WO2016171024A1 - Hard coat layer-forming resin composition and cured product thereof - Google Patents

Abstract

Provided is a hard coat layer-forming resin composition by which is obtained a cured product in which curling is suppressed and which exhibits high surface hardness and scratch resistance. This hard coat layer-forming resin composition contains a polyfunctional alicyclic epoxy compound (A), a polyfunctional (meth)acrylic compound (B), surface-modified inorganic particles (C), a cationic photopolymerization initiator (D) and a radical photopolymerization initiator (E), with the content of component (A) being 3-35 wt.% relative to the overall content (100 wt.%) of components (A) and (B).

Description

Hard coat layer forming resin composition and cured product thereof

The present invention relates to a resin composition for forming a hard coat layer and a cured product thereof. The present invention also relates to a coated product obtained using the above resin composition for forming a hard coat layer. This application claims the priority of Japanese Patent Application No. 2015-086412 for which it applied to Japan on April 21, 2015, and uses the content here.

Liquid crystal monitors such as liquid crystal displays, organic EL displays, and plasma displays have a protective film attached to them, which prevents the screen from being damaged, makes it difficult for fingerprints to adhere to the screen, and stains attached to the screen. The effect of making it easy to wipe off is obtained. A hard coat layer for imparting scratch resistance is formed on the surface of the protective film. In recent years, there are many demands for increasing the surface hardness of the liquid crystal protective film, and there is a demand for improving the performance of the hard coat layer.

The polyfunctionalization of the curable group of the curable compound forming the hard coat layer is widely used as a means for improving the surface hardness of the hard coat layer. However, it is known that a polyfunctionalized curable compound causes an increase in resin density, that is, curing shrinkage before and after curing. And the more functionalized, the more remarkable the shrinkage of curing, and the problem is that the protective film exhibits curling properties.

In addition, as a method for improving the scratch resistance of the hard coat layer, a method in which inorganic particles such as alumina, silica, and titanium oxide are blended with a curable compound, a so-called organic-inorganic hybrid method is known (patent) Reference 1).

However, when a coating film is prepared by dispersing inorganic particles in a resin, a phenomenon such as loss of inorganic particles from the cured coating film (cured coating film), an increase in haze, or occurrence of brittleness is observed. There is. This is believed to be due to poor compatibility between organic and inorganic materials. And the method (patent document 2) using the nano filler which reduced the particle diameter of the inorganic particle to nano size is known as a method of improving the compatibility of organic substance and inorganic substance. However, when nanosized inorganic particles are used, the dispersion stability is lowered and the inorganic particles are easily aggregated, and it is difficult to maintain the transparency of the cured coating film. In addition, a method using a surface-modified inorganic filler in which the outer shell of inorganic particles is surface-modified with an organic substance (Patent Document 3) is also known. However, when inorganic particles whose surface is modified with an organic substance are used, it is difficult to increase the surface hardness of the cured coating film, and the surface hardness is sometimes lowered.

Japanese Patent Publication No. 2-60696 JP 2005-76005 A JP 2003-34761 A

Therefore, an object of the present invention is to provide a resin composition for forming a hard coat layer that gives a cured product having higher surface hardness and scratch resistance while suppressing the development of curling properties.

“Curlability” means a property that causes curling of a base material when a cured film (cured coating film) is formed on the base material. This means that the material is less likely to curl.

As a result of intensive studies to solve the above problems, the present inventor has found that the polyfunctional alicyclic epoxy compound, the polyfunctional (meth) acrylic compound, and the epoxy group and / or polyfunctional (meth) of the polyfunctional alicyclic epoxy compound. A resin composition containing a specific proportion of inorganic particles having a functional group reactive to the (meth) acryloyl group of an acrylic compound suppresses the expression of curling properties when irradiated with active energy rays, that is, has a low curl. It has been found that a cured product having higher surface hardness and scratch resistance can be obtained with high properties (or low cure shrinkage). The present invention has been completed based on these findings.

That is, the present invention relates to a polyfunctional alicyclic epoxy compound (A) having an alicyclic structure and two or more epoxy groups in one molecule (polyfunctional having two or more (meth) acryloyl groups in one molecule ( Surface having a reactive functional group with an epoxy group and / or a (meth) acryloyl group on the surface of an inorganic particle having a meth) acrylic compound (B) and an average particle diameter (by dynamic light scattering method) of 0.1 to 100 nm It contains modified inorganic particles (C), a photocationic polymerization initiator (D), and a photoradical polymerization initiator (E), and the content of (A) is the sum of the content of (A) and (B). Provided is a resin composition for forming a hard coat layer that is 3 to 35% by weight of (100% by weight).

The present invention also provides the resin composition for forming a hard coat layer, wherein the content of (C) is 5 to 40 parts by weight with respect to 100 parts by weight of the total content of (A) and (B). I will provide a.

In the present invention, the concentration of the (meth) acryloyl group in the total amount of (A), (B), (C) contained in the resin composition for forming a hard coat layer is more than 5.0 mmol / g. A hard coat layer forming resin composition is provided.

The present invention also provides the resin composition for forming a hard coat layer, wherein the inorganic particles in the surface-modified inorganic particles (C) are silica.

The present invention further includes a silicon compound, a perfluoroalkyl group-containing (meth) acrylic compound, a silyl group-containing (meth) acrylic compound having a reactive functional group with an epoxy group and / or a (meth) acryloyl group, Polyether-modified (meth) acrylic compound, silicon-modified poly (meth) acrylate, polyether-modified poly (meth) acrylate, perfluoroalkyl group-containing poly (meth) acrylate, perfluoroalkyl group-containing polyether-modified (meth) acrylate, Contains at least one compound selected from acrylic-modified polydimethylsiloxane, polyether-modified polydimethylsiloxane, perfluoroalkyl group-containing polydimethylsiloxane, and polyether-modified perfluoroalkyl group-containing polydimethylsiloxane That provide the hard coat layer-forming resin composition.

The present invention also provides a cured product of the resin composition for forming a hard coat layer.

The present invention also provides a coated article provided with a hard coat layer made of a cured product of the above-described resin composition for forming a hard coat layer on the surface of an article.

That is, the present invention relates to the following.
[1] A polyfunctional alicyclic epoxy compound having an alicyclic structure and two or more epoxy groups in one molecule (A), a polyfunctional (meth) acryl having two or more (meth) acryloyl groups in one molecule Compound (B), surface-modified inorganic particles having a reactive functional group with an epoxy group and / or a (meth) acryloyl group on the surface of an inorganic particle having an average particle diameter (by dynamic light scattering method) of 0.1 to 100 nm (C), a photocationic polymerization initiator (D), and a photoradical polymerization initiator (E), wherein the content of (A) is the sum of the contents of (A) and (B) (100 wt. %) Of the resin composition for forming a hard coat layer.
[2] The resin composition for forming a hard coat layer according to [1], wherein (A) is a compound represented by formula (I) (an alicyclic epoxy compound).
[3] (A) is (3,4,3 ′, 4′-diepoxy) bicyclohexyl, bis (3,4-epoxycyclohexylmethyl) ether, 1,2-epoxy-1,2-bis (3, 4-epoxycyclohexane-1-yl) ethane, 2,2-bis (3,4-epoxycyclohexane-1-yl) propane, 1,2-bis (3,4-epoxycyclohexane-1-yl) ethane, and The resin composition for forming a hard coat layer according to [1], which is at least one compound selected from the group consisting of compounds represented by formulas (I-1) to (I-10).
[4] In [1], (A) is 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate and / or (3,4,3 ′, 4′-diepoxy) bicyclohexyl The resin composition for hard coat layer formation as described.
[5] [1] to [4] wherein (B) is a compound having 3 or more (for example, 3 to 12, preferably 5 or more, particularly preferably 5 to 10) (meth) acryloyl groups. The resin composition for hard-coat layer formation as described in any one of these.
[6] The resin composition for forming a hard coat layer according to any one of [1] to [5], wherein the molecular weight of (B) is 300 to 13000.
[7] The resin composition for forming a hard coat layer according to any one of [1] to [6], wherein the weight average molecular weight of (B) (converted to standard polystyrene by GPC) is 400 to 13000.
[8] The resin composition for forming a hard coat layer according to any one of [1] to [7], wherein (B) is dipentaerythritol poly (meth) acrylate or a derivative thereof.
[9] The resin composition for forming a hard coat layer according to any one of [1] to [8], wherein the inorganic particles in (C) are silica, titania, alumina, or zirconia.
[10] The resin composition for forming a hard coat layer according to any one of [1] to [8], wherein the inorganic particles in (C) are silica.
[11] The resin composition for forming a hard coat layer according to any one of [1] to [10], wherein the average particle size (by dynamic light scattering method) of the inorganic particles in (C) is 1 to 10 nm. object.
[12] The reactive functional group with the epoxy group and / or the (meth) acryloyl group in (C) is a group selected from a hydroxyl group, a glycidyl ether group, and an alicyclic epoxy group (preferably a cyclohexene oxide group). [1] to [11] The resin composition for forming a hard coat layer according to any one of [1] to [11].
[13] Further, a silicon compound, a perfluoroalkyl group-containing (meth) acryl compound, a silyl group-containing (meth) acryl compound, or a polyether-modified compound having a reactive functional group with an epoxy group and / or a (meth) acryloyl group (Meth) acrylic compound, silicon-modified poly (meth) acrylate, polyether-modified poly (meth) acrylate, perfluoroalkyl group-containing poly (meth) acrylate, perfluoroalkyl group-containing polyether-modified (meth) acrylate, acrylic-modified poly Containing at least one compound selected from dimethylsiloxane, polyether-modified polydimethylsiloxane, perfluoroalkyl group-containing polydimethylsiloxane, and polyether-modified perfluoroalkyl group-containing polydimethylsiloxane [1 ] The resin composition for forming a hard coat layer according to any one of [12] to [12].
[14] The resin composition for forming a hard coat layer according to any one of [1] to [12], further comprising a hydroxyl group-containing silicon-modified poly (meth) acrylate.
[15] The resin for forming a hard coat layer according to any one of [1] to [14], wherein the content of (A) is 3 to 50% by weight of the total amount of nonvolatile components contained in the resin composition Composition.
[16] The resin for forming a hard coat layer according to any one of [1] to [15], wherein the content of (B) is 40 to 95% by weight of the total amount of nonvolatile components contained in the resin composition Composition.
[17] The concentration of the (meth) acryloyl group in the total amount of (A), (B), (C) contained in the resin composition for forming a hard coat layer is more than 5.0 mmol / g, [1] The resin composition for forming a hard coat layer according to any one of [16] to [16].
[18] The resin for forming a hard coat layer according to any one of [1] to [17], wherein the content of (C) is 1 to 30% by weight of the total amount of nonvolatile components contained in the resin composition Composition.
[19] In any one of [1] to [18], the content of (C) is 5 to 40 parts by weight with respect to 100 parts by weight of the total content of (A) and (B). The resin composition for hard coat layer formation as described.
[20] The sum of the contents of (A) and (C) is 5 to 60% by weight of the total (100% by weight) of (A), (B) and (C), [1] to [19 ] The resin composition for hard-coat layer formation as described in any one of these.
[21] The content of (D) is 1 to 10 parts by weight with respect to 100 parts by weight of the cationic curable compound (particularly the polyfunctional alicyclic epoxy compound (A)) contained in the resin composition. ] The resin composition for forming a hard coat layer according to any one of [20] to [20].
[22] The content of (E) is 1 to 10 parts by weight with respect to 100 parts by weight of the radical curable compound (particularly the polyfunctional (meth) acrylic compound (B)) contained in the resin composition. [1] The resin composition for forming a hard coat layer according to any one of [21] to [21].
[23] A silicon compound, a perfluoroalkyl group-containing (meth) acryl compound, a silyl group-containing (meth) acryl compound, a polyether-modified (meth) having a reactive functional group with an epoxy group and / or a (meth) acryloyl group ) Acrylic compound, silicon-modified poly (meth) acrylate, polyether-modified poly (meth) acrylate, perfluoroalkyl group-containing poly (meth) acrylate, perfluoroalkyl group-containing polyether-modified (meth) acrylate, acrylic-modified polydimethylsiloxane At least one compound selected from polyether-modified polydimethylsiloxane, perfluoroalkyl group-containing polydimethylsiloxane, and polyether-modified perfluoroalkyl group-containing polydimethylsiloxane [in particular, The content of the con-modified poly (meth) acrylate] is 0.01 to 10 parts by weight with respect to the total (100 parts by weight) of (A), (B), and (C). ] The resin composition for hard-coat layer formation as described in any one of these.
[24] A cured product of the resin composition for forming a hard coat layer according to any one of [1] to [23].
[25] A coated article provided with a hard coat layer made of a cured product of the resin composition for forming a hard coat layer according to any one of [1] to [23] on the surface of an article.
[26] A coated product obtained by applying the resin composition for forming a hard coat layer according to any one of [1] to [23] to the surface of an article and curing it.

Since the resin composition for forming a hard coat layer of the present invention has the above-described configuration, it has high surface hardness, excellent scratch resistance, and low curling property (or low curing shrinkage) when irradiated with active energy rays. Can be suitably used as a resin composition for forming a hard coat layer on the surface of a plastic film such as TAC (cellulose triacetate) or PET (polyethylene terephthalate). In addition, the resin composition for forming a hard coat layer of the present invention can be preferably used as a resin composition for forming a hard coat layer of a glass substrate. In addition to the wrinkle effect that imparts scratch resistance, the effect of preventing the glass substrate from cracking can also be exhibited.

It is the schematic for demonstrating the evaluation method of curl property in an Example.

The resin composition for forming a hard coat layer of the present invention (hereinafter sometimes referred to as “resin composition”) contains a polyfunctional alicyclic epoxy compound (A) and a polyfunctional (meth) acrylic compound (B). To do. In the present specification, “(meth) acryl” means acryl and / or methacryl (any one or both of acryl and methacryl), and the same applies to (meth) acrylate and the like.

[Polyfunctional alicyclic epoxy compound (A)]
The polyfunctional alicyclic epoxy compound (A) is a cationic curable compound having an alicyclic structure and two or more epoxy groups in one molecule. In the resin composition of this invention, a polyfunctional alicyclic epoxy compound (A) can be used individually by 1 type or in combination of 2 or more types.
Specifically, as the polyfunctional alicyclic epoxy compound (A),
(I) Compound having an epoxy group (alicyclic epoxy group) composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring (ii) Compound having an epoxy group directly bonded to the alicyclic ring by a single bond (Iii) Examples include compounds having an alicyclic ring and a glycidyl group.

Examples of the compound (i) having an alicyclic epoxy group include compounds represented by the following formula (I) (alicyclic epoxy compounds).

In the above formula (I), X represents a single bond or a linking group (a divalent group having one or more atoms). Examples of the linking group include a divalent hydrocarbon group, an alkenylene group in which part or all of a carbon-carbon double bond is epoxidized, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, and the like. And a group in which a plurality of are connected. In addition, a substituent such as an alkyl group may be bonded to one or more carbon atoms constituting the cyclohexane ring (cyclohexene oxide group) in the formula (I).

Examples of the divalent hydrocarbon group include a linear or branched alkylene group having 1 to 18 carbon atoms, a divalent alicyclic hydrocarbon group, and the like. Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, and a trimethylene group. Examples of the divalent alicyclic hydrocarbon group include 1,2-cyclopentylene group, 1,3-cyclopentylene group, cyclopentylidene group, 1,2-cyclohexylene group, 1,3-cyclopentylene group, And cycloalkylene groups (including cycloalkylidene groups) such as cyclohexylene group, 1,4-cyclohexylene group, and cyclohexylidene group.

Examples of the alkenylene group in the alkenylene group in which part or all of the carbon-carbon double bond is epoxidized (sometimes referred to as “epoxidized alkenylene group”) include, for example, vinylene group, propenylene group, 1-butenylene group And straight or branched alkenylene groups having 2 to 8 carbon atoms such as 2-butenylene group, butadienylene group, pentenylene group, hexenylene group, heptenylene group, octenylene group, and the like. In particular, the epoxidized alkenylene group is preferably an alkenylene group in which all of the carbon-carbon double bonds are epoxidized, more preferably 2 to 4 carbon atoms in which all of the carbon-carbon double bonds are epoxidized. Alkenylene group.

The linking group in X is particularly preferably a linking group containing an oxygen atom, specifically, —CO—, —O—CO—O—, —COO—, —O—, —CONH—, epoxy. An alkenylene group; a group in which a plurality of these groups are linked; a group in which one or more of these groups are linked to one or more of the divalent hydrocarbon groups, and the like.

Representative examples of the compound represented by the above formula (I) include (3,4,3 ′, 4′-diepoxy) bicyclohexyl, bis (3,4-epoxycyclohexylmethyl) ether, 1,2- Epoxy-1,2-bis (3,4-epoxycyclohexane-1-yl) ethane, 2,2-bis (3,4-epoxycyclohexane-1-yl) propane, 1,2-bis (3,4- And epoxycyclohexane-1-yl) ethane and compounds represented by the following formulas (I-1) to (I-10). L in the following formula (I-5) is an alkylene group having 1 to 8 carbon atoms, and in particular, a linear or branched chain having 1 to 3 carbon atoms such as a methylene group, an ethylene group, a propylene group, and an isopropylene group. -Like alkylene groups are preferred. N ¹ to n ⁸ in the following formulas (I-5), (I-7), (I-9) and (I-10) each represents an integer of 1 to 30.

(I) As the compound having an alicyclic epoxy group, for example, commercially available products such as trade names “Celoxide 2021P” and “Celoxide 2081” (manufactured by Daicel Corporation) can be used.

Examples of the compound (ii) having an epoxy group directly bonded to the alicyclic ring with a single bond include compounds represented by the following formula (II).

In the formula (II), R ′ is a group obtained by removing p hydroxyl groups (—OH) from the structural formula of p-valent alcohol (p-valent organic group), and p and n each represent a natural number. Examples of the p-valent alcohol [R ′-(OH) _p ] include polyhydric alcohols (such as alcohols having 1 to 15 carbon atoms) such as 2,2-bis (hydroxymethyl) -1-butanol. p is preferably 1 to 6, and n is preferably 1 to 30. When p is 2 or more, n in each square bracket (outer bracket) group may be the same or different. Specific examples of the compound represented by the above formula (II) include 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol [for example, , Trade name “EHPE3150” (manufactured by Daicel Corporation), etc.].

Examples of the compound (iii) having an alicyclic ring and a glycidyl group described above include a compound obtained by hydrogenating a bisphenol A type epoxy compound (hydrogenated bisphenol A type epoxy compound), a compound obtained by hydrogenating a bisphenol F type epoxy compound ( Hydrogenated bisphenol F type epoxy compound), hydrogenated biphenol type epoxy compound, hydrogenated phenol novolak type epoxy compound, hydrogenated cresol novolak type epoxy compound, hydrogenated cresol novolak type epoxy compound of bisphenol A, hydrogenated naphthalene type epoxy compound, Examples thereof include hydrogenated aromatic glycidyl ether-based epoxy compounds such as hydrogenated epoxy compounds of epoxy compounds obtained from trisphenolmethane.

The polyfunctional alicyclic epoxy compound (A) is preferably a compound having (i) an alicyclic epoxy group in that a cured product having low curling property, high surface hardness and excellent transparency can be obtained. , 4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate [compound represented by the above formula (I-1), trade name “Celoxide 2021P” (manufactured by Daicel Corporation), etc.], and (3, 4,3 ′, 4′-diepoxy) bicyclohexyl is particularly preferred.

The content (blending amount) of (A) is, for example, 3 to 50% by weight of the total amount of nonvolatile components (components other than the solvent) contained in the resin composition of the present invention, and the upper limit is preferably 38% by weight, Particularly preferred is 33% by weight, most preferred 29% by weight, particularly preferred 25% by weight. The lower limit is preferably 6% by weight, particularly preferably 10% by weight, most preferably 13% by weight, particularly preferably 17% by weight.

The content (blending amount) of (A) is 3 to 35% by weight, preferably 10 to 33% by weight, particularly preferably 13% of the sum (100% by weight) of the contents of (A) and (B). ~ 29% by weight, most preferably 17-25% by weight.

By controlling the content of (A) within the above range, the effect of reducing curling properties can be obtained while maintaining scratch resistance. When the content of (A) exceeds the above range, the content of the polyfunctional (meth) acrylic compound (B) described later is reduced, so that reverse curling properties are exhibited, and it is difficult to obtain a cured product with low curling properties. Become. Moreover, there exists a tendency for abrasion resistance to fall. On the other hand, if the content of (A) is less than the above range, the content of the polyfunctional (meth) acrylic compound (B) described later becomes excessive, so that positive curling properties are exhibited and a low curled cured product is obtained. It becomes difficult.

[Polyfunctional (meth) acrylic compound (B)]
The polyfunctional (meth) acrylic compound (B) in the present invention is a radically curable compound having two or more (meth) acryloyl groups in one molecule. In the resin composition of this invention, a polyfunctional (meth) acryl compound (B) can be used individually by 1 type or in combination of 2 or more types.

The number (total number) of acryloyl groups and / or methacryloyl groups in the molecule of the polyfunctional (meth) acrylic compound (B) is 2 or more, for example 2 to 15, more preferably 3 or more (for example 3 To 12), more preferably 5 or more (for example, 5 to 10).

The molecular weight of the polyfunctional (meth) acrylic compound (B) is, for example, 300 to 13000, preferably 400 to 13000, particularly preferably 500 to 10,000, and most preferably 500 to 3000. The weight average molecular weight (Mw) of the polyfunctional (meth) acrylic compound (B) is, for example, 400 to 13000, preferably 500 to 10,000, and particularly preferably 500 to 3000. When the molecular weight is less than 300 and / or the weight average molecular weight is less than 400, the curled property of the cured product may increase. On the other hand, when the molecular weight and / or the weight average molecular weight exceeds 13,000, the surface hardness of the cured product is lowered, and it may not be able to serve as a top coat (particularly a hard coat) of the protective film. In addition, a weight average molecular weight is a molecular weight of standard polystyrene conversion measured by GPC method.

Examples of the polyfunctional (meth) acrylic compound (B) include non-aromatic (eg, aliphatic (meth) acrylate (linear or branched aliphatic (meth) acrylate), alicyclic (meth) acrylate, etc. (Meth) acrylate); aromatic (meth) acrylate and the like. In the present invention, among them, non-aromatic (meth) acrylate is preferable from the viewpoint of non-coloring property of the cured product, and aliphatic (meth) acrylate is particularly preferable.

Specifically, examples of the polyfunctional (meth) acrylic compound (B) include 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, and glycerin diester. (Meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (Meth) acrylate, neopentyl glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) ) Acrylate, 1,10-decandiol di (meth) acrylate, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, 2,2-bis [4-((meth) acryloyl) Oxydiethoxy) phenyl] propane, and bifunctional (meth) acrylates such as derivatives thereof; ethoxylated isocyanuric acid tri (meth) acrylate, ε-caprolactone-modified tris (2- (meth) acryloyloxyethyl) isocyanurate, glycerin 3 moles of tri (meth) acrylate, ethoxylated glycerin tri (meth) acrylate, propoxylated glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane Tri (meth) acrylate of a tylene oxide adduct, tri (meth) acrylate of a 3 mol propylene oxide adduct of trimethylolpropane, 6 mol of a trimethylolpropane, tri (meth) acrylate of an ethylene oxide adduct, 6 of trimethylolpropane Mole propylene oxide adduct tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol poly (meth) acrylate (e.g., Dipentaerythritol hexa (meth) acrylate, hexa (meth) acrylate of caprolactone adduct of dipentaerythritol, etc.), and derivatives thereof, poly Steal (meth) acrylate, polyether (meth) acrylate, acrylic (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, polyalkadiene (meth) acrylate (for example, polybutadiene (meth) acrylate), melamine Trifunctional or higher polyfunctional (meth) acrylates such as (meth) acrylate and polyacetal (meth) acrylate are exemplified.

As the polyfunctional (meth) acrylic compound (B), for example, a commercial product such as a trade name “DPHA” (manufactured by Daicel Ornex Co., Ltd.) can be suitably used.

(Meth) acryloyl group (for example, (meth) acryloyl group contained in polyfunctional (meth) acrylic compound (B) in the total amount of (A), (B), (C) contained in the resin composition of the present invention ) Is, for example, more than 5.0 mmol / g (for example, more than 5.0 mmol / g and not more than 10.0 mmol / g), preferably 5.5 mmol / g or more, more preferably 6.0. It is at least mmol / g, particularly preferably at least 6.5 mmol / g, most preferably at least 7.0 mmol / g. The upper limit of the (meth) acryloyl group concentration is preferably 9.5 mmol / g, more preferably 9.0 mmol / g, still more preferably 8.5 mmol / g, and particularly preferably 8.0 mmol / g. Most preferably, it is 7.5 mmol / g.

The content of (B) is, for example, 40 to 95% by weight of the total amount of nonvolatile components (components other than the solvent) contained in the resin composition of the present invention, and the upper limit is preferably 90% by weight, more preferably 85%. % By weight, particularly preferably 80% by weight, most preferably 75% by weight. The lower limit is preferably 45% by weight, more preferably 50% by weight, and particularly preferably 55% by weight.

In addition, the content (blending amount) of (B) is 65 to 97% by weight, preferably 65 to 94% by weight of the sum (100% by weight) of the contents of (A) and (B), more preferably Is 65 to 90% by weight, particularly preferably 65 to 87% by weight, most preferably 68 to 83% by weight, particularly preferably 73 to 83% by weight.

By controlling the content of (B) within the above range, the effect of reducing the curling property can be obtained while maintaining the scratch resistance. When the content of (B) exceeds the above range, the content of the above-mentioned polyfunctional alicyclic epoxy compound (A) decreases, so that positive curling properties are expressed and it is difficult to obtain a cured product with low curling properties. Become. On the other hand, if the content of (B) is less than the above range, the content of the polyfunctional alicyclic epoxy compound (A) described above becomes excessive, so that reverse curling properties are exhibited, and a low curled cured product is obtained. It becomes difficult. Moreover, there exists a tendency for abrasion resistance to fall.

[Surface-modified inorganic particles (C)]
The surface-modified inorganic particles (C) in the present invention are reactive functional groups (that is, functional groups having reactivity with epoxy groups) with the epoxy groups and / or (meth) acryloyl groups of the polyfunctional alicyclic epoxy compound (A). , (Meth) acryloyl group-reactive functional group, or epoxy group and (meth) acryloyl group-reactive functional group) on the surface. Since the surface-modified inorganic particles (C) in the present invention have the reactive functional group, they are excellent in compatibility with organic substances. Moreover, it is excellent in dispersibility and can prevent that inorganic particles aggregate. And when the surface modification inorganic particle (C) in this invention has a reactive functional group with an epoxy group, it couple | bonds with the said polyfunctional alicyclic epoxy compound (A), and the surface modification inorganic particle (C) in this invention is. When it has a reactive functional group with a (meth) acryloyl group, it binds to the polyfunctional (meth) acrylic compound (B), and the surface-modified inorganic particles (C) in the present invention have an epoxy group, a (meth) acryloyl group, In the case where it has a reactive functional group, it binds to the polyfunctional alicyclic epoxy compound (A) and the polyfunctional (meth) acrylic compound (B). Excellent scratch resistance can be imparted. Furthermore, it can prevent that haze increases or brittleness generate | occur | produces in hardened | cured material. A surface modification inorganic particle (C) can be used individually by 1 type or in combination of 2 or more types.

The inorganic particles include transparent inorganic particles such as silica, titania, alumina, zirconia and the like. In the present invention, among others, the coloration of the cured product can be suppressed, and the curing of the curable compound (that is, the polyfunctional alicyclic epoxy compound (A) or the polyfunctional (meth) acrylic compound (B)). Silica is preferable in that it does not inhibit the above-mentioned and does not decompose the curable compound and its polymer.

The average particle diameter of the inorganic particles (according to the dynamic light scattering method) is 0.1 to 100 nm, preferably 1 to 50 nm, particularly preferably 3 to 20 nm. When the average particle diameter exceeds the above range, the transparency tends to decrease. On the other hand, if the average particle size is below the above range, scratch resistance tends to be difficult to obtain.

Examples of the reactive functional group with the epoxy group and / or (meth) acryloyl group include (meth) acryloyl group, glycidyl ether group, alicyclic epoxy group, oxetanyl group, vinyl ether group, thiirane group, vinyl group, hydroxyl group. Etc. In the present invention, among them, a group excellent in reactivity with an epoxy group is preferable in that the scratch resistance of the polyfunctional alicyclic epoxy compound (A) can be improved, and in particular, a hydroxyl group, a glycidyl ether group, an alicyclic epoxy group ( For example, a cyclohexene oxide group) is preferable.

In the present invention, for example, a commercial product such as a trade name “Y10C-MFK” (manufactured by Admatechs Co., Ltd.) can be suitably used.

The content (blending amount) of (C) is, for example, 1 to 30% by weight, preferably 3 to 25% by weight, particularly preferably the total amount of nonvolatile components (components other than the solvent) contained in the resin composition of the present invention. 4 to 20% by weight, most preferably 5 to 15% by weight.

The content (blending amount) of (C) is, for example, 5 to 40 parts by weight, preferably 5 to 30 parts by weight, more preferably 7 parts per 100 parts by weight of the total content of (A) and (B). -25 parts by weight, particularly preferably 10-20 parts by weight, most preferably 10-15 parts by weight.

The sum of the contents of (A) and (C) is, for example, 5 to 60% by weight of the total (100% by weight) of the above (A), (B) and (C), and the upper limit is preferably 55%. % By weight, particularly preferably 50% by weight, most preferably 40% by weight. The lower limit is preferably 10% by weight, particularly preferably 15% by weight, most preferably 20% by weight, particularly preferably 25% by weight.

When (C) is contained in the above range, a cured product having scratch resistance, high hardness and low curling property is preferred. When the content of (C) is below the above range, the scratch resistance tends to decrease. On the other hand, when the content of (C) exceeds the above range, transparency tends to be impaired.

In the case where the resin composition of the present invention contains inorganic particles having a reactive functional group on the surface with the epoxy group of the polyfunctional alicyclic epoxy compound (A) as the surface-modified inorganic particles (C), the resin composition is In preparation, the polyfunctional alicyclic epoxy compound (A) and the surface-modified inorganic particles (C) may be added and mixed, respectively, but the composition thus obtained is When the content of the surface-modified inorganic particles (C) is large, haze tends to occur. Usually, when the surface-modified inorganic particles (C) are added to the resin composition, they are added in a state of being dispersed in a solvent. However, if a large amount of the surface-modified inorganic particles (C) is added, the amount of the solvent is increased accordingly. Therefore, when the solvent content is set low, the amount of the surface-modified inorganic particles (C) that can be added is considerably limited. For this reason, the epoxy group of the polyfunctional alicyclic epoxy compound (A) is reacted with a reactive functional group (for example, a hydroxyl group) with the epoxy group of the surface-modified inorganic particle (C), or the surface-modified inorganic particle (C). Are dispersed in the polyfunctional alicyclic epoxy compound (A) without solvent, or the surface-modified inorganic particles (C) dispersed in the solvent are mixed with the polyfunctional alicyclic epoxy compound (A), and then the solvent is added. It is preferable to use the removed one. As what made the polyfunctional alicyclic epoxy compound (A) and the surface modification inorganic particle (C) react, a brand name "NANOPOX C620" (made by EVONIC) etc. can be used conveniently, for example. Further, the surface-modified inorganic particles (C) having a functional group reactive with an epoxy group are dispersed in the polyfunctional alicyclic epoxy compound (A) without a solvent. For example, “Y10C-JFS” (( (Manufactured by Admatechs Co., Ltd.) can be preferably used.

[Photocationic polymerization initiator (D)]
The cationic photopolymerization initiator is a compound that generates an acid upon irradiation with light and initiates the curing reaction of the cationic curable compound contained in the resin composition, and serves as a cation moiety that absorbs light and a source of acid generation. It consists of an anion part.

Examples of the cationic photopolymerization initiator include diazonium salt compounds, iodonium salt compounds, sulfonium salt compounds, phosphonium salt compounds, selenium salt compounds, oxonium salt compounds, ammonium salt compounds, bromine salt compounds, and the like. Can be mentioned.

In the present invention, it is particularly preferable to use a sulfonium salt compound in that a cured product having excellent curability can be formed. Examples of the cation moiety of the sulfonium salt compound include (4-hydroxyphenyl) methylbenzylsulfonium ion, triphenylsulfonium ion, diphenyl [4- (phenylthio) phenyl] sulfonium ion, and 4- (4-biphenylylthio) phenyl. Examples thereof include arylsulfonium ions such as -4-biphenylylphenylsulfonium ion and tri-p-tolylsulfonium ion (particularly, triarylsulfonium ion).

As an anion part of the photocationic polymerization initiator, for example, [(Y) _s B (Phf) _4-s ] ⁻ (wherein Y represents a phenyl group or a biphenylyl group. Phf represents at least one hydrogen atom, A phenyl group substituted with at least one selected from a perfluoroalkyl group, a perfluoroalkoxy group, and a halogen atom (s is an integer of 0 to 3), BF ₄ ⁻ , [(Rf) _t PF _6-t] ^- (wherein, Rf is .t represents an alkyl group in which at least 80% of the hydrogen atoms are substituted with fluorine atoms is an integer of ^{_{0 ~ 5), AsF 6 -}} , SbF 6 -, SbF 5 OH- ^{and the} like can be mentioned.

Examples of the photocationic polymerization initiator in the present invention include (4-hydroxyphenyl) methylbenzylsulfonium tetrakis (pentafluorophenyl) borate, 4- (4-biphenylylthio) phenyl-4-biphenylylphenylsulfonium tetrakis (penta Fluorophenyl) borate, 4- (phenylthio) phenyldiphenylsulfonium phenyltris (pentafluorophenyl) borate, [4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium phenyltris (pentafluorophenyl) borate, Diphenyl [4- (phenylthio) phenyl] sulfonium tris (pentafluoroethyl) trifluorophosphate, diphenyl [4- (phenylthio) phenyl] sulfo Um tetrakis (pentafluorophenyl) borate, diphenyl [4- (phenylthio) phenyl] sulfonium hexafluorophosphate, 4- (4-biphenylylthio) phenyl-4-biphenylylphenylsulfonium tris (pentafluoroethyl) trifluorophosphate, Bis [4- (diphenylsulfonio) phenyl] sulfide phenyltris (pentafluorophenyl) borate, [4- (2-thioxanthonylthio) phenyl] phenyl-2-thioxanthonylsulfonium phenyltris (pentafluorophenyl) borate , 4- (Phenylthio) phenyldiphenylsulfonium hexafluoroantimonate, trade names “Syracure UVI-6970”, “Syracure UVI-6974” "Syracure UVI-6990", "Syracure UVI-950" (manufactured by Union Carbide, USA), "Irgacure 250", "Irgacure 261", "Irgacure 264" (above, manufactured by BASF), "CG-24-61" (Manufactured by Ciba Geigy), “Optomer SP-150”, “Optomer SP-151”, “Optomer SP-170”, “Optomer SP-171” (manufactured by ADEKA Corporation), “DAICAT II” ((Stock Corporation) ) Manufactured by Daicel), “UVAC1590”, “UVAC1591” (manufactured by Daicel Cytec Co., Ltd.), “CI-2064”, “CI-2639”, “CI-2624”, “CI-2481”, “CI” -2734 "," CI-2855 "," CI-2823 "," CI-2 58 "," CIT-1682 "(manufactured by Nippon Soda Co., Ltd.)," PI-2074 "(manufactured by Rhodia, tetrakis (pentafluorophenyl) borate toluylcumyl iodonium salt)," FFC509 "(manufactured by 3M) ), “BBI-102”, “BBI-101”, “BBI-103”, “MPI-103”, “TPS-103”, “MDS-103”, “DTS-103”, “NAT-103”, “NDS-103” (above, manufactured by Midori Chemical Co., Ltd.), “CD-1010”, “CD-1011”, “CD-1012” (above, manufactured by Sartomer, USA), “CPI-100P”, “ Commercial products such as “CPI-101A” (San Apro Co., Ltd.) can be used. These can be used alone or in combination of two or more.

The content of the photocationic polymerization initiator (D) in the resin composition of the present invention is based on 100 parts by weight of the cationic curable compound (particularly the polyfunctional alicyclic epoxy compound (A)) contained in the resin composition. For example, 1 to 10 parts by weight, preferably 1 to 5 parts by weight, particularly preferably 2 to 4 parts by weight. When content of a photocationic polymerization initiator (D) is less than the said range, there exists a possibility of causing a curing defect. On the other hand, when the content of the cationic photopolymerization initiator (D) exceeds the above range, the cured product tends to be colored.

[Photoradical polymerization initiator (E)]
The radical photopolymerization initiator is a compound that generates radicals by irradiation of light and initiates a curing reaction of a radical curable compound contained in the resin composition. For example, benzophenone, acetophenone benzyl, benzyl dimethyl ketone, benzoin, Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, dimethoxyacetophenone, dimethoxyphenylacetophenone, diethoxyacetophenone, diphenyl disulfite, methyl orthobenzoylbenzoate, ethyl 4-dimethylaminobenzoate (manufactured by Nippon Kayaku Co., Ltd., Product name “Kayacure EPA”, etc., 2,4-diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd., product name “Kayacure DETX” etc.), 2-methyl-1- [4- (methyl) phenyl]- 2-mo Holinopropanone-1 (manufactured by Ciba-Gaigi Co., Ltd., trade name “Irgacure 907” etc.), 1-hydroxycyclohexyl phenyl ketone (Ciba-Geigy Co., Ltd., trade name “Irgacure 184” etc.), 2-dimethylamino-2- (4 -Morpholino) 2-amino-2-benzoyl-1-phenylalkane compounds such as benzoyl-1-phenylpropane, tetra (t-butylperoxycarbonyl) benzophenone, benzyl, 2-hydroxy-2-methyl-1-phenyl- Aminobenzene derivatives such as propan-1-one, 4,4′-bis (diethylamino) benzophenone, 2,2′-bis (2-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2 '-Imidazol (made by Hodogaya Chemical Co., Ltd., trade name "B-CIM" etc.) Dazole compounds, halomethylated triazine compounds such as 2,6-bis (trichloromethyl) -4- (4-methoxynaphthalen-1-yl) -1,3,5-triazine, 2-trichloromethyl-5- (2- And halomethyloxadiazole compounds such as benzofuran-2-yl-ethenyl) -1,3,4-oxadiazole. These can be used alone or in combination of two or more.

The content of the photo radical polymerization initiator (E) in the resin composition of the present invention is based on 100 parts by weight of the radical curable compound (particularly, the polyfunctional (meth) acryl compound (B)) contained in the resin composition. For example, 1 to 10 parts by weight, preferably 1 to 5 parts by weight, particularly preferably 1.5 to 3.5 parts by weight. If the content of the photo radical polymerization initiator (E) is below the above range, there is a risk of causing poor curing. On the other hand, when the content of the radical photopolymerization initiator (E) exceeds the above range, the cured product tends to be colored.

[Other curable compounds]
The resin composition of the present invention contains a curable compound other than the polyfunctional alicyclic epoxy compound (A) and the polyfunctional (meth) acrylic compound (B) (sometimes referred to as “other curable compound”). May be. Other curable compounds include, for example, aromatic glycidyl ether type epoxy compounds, aliphatic polyhydric alcohol polyglycidyl ethers, oxetane compounds (compounds having one or more oxetanyl groups), vinyl ether compounds (having one or more vinyl ether groups). Compound) and the like.

The ratio of the total content of the polyfunctional alicyclic epoxy compound (A) and the polyfunctional (meth) acrylic compound (B) in the total amount (100% by weight) of the curable compound contained in the resin composition of the present invention is, for example, 50 % By weight or more, preferably 70% by weight or more, particularly preferably 80% by weight or more, and most preferably 90% by weight or more. In addition, the upper limit of the total content of the polyfunctional alicyclic epoxy compound (A) and the polyfunctional (meth) acrylic compound (B) is 100% by weight. When the ratio of the total content of the polyfunctional alicyclic epoxy compound (A) and the polyfunctional (meth) acrylic compound (B) is below the above range, it has low curling property, high surface hardness, and excellent scratch resistance. It tends to be difficult to obtain a cured product.

[Additive]
In addition to the above, the resin composition of the present invention may contain various additives within a range that does not impair the effects of the present invention. In the present invention, it is particularly preferable that one or more compounds imparting slipperiness are contained from the viewpoint of obtaining a cured product that is further excellent in scratch resistance.

Examples of the compound that imparts slipperiness include, for example, silane compounds, perfluoroalkyl group-containing (meth) acrylic compounds, silyl group-containing (meth) acrylic compounds, polyether-modified (meth) acrylic compounds, and silicon-modified poly (meth). Acrylate, polyether-modified poly (meth) acrylate, perfluoroalkyl group-containing poly (meth) acrylate, perfluoroalkyl group-containing polyether-modified (meth) acrylate, acrylic-modified polydimethylsiloxane, polyether-modified polydimethylsiloxane, perfluoro Examples include alkyl group-containing polydimethylsiloxane and polyether-modified perfluoroalkyl group-containing polydimethylsiloxane. The compound preferably has a reactive functional group with an epoxy group and / or a (meth) acryloyl group (an example similar to the example in the surface-modified inorganic particles (C) can be given).

Examples of the silane compound include triethylsilane and t-butyldimethylsilane.

Examples of the perfluoroalkyl group-containing (meth) acrylic compound include 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, 2- (Perfluorobutyl) ethyl (meth) acrylate, 2- (perfluorooctyl) ethyl (meth) acrylate and the like.

Examples of the silyl group-containing (meth) acrylic compound include trimethylsilyl (meth) acrylate, triisopropylsilyl (meth) acrylate, tri (n-butyl) silyl (meth) acrylate, triisobutylsilyl (meth) acrylate, and tricyclohexyl. Examples thereof include silyl (meth) acrylate and triphenylsilyl (meth) acrylate.

The silicon-modified poly (meth) acrylate is a compound in which a silicon chain (for example, a polydimethylsiloxane chain) is bonded to the terminal and / or side chain of poly (meth) acrylate as a main chain.

The polyether-modified poly (meth) acrylate is a compound in which a polyether chain is bonded to the terminal and / or side chain of poly (meth) acrylate as a main chain.

The perfluoroalkyl group-containing poly (meth) acrylate is a compound having a perfluoroalkyl group at the terminal and / or side chain of the poly (meth) acrylate as the main chain.

The perfluoroalkyl group-containing polyether-modified (meth) acrylate is a compound having a perfluoroalkyl group and a polyether chain at the terminal and / or side chain of the poly (meth) acrylate as the main chain.

The acrylic-modified polydimethylsiloxane is a compound in which a poly (meth) acrylic chain is bonded to the terminal and / or side chain of the main chain polydimethylsiloxane.

The polyether-modified polydimethylsiloxane, the perfluoroalkyl group-containing polydimethylsiloxane, and the polyether-modified perfluoroalkyl group-containing polydimethylsiloxane are the same as described above except that the poly (meth) acrylate is changed to polydimethylsiloxane. .

Examples of the perfluoroalkyl group include a perfluoroalkyl group having 3 to 30 carbon atoms such as a perfluorooctyl group.

In the present invention, a compound containing a hydroxyl group that is particularly excellent in reactivity with the epoxy group of the polyfunctional alicyclic epoxy compound (A) (for example, a hydroxyl group-containing silicon-modified poly (meth) acrylate) may be used. The hydroxyl value is preferably 5 to 150 mgKOH / g, for example.

The amount of the compound that imparts slipperiness (the total amount when two or more compounds are contained) is the sum (100 parts by weight) of (A), (B), and (C) contained in the resin composition of the present invention. On the other hand, it is, for example, 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, particularly preferably 0.1 to 3 parts by weight.

In addition to the resin composition of the present invention, a solvent (for example, butyl acetate, methyl ethyl ketone, etc.), a polyhydric alcohol, a curing aid, an organosiloxane compound, metal oxide particles, rubber particles, an antifoaming agent, a silane cup Conventional additives such as ring agents, fillers, plasticizers, leveling agents, antistatic agents, mold release agents, surfactants, flame retardants, colorants, antioxidants, ultraviolet absorbers, ion adsorbers, phosphors, etc. Can be used. The content of these additives can be appropriately set within a range of, for example, 0 to 40% by weight, preferably 1 to 25% by weight, based on the resin composition (100% by weight) of the present invention.

The resin composition of the present invention can be prepared by stirring and mixing the above-described components while being heated as necessary. In addition, the resin composition of the present invention can be used as a one-component composition in which components mixed in advance are used as they are. For example, components divided into two or more (each component is 2 A mixture of the above components may be used as a multi-liquid composition (for example, a two-liquid composition) that is used by mixing at a predetermined ratio before use. The stirring / mixing method is not particularly limited, and for example, known or conventional stirring / mixing means such as various mixers such as a dissolver and a homogenizer, a kneader, a roll, a bead mill, a self-revolving stirrer and the like can be used. Further, after stirring and mixing, defoaming may be performed under vacuum.

<Composition for hard coat>
By curing the resin composition of the present invention, a cured product having low curl properties and excellent surface hardness and scratch resistance can be obtained. For this reason, the resin composition of the present invention can be preferably used as a composition for hard coat (hard coat agent).

<Painted object>
The resin composition of the present invention is applied to the surface of an article [for example, a substrate or film made of metal or resin (for example, plastic such as TAC or PET)] as an object (object to be coated) and cured. By this, a painted product is obtained. Since the resin composition of the present invention has excellent curability (curing speed) and the cured product of the present invention has low curl properties and excellent surface hardness and scratch resistance, the coated product has high productivity and quality. Excellent for both.

The resin composition of the present invention can be cured in an extremely short time by applying an active energy ray such as an ultraviolet ray or an electron beam after being applied to an article. A high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, or the like is used as a light source for ultraviolet irradiation. The irradiation time varies depending on the type of the light source, the distance between the light source and the coating surface, and other conditions, but is several tens of seconds at most, and usually several seconds. Usually, an irradiation source with a lamp output of about 80 to 300 W / cm is used. In the case of electron beam irradiation, it is preferable to use an electron beam having an energy in the range of 50 to 1000 KeV and to give an irradiation amount of 2 to 5 Mrad. After active energy ray irradiation, curing may be promoted by heating (post-cure) as necessary.

The resin composition of the present invention comprises a coating agent (particularly for hard coat use), ink, adhesive, sealant, sealant, resist, composite material, transparent substrate, transparent film or sheet, and optical material (for example, optical lens). Etc.), stereolithography material, electronic material (eg, electronic paper, touch panel, solar cell substrate, optical waveguide, light guide plate, holographic memory, etc.), mechanical component material, electrical component material, automotive component material, civil engineering building material, molding It can be used for various applications such as materials, plastic forming materials, solvents (for example, reactive diluents, etc.).

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

Example 1
[Preparation of resin composition]
Each component is mixed at the blending ratio shown in the table (unit: parts by weight), and stirred using a self-revolving stirrer (trade name “Awatori Nerita AR-250”, manufactured by Shinky Co., Ltd.) Thus, a resin composition was obtained.

[Production of cured film]
The obtained resin composition was applied onto a PET base material (trade name “Lumirror T60”, manufactured by Toray Industries, Inc .; film thickness 100 ± 5 μm) using a bar coater. At this time, it applied using the bar coater so that the film thickness after drying might be set to 20 micrometers.
Then, after drying at 80 ° C. for 1 minute, it was cured by irradiating with ultraviolet rays under the condition of an irradiation amount of about 1000 mJ / cm ^{2 in} a state where it was put in a sealed container purged with nitrogen.
The laminate (cured film) having the structure of “PET substrate / cured product (cured coating film)” thus obtained was used as a sample for pencil hardness evaluation and scratch resistance evaluation.
Further, a test piece having a square of 10 cm on one side was cut from the laminate (cured film) having the configuration of “PET substrate / cured product (cured coating film)” obtained above. With respect to the above test piece, the film thickness at the measurement points indicated by the numbers 1 to 5 circled in FIG. 1 (1a) was measured. At all these measurement points, the case where the film thickness of the cured coating film obtained by subtracting the film thickness of the PET substrate (the film thickness measured in advance) from the film thickness at the measurement point is 20 μm ± 2 μm, respectively. Was used as a sample for curl evaluation. In the case of failure, the bar coater was changed until the film thickness at the above measurement point passed, and the above coating, drying, and curing steps were repeated to prepare a sample for curl evaluation.

Examples 2 to 10, Comparative Examples 1 to 8
A resin composition and its cured product (sample) were obtained in the same manner as in Example 1 except that the amount of each component was changed as shown in the table. In Examples and Comparative Examples other than Example 1 and Comparative Example 2, post-cure (heating at 80 ° C. for 2 hours) was performed after ultraviolet irradiation.

<Evaluation>
The following evaluation test was implemented about the cured | curing material (sample) of the resin composition obtained by the Example and the comparative example.

[Pencil hardness]
The pencil hardness of the cured films (cured coating film thickness: about 20 μm) obtained in Examples and Comparative Examples was measured by the following method.
The pencil hardness of the cured coating film was evaluated according to JIS K5600. The evaluation was performed by external appearance observation, and the cured coating film on the PET base material was rubbed with a pencil. Specifically, the evaluation is first performed with a pencil with a certain hardness, and when the scratch is not found, the evaluation is repeated with the pencil with the hardness one higher. Re-evaluated by hardness. If scratches cannot be confirmed, use a pencil with a hardness of one level again. If reproducibility is confirmed twice or more, the hardness of the hardest pencil without scratches is the pencil hardness of the cured coating film. The evaluation results were expressed in terms of pencil core hardness. The evaluation conditions are as follows.
Evaluation pencil: "Pencil hardness test pencil" manufactured by Mitsubishi Pencil Co., Ltd.
Load: 750gf
Scratching distance: 50 mm or more Scratching angle: 45 °
Measurement environment: 23 ° C, 50% RH
In addition, the sample (cured film) used for a test used what was humidity-controlled for 24 hours with the constant temperature and humidity machine of 23 degreeC and 50% RH.

[Curl property]
For the curl evaluation samples obtained in the examples and comparative examples, the warpage of the four corners when placed on a horizontal plane as shown in FIG. 1 (1b) was measured, and the average value was taken as the amount of warpage of the cured film. . Those having a large amount of warpage are considered to have a large cure shrinkage or cure expansion. When curing shrinkage occurs (when the surface of the cured film in contact with the horizontal plane in FIG. 1 (1b) is opposite to the cured coating film), the warp is positive, and when curing expansion occurs (the cured film The warpage in FIG. 1 (1b) where the surface in contact with the horizontal plane is on the cured coating film side) is shown in the table as a negative value.

[Abrasion resistance]
For the cured films (thickness of about 20 μm) obtained in the examples and comparative examples, the coated surface was subjected to 20 round trips, 200 round trips and 1000 round trips using # 0000 steel wool at a load of 500 g / cm ² or 1 kg / cm ^2. Rubbing and scratch resistance were evaluated. The evaluation of scratch resistance was as follows.
A: No scratches at 1000 round trips B: No scratches at 200 round trips, minute scratches at 1000 round trips C: No scratches at 200 round trips, slight scratches or slight cloudiness at 1000 round trips D : No flaws at 200 round trips, clear flaws at 1000 round trips, or clear cloudiness E: No flaws at 20 round trips, minor flaws at 200 round trips F: No scratches at 20 round trips, G: No scratches at 200 round trips G: No scratches at 20 round trips, clear scratches at 200 round trips, or clear haze H: Minor scratches at 20 round trips I: 20 round trips Minor scratches or slightly cloudy

In addition, the symbol in Table 1 and Table 2 shows the following compounds.
NANOPOX C620: Compound obtained by reacting hydroxyl group-containing silica (silica average particle size: 10 nm) (40 parts by weight) with Celoxide 2021P (60 parts by weight), trade name “NANOPOX C620”, manufactured by EVONIC Y10C-JFS: Celoxide A mixture of 2021P (80.5 parts by weight) and alicyclic epoxy group-containing silica (silica average particle size: 10 nm) (19.5 parts by weight), trade name “Y10C-JFS”, manufactured by Admatechs Corporation Celoxide 2021P: 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate, trade name “Celoxide 2021P”, manufactured by Daicel Corporation A-9550: Dipentaerythritol polyacrylate, molecular weight: about 554, hydroxyl value: about 56 mg KOH / G, Shinnaka Chemical A-TMM-3L-N: pentaerythritol triacrylate, molecular weight: 246, hydroxyl value: about 112 mg KOH / g, Shin-Nakamura Chemical Co., Ltd. DPHA: dipentaerythritol hexaacrylate, molecular weight: 578, product Name “DPHA”, manufactured by Daicel Ornex Co., Ltd. Y10C-MFK: glycidyl ether group-containing silica (silica average particle size: 10 nm) in methyl ethyl ketone dispersion (silica concentration: 30% by weight), trade name “Y10C-MFK”, CPI-210S manufactured by Admatechs Co., Ltd .: diphenyl [4- (phenylthio) phenyl] sulfonium tris (pentafluoroethyl) trifluorophosphate, trade name “CPI-210S”, Irgacure 184: 1-hydroxycyclohexa manufactured by San Apro Co., Ltd. Le phenyl ketone BYK-SILCLEAN 3700: hydroxyl group-containing silicone-modified polyacrylates, hydroxyl value: about 30 mgKOH / g, trade name "BYK-SILCLEAN 3700", manufactured by BYK Chemie Japan Co.,

The resin composition for forming a hard coat layer of the present invention can form a cured product having high surface hardness, excellent scratch resistance, and low curl properties by irradiation with active energy rays. It can be suitably used for applications in which a hard coat layer is formed on the surface of a plastic film or glass substrate.

1 Cured film 2 Horizontal surface 3 Warpage amount

Claims (7)

1. Polyfunctional alicyclic epoxy compound (A) having an alicyclic structure and two or more epoxy groups in one molecule (B) Multifunctional (meth) acrylic compound having two or more (meth) acryloyl groups in one molecule (B ), Surface-modified inorganic particles (C) having a reactive functional group with an epoxy group and / or a (meth) acryloyl group on the surface of an inorganic particle having an average particle diameter (by dynamic light scattering method) of 0.1 to 100 nm , A cationic photopolymerization initiator (D), and a radical photopolymerization initiator (E), wherein the content of (A) is the sum of the contents of (A) and (B) (100 wt%). A resin composition for forming a hard coat layer, comprising 3 to 35% by weight.
2. The resin composition for forming a hard coat layer according to claim 1, wherein the content of (C) is 5 to 40 parts by weight with respect to 100 parts by weight of the total content of (A) and (B).
3. The concentration of (meth) acryloyl groups in the total amount of (A), (B), and (C) contained in the resin composition for forming a hard coat layer is more than 5.0 mmol / g. Hard coat layer forming resin composition.
4. The resin composition for forming a hard coat layer according to any one of claims 1 to 3, wherein the inorganic particles in the surface-modified inorganic particles (C) are silica.
5. Furthermore, a silicon compound, a perfluoroalkyl group-containing (meth) acrylic compound, a silyl group-containing (meth) acrylic compound, a polyether-modified (meth) having a reactive functional group with an epoxy group and / or a (meth) acryloyl group Acrylic compound, silicon-modified poly (meth) acrylate, polyether-modified poly (meth) acrylate, perfluoroalkyl group-containing poly (meth) acrylate, perfluoroalkyl group-containing polyether modified (meth) acrylate, acrylic-modified polydimethylsiloxane, 5. At least one compound selected from polyether-modified polydimethylsiloxane, perfluoroalkyl group-containing polydimethylsiloxane, and polyether-modified perfluoroalkyl group-containing polydimethylsiloxane. A hard coat layer-forming resin composition according to any one.
6. A cured product of the resin composition for forming a hard coat layer according to any one of claims 1 to 5.
7. 6. A coated article provided with a hard coat layer made of a cured product of the resin composition for forming a hard coat layer according to any one of claims 1 to 5 on the surface of an article.

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