet light curable resin composition and a laminate using the same. Relative to (A) 100 parts by mass of a polyfunctional (meth)acryloyloxy group-containing compound having at least two (meth)acryloyloxy groups in one molecule, the ultraviolet light curable resin composition contains: (B) 0.05-10 parts by mass of at least one selected from the group consisting of a naphthalimide compound having a naphthalimide skeleton and a benzoxazoline compound having a benzoxazoline skeleton; (C) 0.05-10 parts by mass of a fluorine compound having at least one fluorine atom and at least one (meth)acryloyloxy group in one molecule; (D) a photopolymerisation initiator; and (E) an organic solvent.

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, in an apparatus such as an electronic image display device, for example, a hard coating material having a blue light-resistant function is applied to a back surface of a substrate (such as a film of polyethylene terephthalate or the like), and the surface of the substrate is coated. A laminate made of a hard coating material having scratch resistance.

Further, in order to provide an ultraviolet curable resin composition excellent in anti-blue light function, the present applicant proposes an ultraviolet curable resin composition as follows: an ultraviolet curable resin composition having a film and a hardening on a film The coating layer is used for forming a cured coating film of a laminate used in an electronic image display device, and comprises the following components (A) to (C), and the amount of the component (C) is 0.7 to 2.0 mass of the nonvolatile component. Percentage (Patent Document 1),

(A): Polyfunctional (meth) acrylate

(B): Photopolymerization initiator

(C): A blue light absorber containing a compound having a naphthoquinone imine skeleton and/or a compound having an anthracene skeleton.

[Advanced technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 5459446

However, the present inventors have clarified that if a layer having a blue light-resistant function and a layer having scratch resistance are separately provided on a substrate, productivity is deteriorated, but if a layer having a function of resisting blue light is desired to have scratch resistance, Sex, you may not be able to maintain anti-blue light.

Accordingly, an object of the present invention is to provide an ultraviolet curable resin composition which can maintain a high anti-blue light function and is excellent in scratch resistance, and a laminate using the same.

In order to solve the problem, the inventors of the present invention have found that the (100) polyfunctional (meth) propylene oxime compound having at least two (meth) acryloxy groups in one molecule has a mass of 100%. And containing (B) a naphthyl imine compound selected from the group consisting of a naphthoquinone imine skeleton And at least one of 0.05 to 10 parts by mass of the group consisting of the benzoxazoline-based compound having a benzoxazoline skeleton, and (C) having at least one (meth)acrylic acid in one molecule The epoxy group having at least one fluorine atom and 0.05 to 10 parts by mass of the fluorine atom, and the (D) photopolymerization initiator and the ultraviolet curable resin composition of the (E) organic solvent can have excellent anti-blue light function and scratch resistance. And complete the present invention.

In other words, the inventors of the present invention have found that the above problems can be solved by the following configuration.

1. An ultraviolet curable resin composition containing 100 parts by mass of a polyfunctional (meth) acryloxy compound having at least two (meth) acryloxy groups in one molecule (A) (B) at least one selected from the group consisting of a naphthoquinone imine compound having a naphthoquinone imine skeleton and a benzoxazoline compound having a benzoxazoline skeleton, 0.05 to 10 parts by mass, And (C) 0.05 to 10 parts by mass of the fluorine-based compound having at least one (meth)acryloxy group and at least one fluorine atom in one molecule, and (D) a photopolymerization initiator, and (E) organic Solvent.

2. The ultraviolet curable resin composition according to the above 1, wherein the polyfunctional (meth)acryl oxime compound contains at least two (meth) acryloxy groups and at least one or more in one molecule. The urethane bond contains a (meth) acryloxy compound a1.

3. The ultraviolet curable resin composition according to the above 1 or 2, wherein the naphthoquinone imine compound is a compound represented by the following formula (1), (In the 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 's} may be the same or may be different).

4. The ultraviolet curable resin composition according to any one of the above 1 to 3, wherein the skeleton of the fluorine-based compound is polyoxyalkylene.

The ultraviolet curable resin composition according to any one of the above 1 to 4, further comprising a compound having at least one polyoxyalkylene moiety and at least 12 (meth)acryloxyloxy groups in one molecule (F).

6. The ultraviolet curable resin composition according to the above 5, wherein the compound (F) further has an isocyanurate ring.

7. The ultraviolet curable resin composition according to the above-mentioned item 5 or 6, wherein the amount of the compound (F) is 10 parts by mass or less based on 100 parts by mass of the polyfunctional (meth)acryl methoxy compound.

8. The ultraviolet curable resin composition according to any one of the above 1 to 7, which is used for an electronic image display device or an eyeglass lens.

A laminate comprising a substrate and a cured film, wherein the cured film is an ultraviolet light using any one of the above 1 to 8 The composition of the resin is formed.

The ultraviolet curable resin composition of the present invention and the laminate of the present invention are excellent in anti-blue light function and scratch resistance.

100‧‧‧Layer

102‧‧‧Substrate

104‧‧‧ hardened film

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing an example of a laminate of the present invention.

[to implement the form of the Ming] [Ultraviolet curable resin composition]

Hereinafter, the present invention will be described in detail.

Hereinafter, the ultraviolet curable resin composition of the present invention will be described first.

In the ultraviolet curable resin composition of the present invention (the composition of the present invention), the polyfunctional (meth) propylene oxide having at least two (meth) acryloxy groups in one molecule is contained in (A) 100 parts by mass of the base compound, containing (B) at least 1 selected from the group consisting of a naphthoquinone imine compound having a naphthoquinone imine skeleton and a benzoxazoline compound having a benzoxazoline skeleton 0.05 to 10 parts by mass, and (C) having at least one (meth) acryloxy group in one molecule 0.05 to 10 parts by mass of the fluorine-based compound having at least one fluorine atom, (D) a photopolymerization initiator, and (E) an organic solvent.

In the present specification, the (A) polyfunctional (meth) propylene decyloxy compound is referred to as a polyfunctional (meth) propylene oxime compound, or (A) or (A) component. The components described in (B) to (F) are also the same.

Further, it is said that the effect of the present invention is excellent in that the anti-blue light function and the scratch resistance are excellent. It is more excellent that the effect of the present invention is more excellent in that at least one of the anti-blue light function and the scratch resistance is more excellent.

<(A) Polyfunctional (meth) propylene oxime compound>

Hereinafter, the polyfunctional (meth) propylene decyloxy compound will be described.

The polyfunctional (meth)acryl oxime compound contained in the composition of the present invention is a compound having at least two (meth) acryloxy groups in one molecule. In the present invention, as one of preferred embodiments, a compound having Si-O-Si removed from a polyfunctional (meth)acryl oxime compound can be mentioned. Moreover, as one of preferable aspects, a compound having a fluorine atom is removed from a polyfunctional (meth)acryl oxime compound.

Further, "(meth)acryloxy" means propylene methoxy (CH ₂ =CHCOO-) or methacryloxy (CH ₂ =C(CH ₃ )COO-), "(methyl) "Acrylate" shall mean acrylate or methacrylate.

In view of the fact that the effect of the present invention is more excellent, the coating property (coatability), the appearance of the coating film, the compatibility with the additive, and the surface hardness are excellent, and the polyfunctional (meth) propylene oxime compound is contained in one molecule. The amount of the (meth) propylene fluorenyl group is preferably from 2 to 15, more preferably from 4 to 12.

In the polyfunctional (meth) propylene oxime compound, the (meth) propylene oxime group may be bonded to the 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 or a sulfur atom may be mentioned. Examples of the hydrocarbon group include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a combination thereof. At least one of the carbon atoms or hydrogen atoms of the hydrocarbon group may be substituted with a substituent.

Examples of the substituent include a monovalent substituent such as a hydroxyl group, an amine group, a decyl group or a halogen; an ether bond, an imine bond, a sulfide bond, a polysulfide bond, a urethane bond, a urea bond, an ester bond, and the like. A divalent substituent such as a guanamine bond.

In view of the fact that the effect of the present invention is more excellent, the coating property (coatability), the appearance of the coating film, the compatibility with the additive, and the surface hardness are excellent, and the polyfunctional (meth) propylene oxime compound is contained in one molecule. The number of the above substituents may preferably be from 1 to 10, more preferably from 2 to 5. The number of substituents per molecule may also be zero.

In view of the fact that the effect of the present invention is more excellent, the curability (photopolymerizable property), the reactivity (photopolymerization in a short time), the surface hardness, and the like are excellent, and the polyfunctional (meth) propylene decyloxy compound is preferable. The (meth)acryloxy compound a1 having at least two (meth)acryloxy groups and at least one urethane bond in one molecule and/or at least two molecules in one molecule The (meth)acrylomethoxy group contains a (meth)acryloxy compound a2 (excluding the above-mentioned (meth)acryloxy compound a1).

The (meth) propylene oxime compound a2 is a compound having at least two (meth) propylene fluorenyloxy groups in one molecule. Further, in the present invention, the (meth)acryl oxime compound a2 does not include the (meth) propylene oxime compound a1.

The (meth) propylene oxime compound a2 is preferably a compound in which at least two (meth) propylene oxime groups are bonded to a hydrocarbon group in one molecule. The hydrocarbon group may be any of a linear chain, a branched chain, and a cyclic group. The hydrocarbon group may have an unsaturated bond. Examples of the hydrocarbon group include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and the like. The hydrocarbon group preferably has 2 to 8 carbon atoms. The 2 hydrocarbon groups may be bonded by, for example, an oxygen atom.

Examples of the (meth)acryl methoxy compound a2 include a (meth) acrylate of a polyhydric alcohol.

Examples of the (meth) acrylate of the polyhydric alcohol include trifunctional compounds such as trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol tri(meth)acrylate. a tetrafunctional compound such as pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, tripentaerythritol tetra(meth)acrylate; dipentaerythritol penta(meth)acrylate, dipentaerythritol six (a) Acrylate, tripentaerythritol penta (meth) acrylate, tripartite A compound having five or more functional groups such as tetraol hexa(meth) acrylate, tripentaerythritol hepta (meth) acrylate, or tripentaerythritol octa (meth) acrylate.

The (meth) propylene oxime compound a2 may be used alone or in combination of two or more.

The (meth) propylene oxime compound a1 is a compound having at least two (meth) acryloxy groups and at least one urethane bond in one molecule.

Examples of the (meth)acryl methoxy compound a1 include a reaction product of a (meth) acrylate of a polyhydric alcohol and a polyisocyanate compound.

Here, as the (meth) acrylate of the polyol used in the production of the (meth)acrylic urethane, for example, the (meth) acrylate of the above polyol has at least one hydroxyl group.

Further, examples of the polyisocyanate compound used in the production of the (meth)acrylic acid urethane include toluene diisocyanate, diphenylmethane diisocyanate, phenylphenyl diisocyanate, and polymethylene polyphenylene polyisocyanate. An aromatic polyisocyanate such as benzene dimethylene diisocyanate, tetramethyl benzene dimethylene diisocyanate, tolidine diisocyanate, 1,5-naphthalene diisocyanate or triphenylmethane triisocyanate; Methyl diisocyanate, trimethyl hexamethylene diisocyanate, lysine diisocyanate, norbornane diisocyanate, trans cyclohexane-1,4-diisocyanate, isophorone diisocyanate, bis (isocyanate) Aliphatic polyisocyanate such as cyclomethyl or cyclohexane methane diisocyanate An alicyclic polyisocyanate); such isocyanurate, biuret, adduct, and the like.

The (meth) propylene oxime compound a2 may be used alone or in combination of two or more.

The production of the polyfunctional (meth)acryloxy compound is not particularly limited. For example, those well known in the past can be mentioned.

The (meth) propylene oxime compound may be used alone or in combination of two or more.

Examples of the combination of the (meth)acryl methoxy compound include a combination of the (meth) propylene methoxy compound a2 and the (meth) propylene oxy compound a1. Specifically, for example, Selecting at least one of a group consisting of a reaction product of dipentaerythritol pentaacrylate and an aliphatic polyisocyanate and a reaction product of pentaerythritol triacrylate and an aliphatic polyisocyanate, and a selected from the group consisting of dipentaerythritol hexaacrylate and A combination of at least one of the group consisting of pentaerythritol triacrylate.

<(B) is at least one selected from the group consisting of a naphthoquinone imine compound and a benzoxazoline compound> (naphthyl imine compound)

Hereinafter, the naphthoquinone imine compound will be described.

The naphthoquinone imine compound contained in the composition of the present invention is a compound having a naphthoquinone imine skeleton.

Anti-blue of the composition of the present invention by containing a naphthoquinone imine compound Excellent light function.

In view of the fact that the effect of the present invention is more excellent, the high blue light resistance is exhibited, and the compatibility with other components is excellent, the naphthoquinone imine compound is preferably a compound represented by the following formula (1). (In the 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 's} may be the same or may be different).

The hydrocarbon group which may have a hetero atom represented by R ¹ in the above formula (1) may, for example, be an aliphatic hydrocarbon group, an alicyclic hydrocarbon group or an aromatic hydrocarbon group, or a combination thereof. The hydrocarbyl group may also have a hetero atom and/or an unsaturated bond. A hetero atom can be a combination of a plurality of heteroatoms, a combination of a hetero atom and a carbon atom or a hydrogen atom. The bonding position of the hetero atom is not particularly limited.

Examples of the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen.

Examples of the hydrocarbon group having a hetero atom include a *-X-aliphatic hydrocarbon group (X represents an oxygen atom, a nitrogen atom or a sulfur atom. The same applies hereinafter), *-X-lipid. A cyclic hydrocarbon group, a *-X-aromatic hydrocarbon group. In addition, * indicates the bonding position.

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

R ² represents a hydrogen atom or an organic group. Examples of the organic group include a hydrocarbon group which may have a hetero atom; and a functional group.

The hydrocarbon group which may have a hetero atom as R ^{2 is} the same as the hydrocarbon group which may have a hetero atom of R ¹ . The hydrocarbon group which may have a hetero atom is preferably an alkoxy group, more preferably a methoxy group or an ethoxy group.

Examples of the functional group include a hydroxyl group, an amine group, a nitro group and the like.

The naphthoquinone imine compound can reduce at least a portion of the light transmittance in the wavelength range of 385 to 495 nm.

For example, Lumogen F Violet 570 (manufactured by BASF Corporation) is preferable as a commercially available product of such a naphthoquinone imine compound.

(benzoxazoline compound)

Hereinafter, the benzoxazoline-based compound will be described.

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

The composition of the present invention is excellent in blue light resistance by containing a benzoxazoline compound.

The compound having a benzoxazoline skeleton is not particularly limited as long as it is a compound having a benzoxazole ring, but is preferably a compound represented by the following formula (I) in order to further improve the overall anti-blue light function. Among them, a compound represented by the following formula (Ia) is more preferred.

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

The organic group represented by R ^a in the above formula (I) may, for example, be 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 the like. It can also have an unsaturated bond.

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

Further, the number of carbon atoms of the hydrocarbon group represented by R ^a is preferably from 1 to 12, more preferably from 3 to 6.

The benzoxazoline compound can reduce at least a portion of the light transmittance in the wavelength range of 350 to 495 nm.

As a commercial product of such a benzoxazoline-based compound, for example, Tinopal OB CO (manufactured by BASF Corporation), Nikkafluor OB (manufactured by Nippon Chemical Industry Co., Ltd.), and the like can be mentioned.

100 parts by mass of the polyfunctional (meth) propylene oxirane compound selected from the group consisting of naphthyl imine compounds and benzoxazolines The amount of at least one of the groups consisting of the compounds (when the naphthoquinone imine compound and the benzoxazoline compound are used together, the total amount of the two) is 0.05 to 10 parts by mass, and this is considered. The effect of the invention is further excellent, and the high blue light resistance is exhibited, and the compatibility with other components (liquid appearance and coating film appearance at the time of coating) is preferably 0.2 to 8 parts by mass, more preferably 0.7 to 7 mass. Further, it is preferably from 1 to 5 parts by mass.

Considering the viewpoint that the effect of the present invention is more excellent (especially, excellent in blue light resistance), when a naphthoquinone imine compound and a benzoxazoline compound are used, a benzoxazoline compound and a naphthylimine compound are used. The mass ratio of the compound (benzoxazoline compound / naphthylimine compound) is preferably 0.001 to 10, more preferably 0.1 to 5.

The composition of the present invention may further contain at least one selected from the group consisting of an anthraquinone compound, a benzotriazole-based compound, a distyrylbiphenyl derivative, and a hydroxyphenyltriazine-based compound.

(lanthanide compound)

The composition of the present invention may further contain a compound having an anthracene skeleton (lanthanide compound). The compound having an anthracene skeleton is not particularly limited. The anthracene skeleton may also have a substituent. The ruthenium skeleton is represented by the following formula (2).

The commercially available product of the compound having an anthracene skeleton is, for example, Lumogen F Yellow 083 (manufactured by BASF Corporation).

A compound having an anthracene skeleton absorbs a field of a long wavelength end of blue light (420 to 495 nm) as compared with a compound having a naphthoquinone imine skeleton.

(benzotriazole compound)

The composition of the present invention may further contain a compound having a benzotriazole skeleton (benzotriazole-based compound). The compound having a benzotriazole skeleton is not particularly limited. The benzotriazole skeleton may also have a substituent. The benzotriazole-based compound may, for example, be a compound represented by the following formula (3).

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

The hydrocarbon group which may have a hetero atom represented by R ³ in the above formula (3) may, for example, be an aliphatic hydrocarbon group, an alicyclic hydrocarbon group or an aromatic hydrocarbon group, or a combination thereof, or may have an unsaturated bond.

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

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

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

(distyrylbiphenyl derivative)

The composition of the present invention may further contain a distyrylbiphenyl derivative as a fluorescent whitening agent. The distyrylbiphenyl 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). Further, the compound represented by the following formula (II) can be obtained as Tinopal NFW LIQ (manufactured by BASF Corporation).

(hydroxyphenyltriazine-based compound)

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

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

The amount of the above oxime compound, benzotriazole compound, distyrylbiphenyl derivative or hydroxyphenyl triazine compound is not particularly limited. 100 parts by mass of the polyfunctional (meth) propylene oxirane compound, which is selected from the group consisting of a lanthanide compound, a benzotriazole compound, a distyrylbiphenyl derivative, and a hydroxyphenyl triazine compound. The content of at least one of the group (hereinafter, these substances may be simply referred to as an anthraquinone compound or the like) may be 0.001 to 5 parts by mass, preferably 0.001 to 2.0 parts by mass.

<(C) fluorine-based compound>

Hereinafter, the fluorine-based compound will be described.

The fluorine-based compound contained in the composition of the present invention is a compound having at least one (meth)acryloxy group and at least one fluorine atom in one molecule. Further, in the present invention, as one of preferred embodiments, a compound having an isocyanurate ring removed from a fluorine-based compound can be mentioned.

The composition of the present invention is scratch-resistant and slippery by containing a fluorine-based compound Excellent in dynamic and antifouling properties.

In view of the fact that the effect of the present invention is more excellent, and the compatibility with other components is excellent, and the scratch resistance is excellent, the number of (meth)acryloxy groups of the fluorine-based compound in one molecule is preferably from 2 to 15. More preferably, it is 2 to 5.

The skeleton of the fluorine-based compound may be any of a hydrocarbon and a polyoxyalkylene.

The hydrocarbon as the skeleton is not particularly limited. When the skeleton of the fluorine-based compound has a polyoxyalkylene oxide, the skeleton is referred to as a decane skeleton.

In view of the fact that the effect of the present invention is more excellent and the compatibility with other components is excellent, the fluorine-based compound may preferably have a polyoxyalkylene oxide, more preferably a polyalkylene oxide, and further preferably a dialkyl polysiloxane. Preferred is dimethyloxane.

One of the preferable aspects is that the polyoxyalkylene which the fluorine-based compound may have is linear.

The weight average molecular weight of the polyoxyalkylene which the fluorine-based compound may have is not particularly limited.

The weight average molecular weight of the fluorine-based compound is not particularly limited.

In view of the fact that the effect of the present invention is more excellent and the compatibility with other components is excellent, the fluorine-based compound is preferably a compound having a linear dialkyl polysiloxane as a main chain and having at least 1 One (meth) acryloxy group is used as a group of a side chain.

The fluorine-based compounds may be used alone or in combination of two or more. The production of the fluorine-based compound is not particularly limited. For example, it can be cited Well known.

The amount of the fluorine-based compound is 0.05 to 10 parts by mass based on 100 parts by mass of the polyfunctional (meth)acryl oxime compound, and the effect of the present invention is more excellent, and the compatibility with other components and the appearance of the coating film are excellent. The viewpoint is preferably from 0.5 to 10 parts by mass, more preferably from 0.5 to 5.0 parts by mass, particularly preferably from 1.0 to 3 parts by mass.

<(D) Photopolymerization Initiator>

Hereinafter, the photopolymerization initiator will be described.

The photopolymerization initiator contained in the composition of the present invention is not particularly limited as long as it can polymerize an ethylenic functional group (for example, (meth)acryloxy group) by light.

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. Specific examples thereof include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, acetoin, butyl acetoin, toluene, benzyl, benzophenone, p-methoxybenzophenone, Diethoxyacetophenone, α,α-dimethoxy-α-phenylacetophenone, methylphenylglyoxylate, ethylphenylglyoxylate, 4,4′-bis ( Dimethylaminobenzophenone), 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1- a carbonyl compound such as a ketone or a 1-hydroxycyclohexyl phenyl ketone; a sulfur compound such as tetramethylthiuram monosulfide or tetramethylthiuram disulfide; azobisisobutyronitrile or azo-2,4 - an azo compound such as dimethyl valeronitrile; benzamidine peroxide, di-tert-butyl peroxide Such as peroxide compounds and the like.

Among them, 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2-methyl-1 are preferred from the viewpoints of photostability, photocracking efficiency, surface hardenability, compatibility, low volatility, and low odor. -Phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one.

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

The amount of the photopolymerization initiator is preferably from 1 to 10 parts by mass based on 100 parts by mass of the polyfunctional (meth) propylene methoxy compound.

<(E) organic solvent>

Hereinafter, the organic solvent will be described.

The organic solvent contained in the composition of the present invention is not particularly limited. For example, a ketone; an ether; an ester such as ethyl acetate or butyl acetate; an alcohol such as isopropyl alcohol (IPA); a cycloalkane such as cyclohexane; and an aromatic hydrocarbon compound such as toluene, xylene or benzyl alcohol.

Here, it is considered that at least one selected from the group consisting of a naphthoquinone imine compound, a benzoxazoline compound, and a fluorine-based compound is easily compatible with a polyfunctional (meth)acryloxy compound. Therefore, the anti-blue light function and the scratch resistance are more excellent, and the liquid appearance, the coating film appearance or the liquid (storage) stability at the time of coating can be selected from the group consisting of a naphthoquinone imine compound and a benzoxazoline compound. At least one of the group is dissolved in a large amount so as to have a high blue light resistance, and the organic solvent preferably contains at least a ketone. And / or ether.

Examples of the ketone include methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), and cyclohexanone.

Examples of the ether include methylphenyl ether (anisole).

In view of the fact that the effect of the present invention is more excellent and the compatibility is excellent, the amount of the organic solvent is preferably from 30 to 900 parts by mass, more preferably from 100 parts by mass based on 100 parts by mass of the polyfunctional (meth) propylene methoxy compound. Up to 200 parts by mass.

When the organic solvent contains a ketone and/or an ether, the amount of the ketone and/or ether is preferably 60% by mass or more, 100% by mass or less, and more preferably 70 to 95% by mass based on the entire organic solvent.

Considering the effect of the present invention, the compatibility of the present invention, the appearance of the liquid, the appearance of the coating film (leveling property), and the liquid stability are excellent. When the organic solvent contains at least a ketone and an ether, the mass ratio of the ketone to the ether (ether/ketone) It is preferably from 0.5 to 20, more preferably from 0.6 to 1.0.

(compound (F))

The composition of the present invention preferably further contains (F) at least one polyoxyalkylene in one molecule, in view of the fact that the effect of the present invention is more excellent, and the slidability, the antifouling property, the haze reduction, and the optical characteristics are excellent. A compound (F) having at least 12 (meth)acryloxy groups.

The compound (F) has a polyoxyalkylene moiety and is therefore a compound having Si-O-Si.

The compound (F) has a polyoxyalkylene moiety in one molecule There is no particular limitation on the (meth) acryloxy group.

The compound (F) may further have at least one isocyanurate ring in one molecule.

The compound (F) is, for example, a (meth) acrylate compound (A) described in JP-A-2012-144670.

In the present invention, as the compound (F), for example, a (meth) acrylate compound (A) described in JP-A-2012-144670 can be used.

In view of the fact that the effect of the present invention is more excellent, and the adhesion, the appearance of the coating film at the time of liquid/coating, the higher scratch resistance, and the improvement of the surface hardness are excellent, the compound (F) has one molecule. The amount of the acryloxy group is preferably from 12 to 20, more preferably from 12 to 15.

The compound (F) may be used alone or in combination of two or more.

In view of the fact that the effect of the present invention is more excellent, and the adhesion to the coating texture is excellent, the amount of the compound (F) is preferably 10% by mass based on 100 parts by mass of the polyfunctional (meth) propylene methoxy compound. The fraction is preferably 0.5 to 5 parts by mass.

The solid content concentration of the composition of the present invention is preferably from 20 to 80% by mass in the composition, more preferably 30, from the viewpoint that the effect of the present invention is more excellent, the coating film appearance (leveling property), and optical characteristics are excellent. Up to 60% by mass. In the present invention, (A), (B), and (C) are contained in the solid portion. When the composition of the present invention further contains an oxime compound or the like (F), the solid component contains (A), (B), (C), lanthanide compounds, and the like (F). Further, the photopolymerization initiator is not contained in the solid portion.

(other additives)

The composition of the present invention may further contain an additive within the range not impairing the object of the present invention. Examples of the additive include an ethylenic compound other than (A), a blue light absorber other than (B), a fluorine-based compound other than (C), an ultraviolet absorber, a filler, an anti-aging agent, an antistatic agent, and a flame retardant. Agents, tackifiers, dispersants, antioxidants, defoamers, leveling agents, matting agents, light stabilizers, dyes, pigments.

(Production method)

The method for producing the composition of the present invention is not particularly limited. For example, the above-mentioned (A) to (E), an anthraquinone compound which can be used as needed, a compound (F) and an additive are uniformly mixed, whereby the composition of the present invention is prepared.

(use, etc.)

The composition of the present invention can be used, for example, as a composition for forming a coating film having a function of resisting blue light and scratch resistance, a plastic surface protective agent, a hard coat paint, a hard coat agent, an ultraviolet curable paint, Primer composition, etc.

Further, the composition of the present invention can be used for an electronic image display device or an eyeglass lens.

The material of the substrate to which the composition of the present invention can be applied is not particularly limited. example Examples include plastics, rubber, glass, metals, ceramics, and the like. The substrate form can be, for example, a film.

The plastic of the composition of the present invention may be used, and any of a thermosetting resin and a thermoplastic resin may be used. Examples of the plastic include polyethylene terephthalate (PET), a cycloolefin polymer (including a homopolymer, a copolymer, and a hydride), a polymethyl methacrylate resin (PMMA resin), and a poly Carbonate resin, polystyrene resin, acrylonitrile-styrene copolymer resin, polyvinyl chloride resin, acetate resin, acrylonitrile-butadiene-styrene resin (ABS resin), polyester resin, polyamide resin Such as difficult to adhere to the resin.

The substrate may also have been subjected to a surface treatment such as corona treatment.

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

As a hardening method of the composition of this invention, the hardening method by ultraviolet-ray is mentioned. When the composition of the present invention is cured by ultraviolet irradiation, the ultraviolet irradiation amount (accumulated light amount) used for curing the composition of the present invention is preferably from 50 to 3,000 mJ/cm from the viewpoint of quick-curing property and workability. ^2. The means for irradiating ultraviolet rays is not particularly limited. For example, those well known in the past can be mentioned. When hardening, it is also possible to use heat together.

[Layer]

Hereinafter, the laminate of the present invention will be described.

The laminate system of the present invention has a laminate of a substrate and a cured film, The cured film is formed using the above composition of the present invention.

Since the laminate of the present invention has a cured film formed by using the composition of the present invention, it is excellent in anti-blue light function and scratch resistance.

<Substrate>

The substrate is not particularly limited. The same as the above can be cited. The thickness of the substrate is not particularly limited. The thickness of the substrate is preferably about 50 to 2,000 μm.

<hardened film>

The cured film is not particularly limited as long as it is formed by using the composition of the present invention. The thickness of the cured film is not particularly limited. The thickness of the cured film is preferably about 0.01 to 100 μm.

The laminate of the present invention may further have an easy-adhesion layer and/or a rough layer or the like between the substrate and the cured film. The formation method, thickness, and material of the easy-adhesion layer are not particularly limited.

Hereinafter, the constitution of the laminate of the present invention will be described with reference to the drawings. The invention is not limited to the drawings.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing an example of a laminate of the present invention.

In Fig. 1, a laminate 100 has a substrate 102 and a cured film 104 formed using the composition of the present invention.

(Production method)

The method for producing the laminate of the present invention includes, for example, the following The method comprises the steps of applying the composition of the present invention to a film-form substrate (the above-mentioned easy-adhesive layer or a rough layer, which is the above-mentioned easy-adhesion layer or a rough layer), and drying the composition to irradiate ultraviolet rays.

Here, the coating method for 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, or spin coating may be employed.

The coated composition can also be dried. The temperature at which it is dried after coating is preferably from 20 to 110 °C.

In addition, from the viewpoint of the quick-curing property and the workability, the ultraviolet irradiation amount (cumulative light amount) used for curing the composition of the present invention in ultraviolet irradiation after drying is preferably from 50 to 3,000 mJ/cm ² . The means for irradiating ultraviolet rays is not particularly limited. For example, those well known in the past can be mentioned. When hardening, it is also possible to use heat together.

The laminate of the present invention can be used for, for example, an electronic image display device, an eyeglass lens, a shield for illumination (especially LED illumination), a solar cell module member, and the like.

Examples of the electronic image display device include electronic device components for display applications such as a personal computer, a television, a touch panel, and a wearable terminal (for example, a wearable computer terminal such as a glasses type or a wristwatch type).

The laminate of the present invention may be incorporated or externally attached (for example, externally attached) to an electronic image display device or the like. When the laminate of the present invention is placed in an electronic image display device or the like, it can be applied to, for example, a portion other than the reflector. Specifically, it can be applied to, for example, a lens sheet, a diffuser sheet, and a light guide plate.

The composition of the present invention can be directly applied to an electronic image display device to form a cured film.

[Examples]

Hereinafter, the present invention will be specifically described by showing examples. However, the invention is not limited to the embodiments.

<Manufacture of composition>

The components shown in the table below were mixed with a mixture of the components shown in the following Table 1 to prepare a composition.

In addition, the solid (%) column of the first table indicates the solid content (mass percentage) of each component.

In addition to the (A), (C), (F), distyrylbiphenyl derivative 1 and hydroxyphenyltriazine compound 1 of the first table, the other components are used in the form of containing an organic solvent. . In the first table, the amounts of (A), (C), (F), distyrylbiphenyl derivative 1 and hydroxyphenyltriazine compound 1 shown in the respective examples are the amounts of solids. .

The solid portion of (A) contains DPPA-HDI, PETA-IPDI, DPHA, and DPPA.

<Manufacture of laminates>

Each of the compositions produced as described above was applied onto a polyethylene terephthalate film (PET texture: trade name A-4300, manufactured by Toyobo Co., Ltd., 210 mm × 297 mm, thickness: 125 μm) using a bar coater. After drying at 80 ° C for 1 minute, it was irradiated with ultraviolet rays (UV) using a GS UV SYSTEM manufactured by Kawaguchi Spring Co., Ltd. (UV irradiation conditions: illuminance: 300 mW/cm ² , cumulative light amount: 300 mJ/cm ² , UV irradiation device was A high pressure mercury lamp) hardens the composition to form a cured film to produce a laminate. The film thickness of the cured film of the laminate was 5 μm.

<evaluation>

The following evaluation was carried out using the laminate manufactured as above. The results are shown in Table 1.

(anti-blue function: average anti-blue ratio)

Using the Hitachi spectrophotometer 3900H as a device, the laminate produced as above was irradiated with light having a wavelength of 800 to 300 nm, and the average transmittance (%) in the field of 385 nm to 495 nm was measured. The measurement results were substituted into the following formula, and the average blue light resistance ratio of the laminate was calculated.

Average blue light resistance ratio (%) of the laminate = 100 - (average transmittance in the above-mentioned 385 to 495 nm field measured for the laminate)

In the present invention, the average blue light resistance ratio of the laminate is preferably 13% or more, more preferably 21% or more.

Further, the above-mentioned polyethylene terephthalate film (thickness 125 μm) used as a substrate has an average blue light resistance ratio (the method of measuring the blue light resistance is the same as that of the laminate) in the field of 385 nm to 495 nm of about 11%.

(scratch resistance)

The surface of the cured film of the laminate manufactured as above was scraped back and forth 100 times with a load of 250 g/cm ² using steel wool (#0000).

After reciprocating scratching 100 times, it was visually confirmed whether or not the cured film was scratched.

If there is no scratch, it is evaluated as "○", and if there is scratch, it is evaluated as "X".

(film appearance)

The cured film of the laminate produced as above was visually observed.

According to the visual judgment, when the cured film was smoothed, it was regarded as excellent in appearance, and it was evaluated as "○".

According to visual judgment, when the agglomerated particles on the cured film and/or shrinkage were regarded as poor appearance, the evaluation was "x".

(anti-fouling)

A Hi-Mckee Care oil-based pen (bump) manufactured by ZEBBRA Co., Ltd. was used to scribe the surface of the cured film of the laminate manufactured as above. After drying at 23 ° C for 1 minute, the wire was reciprocally rubbed on the cured film under the trade name BEMCOT (size: 150 mm × 150 mm) (manufactured by Asahi Kasei Fiber Co., Ltd.), and the number of reciprocations before the disappearance of the line was evaluated as follows.

The person who disappeared twice after the reciprocation was regarded as the antifouling property, and was evaluated as "◎".

Those who reciprocated three times or more and five times in the inner line were regarded as excellent in antifouling property, and the evaluation was "○".

It is considered that the anti-staining property is poor, and the evaluation is not performed. It is "X".

(slidability)

First, the laminate was placed on a horizontal surface, and water droplets were dropped at the center of the upper layer (the mass per drop of water: 0.04 g).

Next, one of the four sides in which the bottom surface of the laminate is in contact with the horizontal plane is fixed to the horizontal surface, and the short side facing the side is gradually raised from the horizontal plane to incline the laminate.

The angle between the laminate and the horizontal plane when the water droplets began to move toward the horizontal plane from the laminate was measured, and the average value of these was set as the slip angle (°). When the slip angle is 15 or less, it is considered to be excellent in slidability, and it is evaluated as "◎".

When the slip angle is larger than 15° and 30° or less, it is considered to be excellent in slidability, and it is evaluated as “○”.

When the sliding angle is larger than 30°, the water droplets do not slide, and the sliding property is considered to be poor, and the evaluation is “×”.

(Contact angle)

The laminate prepared as above was placed horizontally, and 10 to 20 μL of water droplets were dropped on the cured film of the laminate, and the water contact angle (°) was measured using a contact angle measuring instrument (manufactured by MEIWAFOSIS, Phoenix-300). The water contact angle was measured for 5 drops of water, the average value was calculated, and the obtained value was shown in the first table. The larger the contact angle, the more excellent the antifouling property (for example, hydrophobicity, anti-fingerprint property, and anti-fingerprint property).

(total light transmittance)

The total light transmittance of the laminate produced as above was measured using a haze meter (HM-150, manufactured by Murakami Color Research Laboratory Co., Ltd.) in accordance with JIS K 7361. The 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 laminate produced as above was measured using a haze meter (HM-150, manufactured by Murakami Color Research Laboratory Co., Ltd.) in accordance with JIS K 7105. The 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, there is no haze and the transparency is excellent.

The components shown in Table 1 are as follows.

‧ Polyfunctional (meth) propylene oxirane compound 1: DPPA-HDI 15 parts by mass (react of dipentaerythritol pentaacrylate and hexamethylene diisocyanate. 10 acrylate groups in 1 molecule and 2 a urethane bond), with 15 parts by mass of PETA-IPDI isocyanurate (reactant of pentaerythritol triacrylate and isocyanurate of isophorone diisocyanate. 9 acrylates in one molecule) And having 3 urethane bonds), 50 parts by mass of DPHA (dipentaerythritol hexaacrylate), 20 parts by mass of DPPA (dipentaerythritol pentaacrylate), and ethyl acetate and butyl acetate as organic solvents mixture.

‧Naphthyl imine compound 1: Lumogen F Violet 570 (manufactured by BASF Corporation)

Benzene oxazoline compound 1: Tinopal OB CO (manufactured by BASF Corporation)

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

Benzene triazole compound 1: Tinuvin Carbo protect (manufactured by BASF Corporation)

‧ distyrylbiphenyl derivative 1: Tinopal NFW LIQ (manufactured by BASF Corporation)

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

‧ Fluorine-based compound 1: Trade name Megafac RS-75, manufactured by DIC Corporation. Containing an organic solvent and a compound having a fluorine atom and A compound (solids) having one (meth) acryloxy group per molecule and having a hydrocarbon group as a basic skeleton. The above compounds have no oxoxane skeleton.

‧Fluorine Compound 2: Trade name OPTOOL DAC-HP, manufactured by Daikin Industries. An organic solvent and a compound having a fluorine atom and having two (meth)acryloxycarbonyl groups per molecule and having a hydrocarbon group as a basic skeleton (solids). The above compounds have no oxoxane skeleton.

‧Fluorine Compound 3: Trade name KY-1203 BASE, manufactured by Shin-Etsu Chemical Co., Ltd. An organic solvent and a compound having a fluorine atom and a siloxane chain (polyoxymethylene compound) and having two (terminally) (meth) acryloxy groups per molecule (solids).

‧ Fluorine-based compound 4: An organic solvent and a compound having a fluorine atom and a siloxane chain (polyoxymethylene compound) and having two (meth) acryloxy groups per molecule (solids).

‧ A compound containing no (meth) acryloxy group and F: a product name Megafac F-555, manufactured by DIC Corporation. It has a fluorine atom and has no (meth) acryloxy group and a decane skeleton.

‧Photopolymerization initiator 1:1-hydroxycyclohexyl phenyl ketone, IRGACURE 184 (manufactured by BASF Corporation)

‧Compound (F) 1: First, the mercaptoethanol is reacted with a part of the poly(meth)acrylate having a 15 propylene decyloxy group in one molecule, and the propylene oxime group Into a reaction), thereby introducing a hydroxyl group.

Next, the introduced hydroxyl group and the isocyanate group of the isocyanurate body of IPDI were reacted at room temperature in accordance with the molar ratio of NCO/OH = 2.0.

Next, the isocyanate group of the obtained reactant was reacted with a hydroxyl group of a single-end methanol-denatured polydecane resin (manufactured by Shin-Etsu Chemical Co., Ltd., product name: X-22-170BX) at room temperature.

A mixture of the compound (solid portion) thus obtained and an organic solvent is used as the compound (F) 1.

The details of the synthesis of the compound (F) 1 are as follows.

(Synthesis 1: Addition of mercaptoethanol)

First, dipentaerythritol acrylate is reacted with isocyanurate of isophorone diisocyanate, and 66.5 g of the 15-functional acrylate represented by the following formula (9) and 0.38 g of triethylamine are obtained. The solution was mixed in 60 mL of butyl acetate to prepare a solution.

Next, 3.92 g of mercaptoethanol was added dropwise to the prepared mixed solution at room temperature, and the mixture was stirred at room temperature for 15 hours.

After completion of the stirring, the formation of the compound represented by the following formula (12) was confirmed by ¹ H-NMR (proton nuclear magnetic resonance) analysis.

(Synthesis 2: Addition of diisocyanate)

First, 31.04 g of the compound represented by the above formula (12) produced by the synthesis 1 was dissolved in 15 mL of butyl acetate to prepare a solution.

Next, isophorone diisocyanate is added to the prepared solution in an amount of the molar ratio (NCO/) of the isocyanate group of the isophorone diisocyanate and the hydroxyl group of the compound represented by the formula (12). OH) was 2.0 and stirred at 50 ° C for 6 hours.

After the completion of the stirring, the presence of the isocyanate group and the urethane bond was confirmed by IR analysis (infrared absorption spectrum analysis), and it was confirmed The formation of the compound represented by the formula (16).

(Synthesis 3: introduction of a siloxane moiety and (meth) propylene oxime)

In Synthesis 2, a solution of 35.92 g of methyl ethyl ketone (30 mL) was added to a solution of the reaction of isophorone diisocyanate with a single-terminal hydroxyl-denatured polyfluorene (X-22-170BX, manufactured by Shin-Etsu Chemical Co., Ltd.). The solution was 7.26 g of dipentaerythritol acrylate and stirred at 70 ° C for 5 hours.

After the completion of the stirring, the disappearance of the isocyanate group was confirmed by IR analysis, and the formation of the compound represented by the following formula (5) was confirmed by ¹ H-NMR analysis. The compound represented by the formula (5) is used as the compound (F) 1.

‧Organic solvent 1: methyl ethyl ketone

‧Organic solvent 2: methylphenyl ether (anisole)

As is clear from the results shown in Table 1, the scratch resistances of Comparative Examples 1 and 3 which did not contain a fluorine-based compound were low.

In Comparative Example 2 in which the content of the fluorine-based compound was less than a specific amount, the scratch resistance was low.

On the other hand, Examples 1 to 22 were excellent in the anti-blue light function and the scratch resistance. Further, Examples 1 to 22 were excellent in antifouling properties and slidability.

Further, from the results of Examples 11 to 14, it is understood that the fluorine-based compound further has a polyoxyalkylene skeleton as compared with the case where the fluorine-based compound does not have a polyoxyalkylene skeleton (Examples 1 to 9, 15). At least one of sex and slidability is more excellent.

As shown in Examples 7 and 10, when the composition further contains the compound (F), the antifouling property is compared with the case where the composition does not contain the compound (F). At least one of the slidability is more excellent.

100‧‧‧Layer

102‧‧‧Substrate

104‧‧‧ hardened film

Claims (9)

An ultraviolet curable resin composition containing (A) 100 parts by mass of a polyfunctional (meth) acryloxy compound having at least two (meth) acryloxy groups in one molecule, and containing (B) And at least one selected from the group consisting of a naphthoquinone imine compound having a naphthoquinone imine skeleton and a benzoxazoline compound having a benzoxazoline skeleton, and 0.05 to 10 parts by mass C) 0.05 to 10 parts by mass of the fluorine-based compound having at least one (meth)acryloxy group and at least one fluorine atom in one molecule, and (D) a photopolymerization initiator and (E) an organic solvent. The ultraviolet curable resin composition according to claim 1, wherein the polyfunctional (meth)acryl oxime compound contains at least two (meth) acryloxy groups and at least one amino group in one molecule. The formate bond contains a (meth)acryloxy compound a1. The ultraviolet curable resin composition according to claim 1 or 2, wherein the naphthoquinone imine compound is a compound represented by the following formula (1), (In the 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 's} may be the same or may be different). The ultraviolet curable resin composition according to any one of claims 1 to 3, wherein the skeleton of the fluorine-based compound is polyoxyalkylene. The ultraviolet curable resin composition according to any one of claims 1 to 4, further comprising a compound having at least one polyoxyalkylene moiety and at least 12 (meth)acryloxyloxy groups in one molecule ( F). The ultraviolet curable resin composition of claim 5, wherein the compound (F) further has an isocyanurate ring. The ultraviolet curable resin composition according to claim 5 or 6, wherein the amount of the compound (F) is 10 parts by mass or less based on 100 parts by mass of the polyfunctional (meth) propylene methoxy compound. The ultraviolet curable resin composition according to any one of claims 1 to 7, which is used for an electronic image display device or an eyeglass lens. A laminate comprising a substrate and a cured film, wherein the cured film is formed using the ultraviolet curable resin composition according to any one of claims 1 to 8.