JPWO2016043263A1 - Ultraviolet curable resin composition and laminate using the same - Google Patents

Abstract

An object of this invention is to provide the ultraviolet curable resin composition excellent in a blue light cut function and abrasion resistance, and a laminated body using the same. The present invention relates to (A) naphthalimide having a (B) naphthalimide skeleton with respect to 100 parts by mass of a polyfunctional (meth) acryloyloxy group-containing compound having at least two (meth) acryloyloxy groups in one molecule. 0.05 to 10 parts by mass of at least one selected from the group consisting of a benzoxazoline skeleton having a benzoxazoline skeleton and at least one (C) acrylicyloxy group and at least one (meth) acryloyl group in one molecule UV curable resin composition containing 0.05 to 10 parts by mass of a fluorine-based compound having one fluorine atom, (D) a photopolymerization initiator, and (E) an organic solvent, and the same It is a laminate.

Description

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

Conventionally, for electronic image display devices, for example, a hard coat material having a blue light cut function is applied to the back surface of a base material (such as a film of polyethylene terephthalate), and the hard coat material having scratch resistance is applied to the surface of the base material Laminates produced by painting the material have been used.
In addition, the present applicant has a film and a cured film on the film, and has been used in an electronic image display device for the purpose of providing an ultraviolet curable resin composition having an excellent blue light cut function. An ultraviolet curable resin composition for forming a cured film in a laminate, comprising the following components (A) to (C), wherein the amount of the component (C) is 0.7 to 2.0 mass of the non-volatile component: %, An ultraviolet curable resin composition was proposed (Patent Document 1).
(A): Multifunctional (meth) acrylate (B): Photopolymerization initiator (C): Blue light absorber containing a compound having a naphthalimide skeleton and / or a compound having a perylene skeleton

Japanese Patent No. 5549446

However, it is inferior in productivity to separately provide a layer having a blue light cut function and a layer having scratch resistance on the substrate, so that the layer having a blue light cut function is further made to have scratch resistance. In this case, the present inventors have clarified that the blue light cut function may not be maintained.
Then, an object of this invention is to provide the ultraviolet curable resin composition which is excellent in abrasion resistance, maintaining a high blue light cut function, and a laminated body using this.

As a result of earnest research to solve the above problems, the present inventors,
(A) For 100 parts by mass of a polyfunctional (meth) acryloyloxy group-containing compound having at least two (meth) acryloyloxy groups in one molecule,
(B) 0.05 to 10 parts by mass of at least one selected from the group consisting of a naphthalimide-based compound having a naphthalimide skeleton and a benzoxazoline-based compound having a benzoxazoline skeleton,
(C) 0.05 to 10 parts by mass of a fluorine-based compound having at least one (meth) acryloyloxy group and at least one fluorine atom in one molecule;
(D) a photopolymerization initiator;
(E) It discovered that the ultraviolet curable resin composition containing an organic solvent can make the outstanding blue light cut function and abrasion resistance compatible, and completed this invention.
That is, the present inventors have found that the above problem can be solved by the following configuration.

1. (A) For 100 parts by mass of a polyfunctional (meth) acryloyloxy group-containing compound having at least two (meth) acryloyloxy groups in one molecule,
(B) 0.05 to 10 parts by mass of at least one selected from the group consisting of a naphthalimide-based compound having a naphthalimide skeleton and a benzoxazoline-based compound having a benzoxazoline skeleton,
(C) 0.05 to 10 parts by mass of a fluorine-based compound having at least one (meth) acryloyloxy group and at least one fluorine atom in one molecule;
(D) a photopolymerization initiator;
(E) An ultraviolet curable resin composition containing an organic solvent.
2. The polyfunctional (meth) acryloyloxy group-containing compound includes a (meth) acryloyloxy group-containing compound a1 having at least two (meth) acryloyloxy groups and at least one urethane bond in one molecule. 2. The ultraviolet curable resin composition according to 1 above.
3. 3. The ultraviolet curable resin composition according to 1 or 2 above, wherein the naphthalimide compound is a compound represented by the following formula (1).

(In the formula (1), R ¹ represents a hydrocarbon group which may have a hydrogen atom or a hetero atom, R ² represents a hydrogen atom or an organic group, and a plurality of R ² are the same. May be different.)
4). 4. The ultraviolet curable resin composition according to any one of 1 to 3 above, wherein the skeleton of the fluorine compound is polysiloxane.
5. Furthermore, ultraviolet curing as described in any one of 1 to 4 above, which contains a compound (F) having at least one polysiloxane moiety and at least 12 (meth) acryloyloxy groups in one molecule. Resin composition.
6). 6. The ultraviolet curable resin composition according to 5 above, wherein the compound (F) further has an isocyanurate ring.
7). The ultraviolet curable resin composition of said 5 or 6 whose quantity of the said compound (F) is 10 mass parts or less with respect to 100 mass parts of said polyfunctional (meth) acryloyloxy group containing compounds.
8). The ultraviolet curable resin composition according to any one of 1 to 7 above, which is used for an electronic image display device or a spectacle lens.
9. A laminate having a base material and a cured film,
The laminated body in which the said cured film is formed using the ultraviolet curable resin composition as described in any one of said 1-8.

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

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

[Ultraviolet curable resin composition]
The present invention will be described in detail below.
First, the ultraviolet curable resin composition of this invention is demonstrated below.
The ultraviolet curable resin composition of the present invention (the composition of the present invention)
(A) For 100 parts by mass of a polyfunctional (meth) acryloyloxy group-containing compound having at least two (meth) acryloyloxy groups in one molecule,
(B) 0.05 to 10 parts by mass of at least one selected from the group consisting of a naphthalimide-based compound having a naphthalimide skeleton and a benzoxazoline-based compound having a benzoxazoline skeleton,
(C) 0.05 to 10 parts by mass of a fluorine-based compound having at least one (meth) acryloyloxy group and at least one fluorine atom in one molecule;
(D) a photopolymerization initiator;
(E) An ultraviolet curable resin composition containing an organic solvent.

In the present specification, the (A) polyfunctional (meth) acryloyloxy group-containing compound is sometimes referred to as a polyfunctional (meth) acryloyloxy group-containing compound, (A) or (A) component. The same applies to the components described as (B) to (F).
Moreover, it may be said that it is excellent in the effect of this invention that it is excellent in a blue light cut function and abrasion resistance. What is superior by at least any one of a blue light cut function and abrasion resistance may be excellent by the effect of this invention.

<(A) Polyfunctional (meth) acryloyloxy group-containing compound>
The polyfunctional (meth) acryloyloxy group-containing compound will be described below.
The polyfunctional (meth) acryloyloxy group-containing compound contained in the composition of the present invention is a compound having at least two (meth) acryloyloxy groups in one molecule. In this invention, it is mentioned as one of the preferable aspects to remove | exclude the compound which has Si-O-Si from a polyfunctional (meth) acryloyloxy group containing compound. Moreover, it is mentioned as one of the preferable aspects to remove | exclude the compound which has a fluorine atom from a polyfunctional (meth) acryloyloxy group containing compound.
The “(meth) acryloyloxy group” means an acryloyloxy group (CH ₂ ═CHCOO—) or a methacryloyloxy group (CH ₂ ═C (CH ₃ ) COO—), and “(meth) acrylate” "Means acrylate or methacrylate.

  The number of (meth) acryloyloxy groups contained in one molecule of the polyfunctional (meth) acryloyloxy group-containing compound is excellent due to the effects of the present invention, and the paintability (coating property), coating film appearance, and the phase with additives. From the viewpoint of excellent solubility and surface hardness, the number is preferably 2 to 15, and more preferably 4 to 12.

  In the polyfunctional (meth) acryloyloxy group-containing compound, the (meth) acryloyloxy group can be bonded to an organic group. The organic group is not particularly limited. For example, the hydrocarbon group which may have a hetero atom like 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, or a combination thereof. At least one of the carbon atom or hydrogen atom of the hydrocarbon group may be replaced with a substituent.

Examples of the substituent include monovalent substituents such as hydroxy group, amino group, mercapto group and halogen; ether bond, imino bond, sulfide bond, polysulfide bond, urethane bond, urea bond, ester bond and amide bond. Such divalent substituents can be mentioned.
The number of the above substituents that the polyfunctional (meth) acryloyloxy group-containing compound can have in one molecule is excellent due to the effects of the present invention, and is compatible with paintability (coatability), coating film appearance, and additives. From the viewpoint of excellent solubility and surface hardness, the number is preferably 1 to 10, and more preferably 2 to 5. The number of substituents per molecule may be zero.

  The polyfunctional (meth) acryloyloxy group-containing compound is superior in terms of the effects of the present invention, and is one molecule from the viewpoint of excellent curability (photopolymerization), reactivity (photopolymerization in a short time), surface hardness, and the like. A (meth) acryloyloxy group-containing compound a1 having at least two (meth) acryloyloxy groups and at least one urethane bond therein and / or at least two (meth) acryloyloxy groups in one molecule. It preferably contains a (meth) acryloyloxy group-containing compound a2 (excluding the (meth) acryloyloxy group-containing compound a1).

The (meth) acryloyloxy group-containing compound a2 is a compound having at least two (meth) acryloyloxy groups in one molecule. In the present invention, the (meth) acryloyloxy group-containing compound a1 is excluded from the (meth) acryloyloxy group-containing compound a2.
The (meth) acryloyloxy group-containing compound a2 is preferably a compound in which at least two (meth) acryloyloxy groups are bonded to a hydrocarbon group in one molecule. The hydrocarbon group may be linear, branched or cyclic. The hydrocarbon group can have an unsaturated bond. Examples of the hydrocarbon group include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a combination thereof. It is preferable that the hydrocarbon group has 2 to 8 carbon atoms. Two hydrocarbon groups may be bonded through, for example, an oxygen atom.

Examples of the (meth) acryloyloxy group-containing compound a2 include (meth) acrylic acid esters of polyhydric alcohols.
Examples of (meth) acrylic acid esters of polyhydric alcohols include trifunctional compounds such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate and dipentaerythritol tri (meth) acrylate; pentaerythritol Tetrafunctional compounds such as tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, tripentaerythritol tetra (meth) acrylate; dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri Pentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaery Ritoruokuta (meth) 5 or higher functional compounds, such as acrylate.
The (meth) acryloyloxy group-containing compound a2 can be used alone or in combination of two or more.

The (meth) acryloyloxy group-containing compound a1 is a compound having at least two (meth) acryloyloxy groups and at least one urethane bond in one molecule.
Examples of the (meth) acryloyloxy group-containing compound a1 include a reaction product of a (meth) acrylic acid ester of a polyhydric alcohol and a polyisocyanate compound.
Here, as the (meth) acrylic acid ester of the polyhydric alcohol used when producing the urethane (meth) acrylate, for example, at least one of the (meth) acrylic acid ester of the polyhydric alcohol described above. What has a hydroxy group is mentioned.
Moreover, as a polyisocyanate compound used when manufacturing urethane (meth) acrylate, for example, tolylene diisocyanate, diphenylmethane diisocyanate, phenylene diisocyanate, polymethylene polyphenylene polyisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, Aromatic polyisocyanates such as tolidine diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate; hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, norbornane diisocyanate, transcyclohexane-1,4-diisocyanate, isophorone diisocyanate, Bis (isocyanate methyl) ) Cyclohexane, an aliphatic polyisocyanate (cycloaliphatic polyisocyanates such as dicyclohexylmethane diisocyanate);. These isocyanurate, biuret body, an adduct; and the like are.
The (meth) acryloyloxy group-containing compound a2 can be used alone or in combination of two or more.
The polyfunctional (meth) acryloyloxy group-containing compound is not particularly limited for its production. For example, a conventionally well-known thing is mentioned.

The (meth) acryloyloxy group-containing compounds can be used alone or in combination of two or more.
Examples of the combination of the (meth) acryloyloxy group-containing compound include a combination of the (meth) acryloyloxy group-containing compound a2 and the (meth) acryloyloxy group-containing compound a1, specifically, for example, dipentaerythritol. At least one selected from the group consisting of a reaction product of pentaacrylate and an aliphatic polyisocyanate and a reaction product of pentaerythritol triacrylate and an aliphatic polyisocyanate, and consisting of dipentaerythritol hexaacrylate and pentaerythritol triacrylate The combination with at least 1 sort (s) chosen from a group is mentioned.

<(B) At least one selected from the group consisting of naphthalimide compounds and benzoxazoline compounds>
(Naphthalimide compounds)
The naphthalimide compound will be described below.
The naphthalimide compound contained in the composition of the present invention is a compound having a naphthalimide skeleton.
The composition of this invention is excellent in a blue light cut function by containing a naphthalimide type compound.
The naphthalimide-based compound is preferably a compound represented by the following formula (1) from the viewpoint that it is excellent due to the effects of the present invention, exhibits a high blue light cut rate, and is excellent in compatibility with other components.

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

Examples of the hydrocarbon group optionally having a hetero atom represented by R ¹ in the above formula (1) include, for example, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon. Groups and combinations thereof. The hydrocarbon group may have a hetero atom and / or an unsaturated bond. The hetero atom may be a combination of a plurality of hetero atoms or 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 * -X-aliphatic hydrocarbon group (X represents an oxygen atom, a nitrogen atom or a sulfur atom; the same shall apply hereinafter), * -X-alicyclic hydrocarbon. Group, * -X-aromatic hydrocarbon group. * Indicates the binding position.
Further, the hydrocarbon group represented by R ¹ is preferably a straight-chain or branched alkyl group, it is preferable that a carbon number of 1-12.

R ² represents a hydrogen atom or an organic group. As an organic group, the hydrocarbon group which may have a hetero atom; a functional group is mentioned, for example.
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, and more preferably a methoxy group or an ethoxy group.
Examples of the functional group include a hydroxy group, an amino group, and a nitro group.

The naphthalimide-based compound can reduce the transmittance of at least part of light in the wavelength range of 385 to 495 nm.
As a commercially available product of such a naphthalimide compound, for example, Lumogen F Violet 570 (manufactured by BASF) is preferably mentioned.

(Benzoxazoline compounds)
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.
The composition of this invention is excellent in blue light cut performance by containing a benzoxazoline type compound.
The compound having a benzoxazoline skeleton is not particularly limited as long as it is a compound having a benzoxazole ring, but may be a compound represented by the following formula (I) because the blue light cut function is better overall. Among them, a compound represented by the following formula (Ia) is more preferable.

(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.)

Examples of the organic group represented by R ^a in the above formula (I) include a hydrocarbon group which may have a hetero atom, specifically, for example, an aliphatic hydrocarbon group, an alicyclic ring Formula hydrocarbon groups, aromatic hydrocarbon groups, and combinations thereof may be mentioned and may have an unsaturated bond.
Further, the hydrocarbon group represented by ^Ra is preferably a linear or branched alkyl group, and more preferably a branched alkyl group.
Moreover, it is preferable that carbon number of the hydrocarbon group shown by ^Ra is 1-12, and it is more preferable that it is 3-6.

The benzoxazoline-based compound can reduce the transmittance of at least part of light in the wavelength range of 350 to 495 nm.
Examples of commercially available products of such benzoxazoline compounds include Tinopal OB CO (manufactured by BASF), Nikka Flow OB (manufactured by Nippon Chemical Industry Co., Ltd.), and the like.

  The amount of at least one selected from the group consisting of naphthalimide compounds and benzoxazoline compounds (the total amount of both when naphthalimide compounds and benzoxazoline compounds are used together) is a polyfunctional (meth) acryloyloxy group 0.05 to 10 parts by mass with respect to 100 parts by mass of contained compound, excellent due to the effects of the present invention, high blue light cut rate, compatibility with other components (liquid appearance, coating film during coating From the viewpoint of excellent appearance), it is preferably 0.2 to 8 parts by mass, more preferably 0.7 to 7 parts by mass, and even more preferably 1 to 5 parts by mass.

  When a naphthalimide-based compound and a benzoxazoline-based compound are used in combination, the mass ratio of the benzoxazoline-based compound to the naphthalimide-based compound (benzoxazoline-based compound / naphthalimide-based compound) is superior due to the effects of the present invention (particularly blue light cut). From the viewpoint of (excellent rate), it 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 perylene compounds, benzotriazole compounds, distyryl / biphenyl derivatives, and hydroxyphenyltriazine compounds.

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

As a commercial item of the compound which has a perylene skeleton, Lumogen F Yellow 083 (made by BASF Corporation) is mentioned, for example.
A compound having a perylene skeleton can absorb a region (420 to 495 nm) on a longer wavelength side than a compound having a naphthalimide skeleton in blue light.

(Benzotriazole compounds)
The composition of the present invention can 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 have a substituent. Examples of the benzotriazole-based compound include a compound represented by the following formula (3).

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

Examples of the hydrocarbon group optionally having a heteroatom represented by R ³ in the above formula (3) include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and these Combinations may be mentioned and may have an unsaturated bond.
Moreover, as a hydrocarbon group shown by R < ³ >, it is preferable that it is a linear or branched alkyl group, and it is preferable that carbon number is 1-12.
Examples of commercially available compounds having a benzotriazole skeleton include Tinuvin Carbo protect (manufactured by BASF) and Tinuvin 384-2 (manufactured by BASF).
A compound having a benzotriazole skeleton can absorb light having a wavelength of 220 to 430 nm.

(Distyryl biphenyl derivatives)
The composition of the present invention may further contain a distyryl biphenyl derivative as an optical brightener. The 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). In addition, the compound represented by the following formula (II) can be obtained as Tinopearl NFW LIQ (manufactured by BASF).

(Hydroxyphenyltriazine compound)
The composition of the present invention can further contain a compound having a hydroxyphenyltriazine skeleton (hydroxyphenyltriazine compound) as an ultraviolet absorber. The hydroxyphenyl triazine-based compound is not particularly limited as long as it has a hydroxyphenyl group and a triazine ring, and these are bonded by a single bond.
Examples of commercially available hydroxyphenyl triazine 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 (BASF). Manufactured) and the like.

  The amount of the perylene compound, benzotriazole compound, distyryl biphenyl derivative or hydroxyphenyltriazine compound described above is not particularly limited. The content of at least one selected from the group consisting of perylene compounds, benzotriazole compounds, distyryl / biphenyl derivatives and hydroxyphenyltriazine compounds (hereinafter sometimes referred to as perylene compounds) is polyfunctional ( It can be 0.001-5 mass parts with respect to 100 mass parts of (meth) acryloyloxy group containing compounds, and 0.001-2.0 mass parts is preferable.

<(C) Fluorine compound>
The fluorine compound will be described below.
The fluorine compound contained in the composition of the present invention is a compound having at least one (meth) acryloyloxy group and at least one fluorine atom in one molecule. In addition, in this invention, it is mentioned as one of the preferable aspects to remove | exclude the compound which has an isocyanurate ring from a fluorine-type compound.
The composition of this invention is excellent in abrasion resistance, slip property, and antifouling property by containing a fluorine-type compound.

  The number of (meth) acryloyloxy groups contained in one molecule of the fluorine-based compound is 2 to 15 from the viewpoint of being excellent due to the effects of the present invention and being excellent in compatibility with other components and scratch resistance. Preferably, the number is 2-5.

The skeleton of the fluorine-based compound may be either hydrocarbon or polysiloxane.
The hydrocarbon as the skeleton is not particularly limited. When the skeleton of the fluorine compound has polysiloxane, the skeleton may be referred to as a siloxane skeleton.
The polysiloxane that can be contained in the fluorine-based compound is preferably an organopolysiloxane, more preferably a dialkylpolysiloxane, and more preferably a dimethylsiloxane from the viewpoint of being excellent in the effects of the present invention and excellent in compatibility with other components. More preferably it is.
One preferred embodiment of the polysiloxane that the fluorine compound can have is a straight chain.
The weight average molecular weight of the polysiloxane that the fluorine-based compound can have is not particularly limited.
The weight average molecular weight of the fluorine compound is not particularly limited.

  The fluorine-based compound is excellent due to the effects of the present invention and has excellent compatibility with other components, and thus has a linear dialkylpolysiloxane as the main chain and at least one (meth) acryloyloxy as the side chain. A compound having a group having a group is preferred.

  Fluorine compounds can be used alone or in combination of two or more. The production of the fluorine compound is not particularly limited. For example, a conventionally well-known thing is mentioned.

  The amount of the fluorine-based compound is 0.05 to 10 parts by mass with respect to 100 parts by mass of the polyfunctional (meth) acryloyloxy group-containing compound, and is excellent due to the effects of the present invention. From the viewpoint of excellent appearance, 0.5 to 10 parts by mass is preferable, 0.5 to 5.0 parts by mass is more preferable, and 1.0 to 3 parts by mass or less is particularly preferable.

<(D) Photopolymerization initiator>
The photopolymerization initiator will be described below.
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) acryloyloxy group) by light.
Examples of the photopolymerization initiator include acetophenone compounds, benzoin ether compounds, benzophenone compounds, sulfur compounds, azo compounds, peroxide compounds, phosphine oxide compounds, and the like. Specifically, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, acetoin, butyroin, toluoin, 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, Carbonyl compounds such as 2-diphenylethane-1-one and 1-hydroxycyclohexyl phenyl ketone; Sulfur compounds such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide; Azobis Sobuchironitoriru, azo compounds such as azobis-2,4-dimethylvaleronitrile; benzoyl peroxide, peroxide compounds such as di -t- butyl peroxide and the like.

Among these, 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2-methyl-1-phenyl-propane are preferred in terms of light stability, high efficiency of photocleavage, surface curability, compatibility, low volatility, and low odor. -1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one is preferred.
A photoinitiator can be used individually or in combination of 2 types or more, respectively.

  It is preferable that the quantity of a photoinitiator is 1-10 mass parts with respect to 100 mass parts of polyfunctional (meth) acryloyloxy group containing compounds.

<(E) Organic solvent>
The organic solvent will be described below.
The organic solvent contained in the composition of the present invention is not particularly limited. Examples include ketones; ethers; esters such as ethyl acetate and butyl acetate; alcohols such as isopropyl alcohol (IPA); cycloalkanes such as cyclohexane; and aromatic hydrocarbon compounds such as toluene, xylene, and benzyl alcohol. .

  In particular, at least one selected from the group consisting of naphthalimide compounds, benzoxazoline compounds, and fluorine compounds is easily compatible with the polyfunctional (meth) acryloyloxy group-containing compound, thereby reducing the blue light cut function and resistance. Because it is superior in scratching properties, it is possible to dissolve a large amount of at least one selected from the group consisting of a liquid appearance, a coating film appearance at the time of coating, a liquid (storage) stability, a naphthalimide compound, and a benzoxazoline compound. From the viewpoint of having a high blue light cut rate, the organic solvent preferably contains at least a ketone and / or an ether.

Examples of the ketone include methyl ethyl ketone (MEK), methyl isobutyketone (MIBK), and cyclohexanone.
Examples of the ether include methyl phenyl ether (anisole).

The amount of the organic solvent is preferably 30 to 900 parts by mass with respect to 100 parts by mass of the polyfunctional (meth) acryloyloxy group-containing compound, from the viewpoint that the effect of the present invention is excellent and the compatibility is excellent. More preferably, it is -200 mass parts.
When the organic solvent contains a ketone and / or ether, the amount of the ketone and / or ether is preferably 60% by mass or more and 100% by mass or less, and more preferably 70 to 95% by mass with respect to the whole organic solvent.

  When the organic solvent contains at least a ketone and an ether, the mass ratio between the ketone and the ether (ether / ketone) is superior due to the effects of the present invention, and is compatible, liquid appearance, coating film appearance (leveling property), and liquid stability. From the viewpoint of excellent properties, it is preferably 0.5 to 20, and more preferably 0.6 to 1.0.

(Compound (F))
The composition of the present invention is further excellent due to the effects of the present invention, reduces slipping property, antifouling property, haze, and has excellent optical characteristics. (F) At least one polysiloxane in one molecule It is preferable to contain the compound (F) which has a site | part and at least 12 (meth) acryloyloxy group.
Since the compound (F) has a polysiloxane moiety, it corresponds to a compound having Si—O—Si.
The compound (F) is not particularly limited as long as it has a polysiloxane moiety and a (meth) acryloyloxy group in one molecule.
Compound (F) may further have at least one isocyanurate ring in one molecule.
As a compound (F), the (meth) acrylate compound (A) described in Unexamined-Japanese-Patent No. 2012-144670 is mentioned, for example.
In the present invention, for example, the (meth) acrylate compound (A) described in JP2012-144670A can be used as the compound (F).
The number of (meth) acryloyloxy groups contained in one molecule of the compound (F) is excellent due to the effects of the present invention, and the adhesion, the appearance of the coating film during liquid / coating, higher scratch resistance, and the surface hardness are enhanced. From the standpoint of superiority, the number is preferably 12 to 20, and more preferably 12 to 15.
A compound (F) can be used individually or in combination of 2 types or more, respectively.

  The amount of the compound (F) is 10 parts by mass or less with respect to 100 parts by mass of the polyfunctional (meth) acryloyloxy group-containing compound from the viewpoint of being excellent due to the effects of the present invention and being excellent in adhesion to the coated fabric. It is preferably 0.5 to 5 parts by mass.

  The solid content concentration of the composition of the present invention is preferably 20 to 80% by mass in the composition from the viewpoint of being excellent due to the effects of the present invention and being excellent in coating film appearance (leveling property) and optical properties. More preferably, it is -60 mass%. In the present invention, the solid content includes (A), (B), and (C). When the composition of the present invention further contains (F) such as a perylene compound, the solid content includes (A), (B), (C), a perylene compound and the like (F). The photopolymerization initiator is not included in the solid content.

(Other additives)
The composition of the present invention may further contain an additive as long as the object of the present invention is not impaired. Examples of additives include ethylenic compounds other than (A), blue light absorbers other than (B), fluorine-based compounds other than (C), ultraviolet absorbers, fillers, anti-aging agents, antistatic agents, difficulty Examples include flame retardants, adhesion promoters, dispersants, antioxidants, antifoaming agents, leveling agents, matting agents, light stabilizers, dyes, and pigments.

(Production method)
The production method of the composition of the present invention is not particularly limited. For example, it can be produced by uniformly mixing the compounds (F) and additives such as the above (A) to (E) and perylene compounds that can be used as necessary.

(Use etc.)
The composition of the present invention includes, for example, a composition for forming a film having a blue light cut function and scratch resistance, a plastic surface protective agent, a hard coat paint, a hard coat agent, an ultraviolet curable paint, a primer composition, and the like. Can be used as
The composition of the present invention can be used for an electronic image display device and a spectacle lens.
The material of the base material to which the composition of the present invention can be applied is not particularly limited. For example, plastic, rubber, glass, metal, ceramic and the like can be mentioned. The form of the substrate can be, for example, a film.
The plastic to which the composition of the present invention can be applied may be either a thermosetting resin or a thermoplastic resin. Examples of plastics include polyethylene terephthalate (PET), cycloolefin polymers (including homopolymers, copolymers, and hydrogenated products), polymethyl methacrylate resins (PMMA resins), polycarbonate resins, polystyrene resins, acrylonitrile. -Hardly adhesive resins such as styrene copolymer resins, polyvinyl chloride resins, acetate resins, acrylonitrile butadiene styrene resins (ABS resins), polyester resins, and polyamide resins.

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

Examples of the curing method of the composition of the present invention include a curing method using ultraviolet rays. In the case where the composition of the present invention is cured by ultraviolet irradiation, the irradiation amount (integrated light amount) of the ultraviolet rays used when curing the composition of the present invention is 50 to 3, from the viewpoint of fast curability and workability. 000 mJ / cm ² is preferred. The apparatus used for irradiating ultraviolet rays is not particularly limited. For example, a conventionally well-known thing is mentioned. Heating may be used in combination for curing.

[Laminate]
Next, the laminated body of this invention is demonstrated below.
The laminate of the present invention is a laminate having a substrate and a cured film, and the cured film is a laminate formed using the above-described composition of the present invention.
Since the laminated body of this invention has a cured film formed using the composition of this invention, it is excellent in a blue light cut function and abrasion resistance.

<Base material>
The base material is not particularly limited. The thing similar to the above is mentioned. The thickness of the substrate is not particularly limited. The thickness of the substrate is preferably about 50 to 2,000 μm.
<Curing film>
The cured film is not particularly limited as long as it is formed 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 roughness layer between the substrate and the cured film. The easy adhesion layer and the roughness layer are not particularly limited, for example, with respect to the formation method, thickness, and material.

The structure of the laminated body of this invention is demonstrated below using attached drawing. The present invention is not limited to the attached 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 has the base material 102 and the cured film 104 formed using the composition of this invention.

(Production method)
The production method of the laminate of the present invention includes, for example, coating the composition of the present invention on a film-like base material (the above-mentioned easy-adhesion layer or the above-mentioned easy-adhesion layer or roughness layer when having a roughness layer). And drying and irradiating with ultraviolet rays.
Here, the method of applying the composition of the present invention is not particularly limited, and for example, a known coating method such as brush coating, flow coating, dip coating, spray coating, spin coating or the like can be employed.
You may dry the composition after coating. The drying temperature after coating is preferably 20 to 110 ° C.
Moreover, in the ultraviolet irradiation after drying, the irradiation amount (integrated light amount) of the ultraviolet ray used when the composition of the present invention is cured is 50 to 3,000 mJ / cm ² from the viewpoints of fast curability and workability. Preferably there is. The apparatus used for irradiating ultraviolet rays is not particularly limited. For example, a conventionally well-known thing is mentioned. Heating may be used in combination for curing.

The laminate of the present invention can be used for, for example, an electronic image display device, a spectacle lens, a protective cover for lighting (particularly LED lighting), a solar cell module member, and the like.
Examples of the electronic image display device include display-use electronic device components such as a personal computer, a television, a touch panel, and a wearable terminal (for example, a computer terminal that can be worn on the body such as a glasses type or a wrist watch type).
The laminated body of the present invention can be incorporated in an electronic image display device or the like, or can be retrofitted (for example, attached from the outside). When the laminate of the present invention is built in an electronic image display device or the like, it can be applied to a portion other than the reflector, for example. Specifically, for example, it can be applied to a lens sheet, a diffusion 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.

  The present invention will be specifically described below with reference to examples. However, the present invention is not limited to these.

<Production of composition>
Each component of the following Table 1 was mixed with the composition (parts by mass) shown in the same table using a stirrer to produce a composition.
In addition, the solid content (mass%) of each component was shown in the column of solid content (%) of Table 1.
In Table 1, (A), (C), (F), the distyryl biphenyl derivative 1 and the hydroxyphenyltriazine compound 1 were used in a form containing an organic solvent in addition to a solid content. The amounts of (A), (C), (F), the distyryl biphenyl derivative 1 and the hydroxyphenyl triazine compound 1 shown in each example in Table 1 are solid amounts.
The solid content of (A) includes DPPA-HDI, PETA-IPDI, DPHA and DPPA.

<Manufacture of laminates>
Each composition produced as described above was applied to a polyethylene terephthalate film (PET fabric: trade name A-4300, manufactured by Toyobo Co., Ltd., 210 mm × 297 mm, thickness 125 μm) using a bar coater, and this was applied at 80 ° C. After drying for 1 minute under the above conditions, this was 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 , integrated light quantity 300 mJ / cm ² , UV The irradiation apparatus was a high-pressure mercury lamp), and the composition was cured to form a cured film to produce a laminate. The film thickness of the cured film included in the laminate was 5 μm.

<Evaluation>
The following evaluation was performed using the laminate manufactured as described above. The results are shown in Table 1.

(Blue light cut function: Blue light average cut rate)
The laminate manufactured as described above was irradiated with light in the 800 to 300 nm region using a Hitachi spectrophotometer 3900H as an apparatus, and the average transmittance (%) in the 385 to 495 nm region was measured. The measurement result was applied to the following formula to calculate the average blue light cut rate of the laminate.
Average cut rate (%) of blue light of laminate = 100− (average transmittance of 385 to 495 nm region measured as above for laminate)
In this invention, it is preferable that the blue light average cut rate of a laminated body is 13% or more, and it is more preferable that it is 21% or more.
The average cut rate of blue light in the 385 nm to 495 nm region of the polyethylene terephthalate film (thickness 125 μm) used as the base material (the measurement method of the blue light cut rate is the same as that of the laminate) was about 11%. It was.

(Abrasion resistance)
The surface of the cured film of the laminate produced as described above was rubbed 100 times with a load of 250 g / cm ² using steel wool (# 0000).
After 100 reciprocations, the cured film was visually checked for scratches.
The case where there was no flaw was evaluated as “◯”, and the case where there was a flaw was evaluated as “x”.

(Appearance of coating film)
The cured film of the laminate produced as described above was visually observed.
By visual judgment, the case where the cured film was smooth was evaluated as “◯” as being excellent in appearance.
By visual judgment, when the cured film had aggregated particles and / or repellency, the appearance was evaluated as “x”.

(Anti-fouling property)
On the surface of the cured film of the laminate produced as described above, a line was written with ZEBBRA Himackey Care (bold). After drying for 1 minute under the condition of 23 ° C, the product name BEMCOT (size: 150mm x 150mm) (made by Asahi Kasei Fibers Co., Ltd.) is reciprocated over the cured film to wipe the wire, and the number of reciprocations until the wire disappears. The evaluation was as follows.
A case where the line disappears within two round trips was marked as “◎” as being very excellent in antifouling property.
The case where the line disappeared within 3 to 5 round trips was marked as “◯” as excellent antifouling property.
The case where the line did not disappear after 6 round-trips was marked as “x” because the antifouling property was poor.

(Slip property)
First, the laminate was placed on a horizontal plane, and water drops (mass per piece: 0.04 g) were dropped onto the center of the laminate.
Next, the short side facing the one side was slowly raised from the horizontal plane while tilting the stacked body while one of the four sides whose bottom surface was in contact with the horizontal plane was fixed to the horizontal plane.
The angle between the laminate and the horizontal plane when the water droplet started to move on the laminate toward the horizontal plane was measured, and the average value thereof was defined as the tumbling angle (°).
When the sliding angle was 15 ° or less, “ス リ ッ プ” was evaluated as being extremely excellent in slip property.
A case where the sliding angle was greater than 15 ° and 30 ° or less was evaluated as “◯” as being excellent in slip property.
A case where water droplets did not slip even when the sliding angle was larger than 30 ° was evaluated as “x” because the slip property was poor.

(Contact angle)
The laminated body produced as described above is placed horizontally, 10 to 20 μL of water droplets are dropped on the cured film of the laminated body, and water is used using a contact angle measuring device (Meiwa Forsys, Phoenix-300). The contact angle (°) was measured. Table 1 shows the values obtained by measuring the water contact angle for 5 drops and calculating the average value. The greater the contact angle, the better the antifouling property (for example, water repellency, fingerprint resistance, fingerprint resistance).

(Total light transmittance)
Using a haze meter (HM-150, manufactured by Murakami Color Research Laboratory), the total light transmittance of the laminate produced as described above was measured according to JIS K 7361. The result is shown as an average value of the number of samples n = 3.
The total light transmittance is preferably 90% or more.

(Haze)
Using a haze meter (HM-150, manufactured by Murakami Color Research Laboratory), the haze of the laminate produced as described above was measured according to JIS K 7105. The result is shown as an average value of the number of samples n = 3.
In this invention, when haze is 1.0 or less, there is no cloudiness and it is excellent in transparency.

Details of each component shown in Table 1 are as follows.
Polyfunctional (meth) acryloyloxy group-containing compound 1: DPPA-HDI 15 parts by mass (reaction product of dipentaerythritol pentaacrylate and hexamethylene diisocyanate. It has 10 acrylate groups and 2 urethane bonds in one molecule. ), 15 parts by mass of PETA-IPDI nurate (reaction product of pentaerythritol triacrylate and an isocyanurate of isophorone diisocyanate, having 9 acrylate groups and 3 urethane bonds in one molecule), DPHA50 A mixture of parts by mass (dipentaerythritol hexaacrylate), 20 parts by mass of DPPA (dipentaerythritol pentaacrylate), and ethyl acetate and butyl acetate as organic solvents.

・ Naphthalimide compound 1: Lumogen F Violet 570 (BASF)
Benzoxazoline compound 1: Tinopearl OB CO (manufactured by BASF)
Perylene compound 1: Lumogen F Yellow 083 (manufactured by BASF)
・ Benzotriazole compound 1: Tinuvin Carbo protect (manufactured by BASF)
-Distyryl biphenyl derivative 1: Tinopal NFW LIQ (BASF)
Hydroxyphenyltriazine compound 1: Tinuvin 479 (BASF)

  -Fluorine-based compound 1: Trade name Megafax RS-75, manufactured by DIC Corporation. A compound (solid content) having a fluorine atom and one (meth) acryloyloxy group per molecule and having a hydrocarbon group as a basic skeleton, and an organic solvent. The above compound does not have a siloxane skeleton.

  Fluorine-based compound 2: trade name OPTOOL DAC-HP, manufactured by Daikin Industries, Ltd. A compound having a fluorine atom and two (meth) acryloyloxy groups per molecule, a hydrocarbon group as a basic skeleton (solid content), and an organic solvent. The above compound does not have a siloxane skeleton.

  Fluorine-based compound 3: trade name KY-1203 base, manufactured by Shin-Etsu Chemical Co., Ltd. A compound (solid content) having a fluorine atom, two (meth) acryloyloxy groups (both ends) and a siloxane skeleton (silicone compound) per molecule, and an organic solvent are contained.

  Fluorine-based compound 4: Contains a compound (solid content) having a fluorine atom, two (meth) acryloyloxy groups per molecule, and a siloxane skeleton (silicone compound), and an organic solvent.

-(Meth) acryloyloxy group-free F-containing compound: Trade name Megafax F-555, manufactured by DIC Corporation. It has a fluorine atom and does not have a (meth) acryloyloxy group and a siloxane skeleton.
Photopolymerization initiator 1: 1-hydroxycyclohexyl phenyl ketone, Irgacure 184 (manufactured by BASF)

Compound (F) 1: First, mercaptoethanol is reacted with a part of acryloyloxy group of polyfunctional (meth) acrylate having 15 acryloyloxy groups in one molecule (Michael of mercapto group and acryloyloxy group). (Addition reaction) to introduce a hydroxy group.
Next, the introduced hydroxy group and the isocyanate group of the isocyanurate of IPDI were reacted at room temperature at a molar ratio of NCO / OH = 2.0.
Subsequently, the isocyanate group of the obtained reaction product was reacted with the hydroxy group of one-terminal carbinol-modified silicone resin (manufactured by Shin-Etsu Chemical Co., Ltd., product name: X-22-170BX) at room temperature.
A mixture of the compound (solid content) thus obtained and the organic solvent is designated as Compound (F) 1.

Details of the synthesis of compound (F) 1 are as follows.
(Synthesis 1: Addition of mercaptoethanol)
First, 66.5 g of a 15-functional acrylate represented by the following formula (9) obtained by reacting dipentaerythritol acrylate and an isocyanurate form of isophorone diisocyanate and 0.38 g of triethylamine are mixed in 60 mL of butyl acetate. A prepared solution was prepared.

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 production 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, a solution was prepared by dissolving 31.04 g of the compound represented by the above formula (12) produced in Synthesis 1 in 15 mL of butyl acetate.
Next, isophorone diisocyanate is added to the prepared solution in such an amount that the molar ratio (NCO / OH) of the isocyanate group of isophorone diisocyanate to the hydroxy group of the compound represented by formula (12) is 2.0, Stir at 50 ° C. for 6 hours.

After completion of stirring, the presence of an isocyanate group and a urethane bond was confirmed by IR analysis (infrared absorption analysis), and the production of a compound represented by the following formula (16) was confirmed.

(Synthesis 3: Introduction of siloxane moiety and (meth) acryloyloxy group)
In the solution after reacting isophorone diisocyanate in Synthesis 2, 35.92 g of methyl ethyl ketone (30 mL) solution with one terminal hydroxyl group-modified silicone (X-22-170BX, manufactured by Shin-Etsu Chemical Co., Ltd.), 7.26 g of dipentaerythritol acrylate, And stirred at 70 ° C. for 5 hours.
After completion of stirring, disappearance of the isocyanate group was confirmed by IR analysis, and formation of a compound represented by the following formula (5) was confirmed by ¹ H-NMR analysis. The compound represented by Formula (5) was used as Compound (F) 1.

・ Organic solvent 1: Methyl ethyl ketone ・ Organic solvent 2: Methyl phenyl ether (anisole)

As is clear from the results shown in Table 1, Comparative Examples 1 and 3 not containing a fluorine-based compound had low scratch resistance.
In Comparative Example 2 where the amount of the fluorine-based compound was less than a predetermined amount, the scratch resistance was low.

  On the other hand, Examples 1-22 were excellent in the blue light cut function and abrasion resistance. Moreover, Examples 1-22 were excellent in antifouling property and slip property.

Moreover, from the results of Examples 11 to 14, when the fluorine-based compound further has a polysiloxane skeleton, the antifouling property is higher than when the fluorine-based compound does not have a polysiloxane skeleton (Examples 1 to 9 and 15). And at least one of slip properties.
When the composition further contained the compound (F) as in Examples 7 and 10, it was superior to at least one of the antifouling property and the slip property as compared with the case where the compound (F) was not contained.

100 Laminated body 102 Base material 104 Cured film

Claims (9)

(A) For 100 parts by mass of a polyfunctional (meth) acryloyloxy group-containing compound having at least two (meth) acryloyloxy groups in one molecule,
(B) 0.05 to 10 parts by mass of at least one selected from the group consisting of a naphthalimide-based compound having a naphthalimide skeleton and a benzoxazoline-based compound having a benzoxazoline skeleton,
(C) 0.05 to 10 parts by mass of a fluorine-based compound having at least one (meth) acryloyloxy group and at least one fluorine atom in one molecule;
(D) a photopolymerization initiator;
(E) An ultraviolet curable resin composition containing an organic solvent.   The polyfunctional (meth) acryloyloxy group-containing compound includes a (meth) acryloyloxy group-containing compound a1 having at least two (meth) acryloyloxy groups and at least one urethane bond in one molecule. The ultraviolet curable resin composition according to claim 1. The ultraviolet curable resin composition of Claim 1 or 2 whose said naphthalimide type compound is a compound represented by following formula (1).

(In the formula (1), R ¹ represents a hydrocarbon group which may have a hydrogen atom or a hetero atom, R ² represents a hydrogen atom or an organic group, and a plurality of R ² are the same. May be different.)   The ultraviolet curable resin composition of any one of Claims 1-3 whose frame | skeleton of the said fluorine-type compound is polysiloxane.   Furthermore, the ultraviolet-ray of any one of Claims 1-4 which contains the compound (F) which has at least 1 polysiloxane site | part and at least 12 (meth) acryloyloxy group in 1 molecule. Curable resin composition.   The ultraviolet curable resin composition according to claim 5, wherein the compound (F) further has an isocyanurate ring.   The ultraviolet curable resin composition of Claim 5 or 6 whose quantity of the said compound (F) is 10 mass parts or less with respect to 100 mass parts of said polyfunctional (meth) acryloyloxy group containing compounds.   The ultraviolet curable resin composition of any one of Claims 1-7 used for an electronic image display apparatus or a spectacles lens. A laminate having a base material and a cured film,
The laminated body in which the said cured film is formed using the ultraviolet curable resin composition of any one of Claims 1-8.