TW201700650A - 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

Resin composition for forming a hard coat layer and cured product thereof

The present invention relates to a resin composition for forming a hard coat layer and a cured product thereof. Moreover, the present invention relates to a coated article obtained by using the above-described resin composition for forming a hard coat layer. Priority is claimed on Japanese Patent Application No. 2015-086412, the entire disclosure of which is hereby incorporated by reference.

A liquid crystal monitor such as a liquid crystal display, an organic EL display, or a plasma display is attached with a protective film, whereby the following effects can be obtained: or the screen is prevented from being damaged, or the fingerprint is not easily attached to the screen, or the attached image is attached. The dirt on the screen is easy to wipe off. On the surface of the aforementioned protective film, a hard coat layer which is useful for imparting scratch resistance is formed. Then, in recent years, there has been a demand for increasing the surface hardness of the liquid crystal protective film, and it is required to improve the performance of the hard coat layer.

As a means for increasing the surface hardness of the hard coat layer, it is widely used as a means for forming a hardenable group of a hard coat layer. However, it is known that a polyfunctionalized hardenable compound causes an increase in resin density, that is, hardening shrinkage, before and after hardening. Then, the more the functionalization, the more pronounced the hardening shrinkage, and the fact that the protective film exhibits curling property is a problem.

Further, in order to improve the scratch resistance of a hard coat layer, a method of blending inorganic particles such as alumina, cerium oxide, or titanium oxide into a curable compound, a so-called organic-inorganic hybrid method is known (Patent Literature) 1).

However, when the inorganic particles are dispersed in the resin to form a coating film, the inorganic particles may be deficient from the cured coating film (hardened coating film), or an increase in haze or a brittleness may be observed. This is considered to be due to the poor compatibility of organic matter with inorganic matter. Then, as a method of improving the compatibility between the organic substance and the inorganic substance, a method of using a nano filler having a particle diameter of the inorganic particles reduced to a nanometer size is known (Patent Document 2). However, when nanometer-sized inorganic particles are used, the dispersion stability is lowered, and the inorganic particles are easily aggregated with each other, and it is difficult to maintain the transparency of the cured coating film. Further, a method of using a surface-modified inorganic filler whose surface is externally modified with an organic material is also known (Patent Document 3). However, when inorganic particles surface-modified with an organic substance are used, it is difficult to increase the surface hardness of the cured coating film, and the surface hardness may be lowered.

[Previous Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Publication No. 2-60696

Patent Document 2: Japanese Laid-Open Patent Publication No. 2005-76005

Patent Document 3: Japanese Patent Laid-Open Publication No. 2003-34761

In view of the above, it is an object of the present invention to provide a resin composition for forming a hard coat layer which is provided with a cured product having higher surface hardness and scratch resistance while suppressing the appearance of curling property.

In addition, the term "crimpness" means a property of causing curling on a substrate when a cured film (hardened coating film) is formed on a substrate, and the term "low curling property" means that it is difficult to similarly The properties produced by the substrate in the curl.

As a result of intensive investigations to solve the above problems, the present inventors have found that a polyfunctional alicyclic epoxy compound, a polyfunctional (meth)acrylic compound, and an inorganic particle having a functional group are contained in a specific ratio. a resin composition reactive with an epoxy group of the above polyfunctional alicyclic epoxy compound and/or a (meth) acryl oxime group of a polyfunctional (meth)acrylic compound, which is irradiated with an active energy ray, that is, It is possible to obtain a cured product which suppresses curling property, that is, has low curling property (or low hardening shrinkage property) and has higher surface hardness and scratch resistance. The present invention is based on the knowledge of the knowledge.

In other words, the present invention provides a resin composition for forming a hard coat layer, which comprises a polyfunctional alicyclic epoxy compound (A) having an alicyclic structure and two or more epoxy groups in one molecule, and having one molecule; Two or more (meth)acrylonitrile-based polyfunctional (meth)acrylic compounds (B) and an average particle diameter (based on dynamic light scattering method) of 0.1 to 100 nm have surface and epoxy groups and/or Surface-modified inorganic particles (C), photocationic polymerization initiator (D), and photoradical polymerization initiator (E) of a reactive functional group of (meth)acryl fluorenyl group, and the content of the above (A) For the contents of (A) and (B) And (100% by weight) of 3 to 35% by weight.

Furthermore, the present invention provides a resin composition for forming a hard coat layer, wherein the content of the above (C) is 5 to 40 parts by weight based on 100 parts by weight of the total of the above (A) and (B).

Moreover, the present invention provides a resin composition for forming a hard coat layer, wherein (meth)acryloyl group is contained in the total amount of (A), (B), and (C) contained in the resin composition for forming a hard coat layer. The concentration is greater than 5.0 millimoles/g.

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

Moreover, the present invention provides the resin composition for forming a hard coat layer, which further contains at least one selected from the group consisting of the following compounds having a reactive functional group with an epoxy group and/or a (meth) acryl group; Compound: hydrazine compound, (meth)acrylic compound containing perfluoroalkyl group, (meth)acrylic compound containing mercapto group, polyether modified (meth)acrylic compound, cerium modified poly(meth)acrylate Polyether modified poly(meth)acrylate, poly(meth)acrylate containing perfluoroalkyl group, polyether modified (meth)acrylate containing perfluoroalkyl group, propylene-based modified poly Dimethyl decane, polyether modified polydimethyl siloxane, polydimethyl siloxane containing perfluoroalkyl, and polyether modified polydimethyl oxime containing perfluoroalkyl alkyl.

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

Moreover, the present invention provides a coated article having a hard coat layer containing a cured product of the resin composition for forming a hard coat layer on the surface of the article. Floor.

That is, the present invention relates to the following.

[1] A resin composition for forming a hard coat layer, comprising: a polyfunctional alicyclic epoxy compound (A) having an alicyclic structure and two or more epoxy groups in one molecule, and two in one molecule The surface of the above (meth)acryloyl group-containing polyfunctional (meth)acrylic compound (B) and the average particle diameter (based on dynamic light scattering method) of 0.1 to 100 nm have an epoxy group and/or (A) a surface-modified inorganic particle (C), a photocationic polymerization initiator (D), and a photoradical polymerization initiator (E) of a reactive functional group of an acrylonitrile group, and the content of the above (A) is ( 3 to 35% by weight of the sum of the contents of A) and (B) (100% by weight).

[2] The resin composition for forming a hard coat layer according to [1], wherein (A) is a compound represented by the formula (I) (alicyclic epoxy compound).

[3] The resin composition for forming a hard coat layer according to [1], wherein (A) is selected from the group consisting of (3,4,3',4'-diepoxy)bicyclohexane, bis (3) , 4-epoxycyclohexylmethyl)ether, 1,2-epoxy-1,2-bis(3,4-epoxycyclohexane-1-yl)ethane, 2,2-double (3,4-epoxycyclohexane-1-yl)propane, 1,2-bis(3,4-epoxycyclohexane-1-yl)ethane, and formula (I-1)~ At least one compound of the group of compounds represented by (I-10).

[4] The resin composition for forming a hard coat layer according to [1], wherein (A) is 3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexanecarboxylate and / or (3,4,3',4'-dicyclooxy)bicyclohexane.

[5] The resin composition for forming a hard coat layer according to any one of [1], wherein (B) has three or more (for example, 3 to 12, preferably 5 or more, Preferably, it is a compound of 5 to 10 (meth)acrylonitrile groups.

[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 from 300 to 13,000.

[7] The resin composition for forming a hard coat layer according to any one of [1], wherein the weight average molecular weight of (B) (in terms of GPC standard polystyrene) is 400 to 13,000.

[8] The resin composition for forming a hard coat layer according to any one of [1], 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], wherein the inorganic particles in (C) are cerium oxide, titanium oxide, aluminum oxide, or zirconium oxide.

[10] The resin composition for forming a hard coat layer according to any one of [1], wherein the inorganic particles in (C) are cerium oxide.

[11] The resin composition for forming a hard coat layer according to any one of [1], wherein the average particle diameter (based on dynamic light scattering method) of the inorganic particles in (C) is 1 to 10 nm. .

[12] The resin composition for forming a hard coat layer according to any one of [1], wherein the reactivity with the epoxy group and/or the (meth) acrylonitrile group in (C) The functional group is a group selected from the group consisting of a hydroxyl group, a glycidyl ether group, and an alicyclic epoxy group (preferably an epoxycyclohexane group).

[13] The resin composition for forming a hard coat layer according to any one of [1], which further comprises a reactive functional group selected from the group consisting of an epoxy group and/or a (meth) acrylonitrile group. At least one of the following compounds of the group: an anthracene compound, a (meth)acrylic compound containing a perfluoroalkyl group, a (meth)acrylic compound containing a mercapto group, and a polyether-modified (meth)acrylic acid Compound, cerium modified poly(meth) acrylate, polyether modified poly(meth) acrylate, poly(meth) acrylate containing perfluoroalkyl group, polyether modified with perfluoroalkyl group ( Methyl) acrylate, propylene fluorenyl modified polydimethyl methoxy oxane, polyether modified polydimethyl methoxy oxane, polydimethyl siloxane containing perfluoroalkyl group, and polyether modification Polydimethylsiloxane having a perfluoroalkyl group.

[14] The resin composition for forming a hard coat layer according to any one of [1] to [12] further comprising a hydrazine-modified poly(meth)acrylate containing a hydroxyl group.

[15] The resin composition 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 the nonvolatile component contained in the resin composition. %.

[16] The resin composition 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 the nonvolatile component contained in the resin composition. %.

The resin composition for forming a hard-coat layer according to any one of [1] to [16], wherein (A), (B), and (C) are contained in the resin composition for forming a hard coat layer. The concentration of (meth) acrylonitrile in the total amount is greater than 5.0 millimoles/g.

[18] The resin composition for forming a hard coat layer according to any one of [1], wherein the content of (C) is 1 to 30 by weight of the total amount of the nonvolatile component contained in the resin composition. %.

[19] The resin composition for forming a hard coat layer according to any one of the above [1], wherein the content of (C) is 5 based on the total content of the above (A) and (B). ~40 parts by weight.

[20] The resin for forming a hard coat layer according to any one of [1] to [19] The composition wherein the sum of the contents of (A) and (C) is 5 to 60% by weight based on the total of (A), (B), and (C) (100% by weight).

[21] The resin composition for forming a hard coat layer according to any one of [1] to [20] wherein a cationic hardening compound (particularly a polyfunctional alicyclic epoxy compound) is contained with respect to the resin composition. A)) 100 parts by weight, and the content of (D) is 1 to 10 parts by weight.

The resin composition for forming a hard coat layer according to any one of the above aspects, wherein the radical curable compound (especially polyfunctional (meth)acrylic acid) is contained with respect to the resin composition. The compound (B)) is 100 parts by weight, and the content of (E) is 1 to 10 parts by weight.

[23] The resin composition for forming a hard coat layer according to any one of [1] to [22], wherein the resin composition for hard coat layer formation is selected from the total (100 parts by weight) of (A), (B), and (C). The content of at least one of the following compounds having a reactive functional group with an epoxy group and/or a (meth) acrylonitrile group (especially a hydrazine-modified poly(meth) acrylate having a hydroxyl group) is 0.01 to 10 parts by weight: an antimony compound, a (meth)acrylic compound containing a perfluoroalkyl group, a (meth)acrylic compound containing a mercapto group, a polyether modified (meth)acrylic compound, and a rhodium-modified poly(A) Acrylate, polyether modified poly(meth)acrylate, poly(meth)acrylate containing perfluoroalkyl group, polyether modified (meth)acrylate containing perfluoroalkyl group, acrylonitrile Modified polydimethyl siloxane, polyether modified polydimethyl siloxane, polydimethyl siloxane containing perfluoroalkyl group, and polyether modified poly fluoroalkyl group Methyl decane.

[24] A cured product of a resin composition for forming a hard coat layer according to any one of [1] to [23].

[25] A coated article comprising, for example, [1]~ on the surface of the article [23] A hard coat layer of a cured product of the resin composition for forming a hard coat layer according to any one of [23].

[26] A coating material obtained by applying a resin composition for forming a hard coat layer according to any one of [1] to [23] to a surface of an article and curing the composition.

Since the resin composition for forming a hard coat layer of the present invention has the above-described configuration, by irradiating the active energy ray, it is possible to form a hardened film having high surface hardness and excellent scratch resistance and having low curling property (or low hardening shrinkage). The material 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). Further, 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, and when used for the purpose, imparts high surface hardness and excellent scratch resistance. At the same time, the effect of preventing the crack of the glass substrate can be exerted.

1‧‧‧hardened film

2‧‧‧ horizontal plane

3‧‧‧Shaft volume

Fig. 1 is a schematic view for explaining a method of evaluating curling property in the examples.

[Formation of the Invention]

The resin composition for forming a hard coat layer (hereinafter sometimes referred to as "resin composition") of the present invention contains a polyfunctional alicyclic epoxy compound (A) and a polyfunctional (meth)acrylic compound (B). Furthermore, in this manual The term "(meth)acrylonitrile" means propylene fluorenyl and/or methacryl fluorenyl (either or both of propylene fluorenyl and methacryl fluorenyl), and is derived from (meth) acrylate or the like. Said the same.

[Polyfunctional alicyclic epoxy compound (A)]

The polyfunctional alicyclic epoxy compound (A) is a cationically curable compound having an alicyclic structure and two or more epoxy groups in one molecule. In the resin composition of the present invention, the polyfunctional alicyclic epoxy compound (A) may be used singly or in combination of two or more.

The polyfunctional alicyclic epoxy compound (A) specifically includes (i) an epoxy group (alicyclic epoxy group) having two carbon atoms and an oxygen atom adjacent to each other constituting the alicyclic ring. a compound; (ii) a compound having an epoxy group directly bonded to an alicyclic ring; (iii) a compound having an alicyclic ring and a glycidyl group, and the like.

The compound (i) having an alicyclic epoxy group may, for example, be a compound represented by the following formula (I) (alicyclic epoxy compound).

In the above formula (I), X represents a single bond or a linking group (having a divalent group of one or more atoms). Examples of the above-mentioned linking group include a divalent hydrocarbon group, an alkylene group in which a part or all of a carbon-carbon double bond is epoxidized, a carbonyl group, an ether bond, an ester bond, a carbonate group, a guanamine group, and the like. The basis of a plurality of links, etc. In addition, one or more carbon atoms constituting the cyclohexane ring (epoxycyclohexane group) in the formula (I) may be bonded to a substituent such as an alkyl group.

For the above divalent hydrocarbon group, the carbon number is 1 to 18 A linear or branched chain alkyl group, a divalent alicyclic hydrocarbon group or the like. Examples of the linear or branched chain alkylene group having a carbon number of 1 to 18 include a methylene group, a methylmethylene group, a dimethylmethylene group, an exoethyl group, and a propylene group. Base, trimethylene group, etc. The above-mentioned divalent alicyclic hydrocarbon group may, for example, be a 1,2-cyclopentyl group, a 1,3-cyclopentyl group, a cyclopentylene group, a 1,2-extended cyclohexyl group, or a 1,3-cyclohexyl group. a cycloalkyl group (including a cycloalkylidene) such as a cyclohexylene group, a 1,4-cyclohexylene group or a cyclohexylene group.

In the case of an alkenyl group in the epoxidized alkenyl group (sometimes referred to as "epoxidized alkenyl group") of a part or all of the above carbon-carbon double bond, for example, a vinyl group or a stretch may be mentioned. Propylene, 1-butenyl, 2-butenyl, butadienylene, pentenylene, hexenylene, heptenylene, A linear or branched chain extending alkenyl group having 2 to 8 carbon atoms such as octenylene. In particular, in the case of the above epoxidized alkenyl group, it is preferred that the carbon-carbon double bond is all epoxidized to form an alkenyl group, and more preferably the carbon-carbon double bond is epoxidized to have a carbon number of from 2 to 4 base.

The linking group in the above X is particularly preferably a linking group containing an oxygen atom, and specifically, -CO-, -O-CO-O-, -COO-, -O-, -CONH- And an epoxidized alkenyl group; a group obtained by linking a plurality of the groups; and one or more of the groups having one or two or more of the divalent hydrocarbon groups.

Representative examples of the compound represented by the above formula (I) include (3,4,3',4'-diepoxy)bicyclohexane and bis(3,4-epoxy group). Cyclohexylmethyl)ether, 1,2-epoxy-1,2-bis(3,4-epoxycyclohexane-1-yl)ethane, 2,2-bis(3,4-ring Oxycyclohexane-1-yl)propane, 1,2-bis(3,4-epoxycyclohexane-1-yl)ethane, and the following formula (I-1)~(I-10 ) the compound shown, and the like. In the following formula (I-5), L is an alkylene group having 1 to 8 carbon atoms, and among them, a linear chain having 1 to 3 carbon atoms such as a methylene group, an exoethyl group, a propyl group and an exopropyl group is preferable. A branched or branched chain alkyl group. n ¹ to n ⁸ in the following formulas (I-5), (I-7), (I-9), and (I-10) each represent an integer of 1 to 30.

For the compound having an alicyclic epoxy group, for example, a commercially available product such as "Celloxide 2021P" or "Celloxide 2081" (manufactured by Daicel Co., Ltd.) can be used.

In the above (ii), the compound having an epoxy group which is directly bonded to the alicyclic ring by a single bond, for example, a compound represented by the following formula (II) or the like can be given.

In the formula (II), R' is a group (p-valent organic group) obtained by removing p hydroxyl groups (-OH) from the structural formula of the p-valent alcohol, and p and n each represent a natural number. The p-valent alcohol [R'-(OH) _p ] may, for example, be a polyhydric alcohol such as 2,2-bis(hydroxymethyl)-1-butanol (such as an alcohol having 1 to 15 carbon atoms). p is preferably from 1 to 6, and n is preferably from 1 to 30. When p is 2 or more, n may be the same or different in the base in each square bracket (outer bracket). With respect to the compound represented by the above formula (II), specifically, 1,2-epoxy-4-(2-ring) of 2,2-bis(hydroxymethyl)-1-butanol An oxyethylene group) cyclohexane adduct (for example, trade name "EHPE 3150" (made by Daicel Co., Ltd.), etc.).

In the above (iii) compound having an alicyclic ring and a glycidyl group, for example, a compound obtained by hydrogenating a bisphenol A type epoxy compound (hydrogenated bisphenol A type epoxy compound), bisphenol a compound obtained by hydrogenating a F-type epoxy compound (hydrogenated bisphenol F-type epoxy compound), a hydrogenated biphenol-type epoxy compound, a hydrogenated phenol novolak type epoxy compound, a hydrogenated cresol novolac type epoxy Hydrogenated aromatic glycidyl ether ring such as hydrogenated cresol novolak type epoxy compound of bisphenol A, hydrogenated naphthalene type epoxy compound, hydrogenated epoxy compound of epoxy compound obtained from phenolic methane Oxygen compounds, etc.

The polyfunctional alicyclic epoxy compound (A) is preferably a compound having an alicyclic epoxy group, in that a cured product having low curling property, high surface hardness, and excellent transparency is obtained. Particularly preferred is 3,4-epoxycyclohexylmethyl(3,4-epoxy)cyclohexanecarboxylate [the compound of the above formula (I-1), trade name "Celloxide 2021P" (Daicel) (Stock), etc.], and (3,4,3',4'-dicyclooxy)bicyclohexane.

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

Further, the content (mixing amount) of (A) is 3 to 35% by weight, preferably 10 to 33% by weight, based on the sum of the contents (A) and (B) (100% by weight), particularly preferably It is 13 to 29% by weight, preferably 17 to 25% by weight.

By controlling the content of (A) to the above range, it is possible to obtain an effect of reducing the curling property while maintaining the scratch resistance. When the content of the (A) is outside the above range, the content of the polyfunctional (meth)acrylic compound (B) to be described later is reduced, and the curling property is exhibited, and it is difficult to obtain a cured product having a low crimping property. . Moreover, the scratch resistance tends to be lowered. On the other hand, when the content of the (A) is less than the above range, the content of the polyfunctional (meth)acrylic compound (B) to be described later becomes excessive, and the positive crimping property is exhibited, and the low crimping property is obtained. Hardened materials become difficult.

[Polyfunctional (meth)acrylic compound (B)]

The polyfunctional (meth)acrylic compound (B) in the present invention is a radical curable compound having two or more (meth)acrylonium groups in one molecule. In the resin composition of the present invention, the polyfunctional (meth)acrylic compound (B) may be used alone or in combination of two or more.

The polyfunctional (meth)acrylic compound (B) has two or more propylene fluorenyl groups and/or methacryl fluorenyl groups in the molecule, and is, for example, 2 to 15, more preferably 3 or more. (for example, 3 to 12), and preferably 5 or more (for example, 5 to 10).

The molecular weight of the polyfunctional (meth)acrylic compound (B) is, for example, 300 to 13,000, preferably 400 to 13,000, particularly preferably 500 to 10,000, and most preferably 500 to 3,000. Further, the weight average molecular weight (Mw) of the polyfunctional (meth)acrylic compound (B) is, for example, 400 to 13,000, preferably 500 to 10,000, particularly preferably 500 to 3,000. When the molecular weight is less than 300 and/or the weight average molecular weight is less than 400, the curling property of the cured product is increased. . On the other hand, when the molecular weight and/or the weight average molecular weight is more than 13,000, the surface hardness of the cured product is lowered, and it becomes impossible to achieve the action of top coating (especially hard coating) as a protective film. Further, the weight average molecular weight is a standard polystyrene-equivalent molecular weight measured by a GPC method.

The polyfunctional (meth)acrylic compound (B) may, for example, be an aliphatic (meth) acrylate (linear or branched chain aliphatic (meth) acrylate) or alicyclic Non-aromatic (meth) acrylate such as (meth) acrylate); aromatic (meth) acrylate or the like. In the present invention, from the viewpoint of non-coloring property of the cured product, a non-aromatic (meth) acrylate is preferable, and an aliphatic (meth) acrylate is particularly preferable.

Specifically, examples of the polyfunctional (meth)acrylic compound (B) include 2-hydroxy-3-(meth)acryloxypropyl (meth)acrylate and tricyclic anthracene. Alkanediethanol di(meth)acrylate, glycerol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(a) 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-decanediol Di(meth)acrylate, 9,9-bis[4-(2-(methyl)acryloxyethoxy)phenyl]anthracene, 2,2-bis[4-((meth)propene) Difunctional (meth) acrylate such as decyloxydiethoxy)phenyl]propane, and the like; ethoxylated tris(meth)acrylate, ε-hexyl Lactone modified ginseng (2-(methyl) propylene oxiranyl ethyl) isocyanate, glycerol tri(meth) acrylate , ethoxylated glycerol tri(meth) acrylate, propoxylated glycerol tri (meth) acrylate, neopentyl alcohol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate Tris(meth)acrylate of 3 mol ethylene oxide adduct of ester, trimethylolpropane, tris(meth)acrylate of 3 mol propylene oxide adduct of trimethylolpropane, three Tris(meth)acrylate of a 6 molar ethylene oxide adduct of methylolpropane, tris(meth)acrylate of a 6 molar propylene oxide adduct of trimethylolpropane, di-trishydroxyl Methylpropane tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol poly(meth)acrylic acid An ester (for example, dipentaerythritol hexa(meth) acrylate, a hexa(meth) acrylate of a caprolactone adduct of dipentaerythritol, etc.), and the like, a polyester ( Methyl) acrylate, polyether (meth) acrylate, acryl (meth) acrylate, urethane (meth) acrylate, epoxy (methyl) ) acrylates, polydiene ( Trifunctional or higher such as polyalkadiene (meth)acrylate (for example, polybutadiene (meth) acrylate), melamine (meth) acrylate or polyacetal (meth) acrylate Polyfunctional (meth) acrylate and the like.

For the polyfunctional (meth)acrylic compound (B), for example, a commercially available product such as "DPHA" (manufactured by Daicel-Allnex Co., Ltd.) can be suitably used.

a (meth)acrylonitrile group (for example, a polyfunctional (meth)acrylic compound (B) (meth) contained in the total amount of (A), (B), and (C) contained in the resin composition of the present invention The concentration of the acrylonitrile group is, for example, greater than 5.0 millimoles/g (for example, more than 5.0 millimoles/g, and 10.0 millimoles/gram or less), preferably It is 5.5 millimoles/g or more, more preferably 6.0 millimoles/g or more, particularly preferably 6.5 millimoles/g or more, and most preferably 7.0 millimoles/g or more. Further, the upper limit of the (meth)acrylonitrile 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, preferably 7.5 millimoles/g.

The content of (B) is the total amount of the nonvolatile component (component other than the solvent) contained in the resin composition of the present invention, for example, 40 to 95% by weight, 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, particularly preferably 55% by weight.

Further, the content (mixing amount) of (B) is 65 to 97% by weight, preferably 65 to 94% by weight, and more preferably 65 to 90% by weight (100% by weight) of the sum of (A) and (B). The weight % is 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) to the above range, it is possible to obtain an effect of reducing the curling property while maintaining the scratch resistance. When the content of the (B) is outside the above range, the content of the polyfunctional alicyclic epoxy compound (A) described above is reduced, and the positive crimping property is exhibited, and it is difficult to obtain a cured product having a low crimping property. On the other hand, when the content of the (B) is less than the above range, the content of the polyfunctional alicyclic epoxy compound (A) is excessive, and the curling property is exhibited, and the low-curing hardening is obtained. Things become difficult. Moreover, the scratch resistance tends to be lowered.

[Surface modified inorganic particles (C)]

The surface-modified inorganic particles (C) in the present invention have an epoxy group and/or a (meth) acrylonitrile group having a polyfunctional alicyclic epoxy compound (A) on the surface. a reactive functional group (that is, a functional group reactive with an epoxy group, a functional group reactive with a (meth)acryl fluorenyl group, or reactive with an epoxy group and a (meth) acrylonitrile group Inorganic particles of the functional group). In the present invention, the surface-modified inorganic particles (C) have excellent compatibility with an organic substance because of the reactive functional group. Moreover, it is excellent in dispersibility, and it can prevent that an inorganic particle aggregates mutually. Then, in the present invention, when the surface-modified inorganic particles (C) have a reactive functional group with an epoxy group, they are combined with the aforementioned polyfunctional alicyclic epoxy compound (A); in the present invention, when the surface When the modified inorganic particles (C) have a reactive functional group with a (meth)acryl fluorenyl group, they are combined with the aforementioned polyfunctional (meth)acrylic compound (B); and in the present invention, when the surface is modified with inorganic particles (C) in the case of having a reactive functional group with an epoxy group and a (meth) acrylonitrile group, it is bonded to the aforementioned polyfunctional alicyclic epoxy compound (A) and a polyfunctional (meth)acrylic compound (B) For this reason, the inorganic particles are not damaged from the cured product, and excellent scratch resistance can be imparted to the cured product. Further, it is also possible to prevent an increase in haze and a brittleness in the cured product. The surface-modified inorganic particles (C) may be used alone or in combination of two or more.

The inorganic particles include inorganic particles having transparency such as cerium oxide, titanium oxide, aluminum oxide, and zirconium oxide. In the present invention, it is possible to suppress the coloring of the cured product and to prevent the curable compound (that is, the polyfunctional alicyclic epoxy compound (A) and the polyfunctional (meth)acrylic compound (B)). It is hardened and does not decompose the aforementioned curable compound and its polymer, and is preferably cerium oxide.

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, and particularly preferably 3 to 20 nm. Average grain If the diameter is outside the above range, the transparency tends to be lowered. On the other hand, if the average particle diameter is less than the above range, it tends to be difficult to obtain scratch resistance.

Examples of the reactive functional group with an epoxy group and/or a (meth) acrylonitrile group include a (meth) acrylonitrile group, a glycidyl ether group, an alicyclic epoxy group, and an oxa compound. Cyclobutane, vinyl ether group, thiirane group, vinyl group, hydroxyl group, and the like. In the present invention, in the point that the scratch resistance of the polyfunctional alicyclic epoxy compound (A) can be improved, a group having excellent reactivity with an epoxy group is preferred, and a hydroxyl group or a glycidyl ether is preferred. An alicyclic epoxy group (for example, an epoxycyclohexane group).

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

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

The content (mixing amount) of (C) is, for example, 5 to 40 parts by weight, preferably 5 to 30 parts by weight, more preferably 7 to 25, based on 100 parts by weight of the total content of the above (A) and (B). The parts by weight are particularly preferably 10 to 20 parts by weight, preferably 10 to 15 parts by weight.

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

If (C) is contained in the above range, it is preferable to obtain a cured product having both scratch resistance, high hardness, and low curling property. If the content of (C) is less than the above range, the scratch resistance tends to be lowered. On the other hand, if the content of (C) is outside 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 having an epoxy group with a polyfunctional alicyclic epoxy compound (A) as the surface-modified inorganic particles (C), the resin is prepared. At the time of the composition, a polyfunctional alicyclic epoxy compound (A) and a surface-modified inorganic particle (C) may be separately added and prepared by mixing, but the obtained composition is subjected to the surface modification of the inorganic particles (C) When the content is too large, there is a tendency that haze tends to occur. In addition, 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 number of surface-modified inorganic particles (C) are to be added, the solvent also becomes In the case where the amount of the solvent to be blended is set to be low, the amount by which the surface-modified inorganic particles (C) can be added is considerably limited. Therefore, it is preferred to use a reactive functional group (for example, a hydroxyl group) of the surface-modified inorganic particle (C) and an epoxy group to react with an epoxy group of the polyfunctional alicyclic epoxy compound (A). Or the surface-modified inorganic particles (C) are dispersed in the polyfunctional alicyclic epoxy compound (A) without a solvent, or the surface-modified inorganic particles (C) and the polyfunctional alicyclic ring which have been dispersed in the solvent. The oxygen compound (A) is mixed and the solvent is removed. For the reaction of the polyfunctional alicyclic epoxy compound (A) with the surface-modified inorganic particles (C), for example, the product name "NANOPOX C620" (manufactured by EVONIC Co., Ltd.) or the like can be suitably used. Again, When the surface-modified inorganic particles (C) of the reactive functional group of the epoxy group are dispersed in the polyfunctional alicyclic epoxy compound (A) without a solvent, for example, "Y10C-JFS" can be suitably used. Admatechs (share) system, etc.

[Photocationic polymerization initiator (D)]

The photocationic polymerization initiator is a compound which generates an acid by irradiation of light, and the curing reaction of the cationically curable compound contained in the starting resin composition includes a cationic portion that absorbs light and an anion portion that serves as an acid generating source.

Examples of the photocationic polymerization initiator include a diazonium salt compound, a phosphonium salt compound, a phosphonium salt compound, a phosphonium salt compound, and a selenium salt compound. A salt compound, an ammonium salt compound, a bromine salt compound or the like.

In the present invention, it is preferred to use a phosphonium salt compound in order to form a cured product having excellent curability. Examples of the cation portion of the onium salt compound include (4-hydroxyphenyl)methylbenzylphosphonium ion, triphenylsulfonium ion, and diphenyl[4-(phenylthio)phenyl]. An arsonium ion such as a cerium ion, a 4-(4-biphenylthio)phenyl-4-biphenylphenyl sulfonium ion or a tri-p-tolylhydrazine ion (especially a triarylphosphonium ion).

The anion portion of the photocationic polymerization initiator may, for example, be [(Y) _s B(Phf) _4-s ] ^- (wherein Y represents a phenyl group or a biphenyl group. Phf represents a hydrogen atom) At least one phenyl group substituted with at least one selected from the group consisting of 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 represents an alkyl group in which 80% or more of a hydrogen atom is substituted by a fluorine atom. _t represents an integer of 0 to 5), AsF ₆ ^- , SbF ₆ ^- , SbF ₅ OH ^- etc. .

As the photocationic polymerization initiator in the present invention, for example, (4-hydroxyphenyl)methylbenzyl ruthenium (pentafluorophenyl) borate, 4-(4-biphenyl) can be used. Thio)phenyl-4-biphenylphenylphosphonium (pentafluorophenyl)borate, 4-(phenylthio)phenyldiphenylsulfonylphenyl (pentafluorophenyl)borate, [ 4-(4-biphenylthio)phenyl]-4-biphenylphenyl phenyl phenyl(pentafluorophenyl)borate, diphenyl[4-(phenylthio)phenyl]anthracene Refractory (pentafluoroethyl)trifluorophosphate, diphenyl[4-(phenylthio)phenyl]indole (pentafluorophenyl)borate, diphenyl[4-(phenylthio)phenyl鋶 hexafluorophosphate, 4-(4-biphenylthio)phenyl-4-biphenylphenyl hydrazine (pentafluoroethyl)trifluorophosphate, bis[4-(diphenylhydrazine) Phenyl]sulfide phenyl cis (pentafluorophenyl) borate, [4-(2-thioxanthylthio)phenyl]phenyl-2-thioxanthenyl phenyl phenyl Fluorophenyl)borate, 4-(phenylthio)phenyldiphenylphosphonium hexafluoroantimonate; trade name "CYRACURE UVI-6970", "CYRACURE UVI-6974", "CYRACURE UVI-6990", " CYRACURE UVI-950" (above, made by Union Carbide, USA); "Irgac Ure250", "Irgacure261", "Irgacure264" (above, BASF); "CG-24-61"(Ciba-Geigy);"OptomerSP-150","OptomerSP-151","OptomerSP"-170","OptomerSP-171" (above, ADEKA (share) system); "DAICAT II" (Daicel (share) system); "UVAC1590", "UVAC1591" (above, Daicel-Cytech (share) system) "CI-2064", "CI-2639", "CI-2624", "CI-2481", "CI-2734", "CI-2855", "CI-2823", "CI-2758", "CIT-1682" (above, Japan's Soda (share) system); "PI-2074" (Rhodia company, bismuth (pentafluorophenyl) borate "Mefyl cumene sulfonium salt";"FFC509" (manufactured by 3M Company); "BBI-102", "BBI-101", "BBI-103", "MPI-103", "TPS-103", "MDS-103", "DTS-103", "NAT-103", "NDS-103" (above, Midori Chemical (share) system); "CD-1010", "CD-1011", "CD-1012" (The above, the United States, Sartomer company); "CPI-100P", "CPI-101A" (above, San-Apro (share) system) and other commercial products. These may 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, relative to 100 parts by weight of the cationically curable compound (particularly, the polyfunctional alicyclic epoxy compound (A)) contained in the resin composition, For example, it is 1 to 10 parts by weight, preferably 1 to 5 parts by weight, particularly preferably 2 to 4 parts by weight. When the content of the photocationic polymerization initiator (D) is less than the above range, there is a problem of causing hardening failure. On the other hand, when the content of the photocationic polymerization initiator (D) is outside the above range, the cured product tends to be easily colored.

[Photoradical polymerization initiator (E)]

The photoradical polymerization initiator is a compound which generates a radical by irradiation of light, and a compound which hardens the radical curable compound contained in the starting resin composition, for example, benzophenone or acetophenone Acetophenone benzyl, benzyl dimethyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, dimethoxy acetophenone, dimethoxy phenyl Acetophenone, diethoxyacetophenone, diphenyldisulfite, methyl ortho-benzoyl benzoate, ethyl 4-dimethylaminobenzoate (manufactured by Nippon Kayaku Co., Ltd.) Product name "Kayacure EPA", etc., 2,4-diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd., trade name "Kayacure DETX", etc.), 2-methyl-1 -[4-(methyl)phenyl]-2- Lolinylacetone-1 (manufactured by Ciba-Geigy Co., Ltd., trade name "Irgacure 907"), 1-hydroxycyclohexyl phenyl ketone (manufactured by Ciba-Geigy Co., Ltd., trade name "Irgacure 184", etc.), 2-two Methylamino-2-(4- 2-Amino-2-benzylidene-1-phenylalkane compound such as phenyl)benzimidyl-1-phenylpropane, tetrakis(tert-butylperoxycarbonyl)benzophenone, benzyl , 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 4,4'-bis(diethylamino)benzophenone, and the like, 2,2'- Imidazole such as bis(2-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole (manufactured by Hodogaya Chemical Co., Ltd., trade name "B-CIM") Compound, 2,6-bis(trichloromethyl)-4-(4-methoxynaphthalen-1-yl)-1,3,5-three Isohalogen methylation Compound, 2-trichloromethyl-5-(2-benzofuran-2-yl-vinyl)-1,3,4- Halogen methyl group Diazole compounds and the like. These may be used alone or in combination of two or more.

The content of the photoradical polymerization initiator (E) in the resin composition of the present invention with respect to 100 parts by weight of the radical curable compound (particularly, the polyfunctional (meth)acrylic compound (B)) contained in the resin composition For example, it is 1 to 10 parts by weight, preferably 1 to 5 parts by weight, particularly preferably 1.5 to 3.5 parts by weight. When the content of the photoradical polymerization initiator (E) is less than the above range, there is a problem of causing hardening failure. On the other hand, when the content of the photoradical polymerization initiator (E) is outside the above range, the cured product tends to be easily colored.

[Other hardening compounds]

The resin composition of the present invention may further contain a curable compound other than the polyfunctional alicyclic epoxy compound (A) and the polyfunctional (meth)acrylic compound (B) (may be referred to as "another curable compound"). Other hard Examples of the compound include an aromatic glycidyl ether type epoxy compound, an aliphatic polyol polyglycidyl ether, and an oxetane compound (a compound having one or more oxetanyl groups). A vinyl ether compound (a compound having one or more vinyl ether groups) or the like.

The ratio of the total content of the polyfunctional alicyclic epoxy compound (A) to 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. Further, 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 less than the above range, it is required to have both low curling property, high surface hardness, and excellent scratch resistance. Hardened materials tend to become difficult.

[additive]

The resin composition of the present invention may contain various additives in addition to the above, within a range that does not impair the effects of the present invention. In the present invention, it is preferred to contain one or two or more compounds which impart lubricity at the point of obtaining a cured product which is more excellent in scratch resistance.

Examples of the compound imparting lubricity include a decane compound, a (meth)acrylic compound containing a perfluoroalkyl group, a (meth)acrylic compound containing a mercapto group, and a polyether modified (methyl). Acrylic compound, cerium modified poly(meth) acrylate, polyether modified poly(meth) acrylate, poly(meth) acrylate containing perfluoroalkyl group, polyether modified with perfluoroalkyl group (meth) acrylate, propylene fluorenyl modified poly Methyl decane, polyether modified polydimethyl siloxane, polydimethyl siloxane containing perfluoroalkyl group, polyether modified polydimethyl siloxane containing perfluoroalkyl group, etc. . The compound preferably has a reactive functional group with an epoxy group and/or a (meth) acrylonitrile group (may be the same as the example of the surface-modified inorganic particle (C)).

The decane compound may, for example, be triethyl decane or tertiary dimethyl dimethyl decane.

The (meth)acrylic acid compound containing a perfluoroalkyl group may, for example, be 2,2,2-trifluoroethyl (meth) acrylate or 2, 2, 3, 3, 3 - 5 Fluoropropyl (meth) acrylate, 2-(perfluorobutyl)ethyl (meth) acrylate, 2-(perfluorooctyl)ethyl (meth) acrylate, and the like.

Examples of the thiol group-containing (meth)acrylic compound include trimethylsulfonyl (meth) acrylate, triisopropyl decyl (meth) acrylate, and tri(n-butyl). Mercapto (meth) acrylate, triisobutyl decyl (meth) acrylate, tricyclohexyl decyl (meth) acrylate, triphenyl decyl (meth) acrylate, and the like.

The oxime-modified poly(meth) acrylate is bonded to an end chain of a poly(meth) acrylate of a main chain and/or a side chain to which an oxime chain (for example, a polydimethyl siloxane chain) is bonded. Compound.

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

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

The polyfluoroalkyl-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 of the main chain.

The acrylonitrile-modified polydimethyl siloxane is a compound in which a poly(meth) propylene fluorenyl chain is bonded to a terminal and/or a side chain of a polydimethyl siloxane of a main chain.

The polyether modified polydimethyl methoxy oxane, the polyfluoroalkyl siloxane containing a perfluoroalkyl group, and the polyether modified polydimethyl siloxane containing a perfluoroalkyl group, except for poly(A) The base acrylate is changed to a polydimethyl siloxane other than the above.

The perfluoroalkyl group may, for example, be a perfluoroalkyl group having 3 to 30 carbon atoms such as a perfluorooctyl group.

In the present invention, it is particularly preferred to use a compound having a hydroxyl group which is particularly excellent in reactivity with an epoxy group of the polyfunctional alicyclic epoxy compound (A) (for example, a hydrazine-modified poly(meth)acrylic acid having a hydroxyl group. The ester or the like) preferably has a hydroxyl value of, for example, 5 to 150 mgKOH/g.

The amount of the compound to which lubricity is added (the total amount when two or more kinds are contained) with respect to the total (100 parts by weight) of (A), (B), and (C) contained in the resin composition of the present invention For example, it is 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 the resin composition of the present invention, a solvent (for example, butyl acetate, methyl ethyl ketone, etc.), a polyol, a hardening aid, an organic siloxane compound, metal oxide particles, rubber particles, and an antifoaming agent may be further used. , decane coupling agent, filler, plasticizer, leveling agent, antistatic agent, release agent, surfactant, flame retardant, colorant, antioxidant Conventional additives such as ultraviolet absorbers, ion adsorbents, and phosphors. The content of the additives may be suitably set in the range of 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/mixing the above components in a heated state as needed. In addition, the resin composition of the present invention can be used as a one-liquid composition which is used as it is if the components are mixed in advance, or can be divided into two or more components (each component can also be used) A mixture of two or more components) is a composition of a multi-liquid system (for example, a two-liquid system) which is used in a predetermined ratio before use. The method of stirring/mixing is not particularly limited. For example, various known mixers such as a dissolver, a homogenizer, a kneader, a roll, a bead mill, a self-propagating stirring device, or the like may be used. Mixed means. Further, after stirring/mixing, defoaming can also be carried out under vacuum.

<Hard coating composition>

The resin composition of the present invention can be cured to obtain a cured product having low curling property and excellent surface hardness and scratch resistance. Therefore, the resin composition of the present invention can be preferably used as a composition for hard coating (hard coating agent).

<paint>

The resin composition of the present invention is applied to the surface of an object (such as a substrate or a film made of a metal or a resin (for example, a plastic such as TAC or PET), which is an object (the object to be coated), and is hardened. This gives a coating. The resin composition of the present invention is excellent in hardenability (hardening speed), and Since the brightening property is low in curling property and excellent in surface hardness and scratch resistance, both of the coating product productivity and quality are excellent.

The resin composition of the present invention can be hardened in a very short time by application of an active energy ray such as ultraviolet rays or an electron beam after being applied to an article. For the light source for ultraviolet irradiation, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, or the like can be used. The irradiation time varies depending on the type of the light source, the distance between the light source and the coated surface, and other conditions, but the longest factor is also a factor of ten seconds, usually a factor of two. Generally, an illumination source of about 80 to 300 W/cm can be used for the lamp. For electron beam irradiation, it is preferable to use an electron beam having an energy in the range of 50 to 1000 KeV and to make an irradiation amount of 2 to 5 Mrad. After the active energy ray is irradiated, heating (post-cure) may be performed as needed to promote the hardening.

The resin composition of the present invention can be used for a coating agent (especially for hard coating applications), an ink, an adhesive, a sealant, an encapsulant, a resist, a composite material, a transparent substrate, a transparent film or sheet, an optical material. (for example, optical lenses, etc.), light-forming materials, electronic materials (for example, electronic paper, touch panel, solar cell substrate, optical waveguide, light guide plate, holographic memory, etc.), mechanical component materials, electrical component materials, automobiles Various uses such as component materials, civil construction materials, molding materials, plastic forming materials, solvents (for example, reactive diluents, etc.).

[Examples]

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

Example 1

[Modulation of Resin Composition]

The components were mixed in the blending ratio (unit: parts by weight) shown in the table, and the resin composition was obtained by stirring and defoaming using a self-revolving stirring apparatus (trade name "THINKY MIXERAR-250", Thinky). Things.

[Production of hardened film]

The obtained resin composition was applied onto a PET substrate (trade name "Lumilar T60", manufactured by Toray Industries, Inc.; film thickness: 100 ± 5 μm) using a bar coater. At this time, the coating was performed using a bar coater so that the film thickness after drying became 20 μm.

Thereafter, it was dried at 80 ° C for 1 minute, and then irradiated with ultraviolet rays under the conditions of an irradiation amount of about 1000 mJ/cm ² in a state in which a nitrogen-substituted closed container was placed, and hardened.

The laminate (cured film) having the structure of "PET substrate/cured material (cured coating film)" thus obtained was used as a sample for pencil hardness evaluation and scratch resistance evaluation.

In addition, a test piece having a square of 10 cm on one side was cut out from the laminate (cured film) having the structure of "PET substrate/cured material (cured coating film)" obtained as described above. With respect to the above test piece, the film thickness of the measurement point indicated by the numbers 1 to 5 circled in Fig. 1 (1a) was measured. At all of these measurement points, when the film thickness of the PET substrate (the film thickness measured in advance) was subtracted from the film thickness of the measurement spot, the thickness of the cured coating film was 20 μm ± 2 μm, respectively, and it was used as a curl. Sample for evaluation. In the case of failure, the bar coater was changed, and the coating/drying/hardening step was repeated until the film thickness of the measurement point was passed, and a sample for evaluation of curling property was produced.

Examples 2 to 10 and Comparative Examples 1 to 8

The resin composition and the cured product (sample) were obtained in the same manner as in Example 1 except that the blending amount of each component was changed as shown in the table. Further, in Examples and Comparative Examples other than Example 1 and Comparative Example 2, post-curing (heating at 80 ° C for 2 hours) was carried out after ultraviolet irradiation.

<evaluation>

The following evaluation tests were carried out on the cured product (sample) of the resin compositions obtained in the examples and the comparative examples.

[pencil hardness]

The pencil hardness of the cured film (thickness of the cured coating film: about 20 μm) obtained in the examples and the comparative examples was measured by the following method.

The evaluation of the pencil hardness of the cured coating film was carried out in accordance with JIS K5600. The evaluation was carried out by visual observation, and the hardened coating film on the PET substrate was scraped with a pencil, and the flaw on the surface or the substrate was confirmed to be NG (poor). Specifically, it is repeated: first, it is evaluated by a pencil of a certain hardness, and when there is no flaw, the pencil of the above-mentioned one-layer hardness is evaluated, and if the flaw is confirmed, the hardness of the next layer is re-evaluated. . In addition, if a scratch is not confirmed, a pencil having a higher hardness is used. When the reproducibility of two or more times is confirmed, the pencil hardness of the hardened coating film is set to the pencil hardness of the hardened coating film. It is expressed by the hardness of the core of the pencil. The evaluation conditions are as follows.

Evaluation pencil: Mitsubishi pencil (stock) "pencil hardness test pencil"

Load: 750gf

Scratch distance: 50mm or more

Scratch angle: 45°

Measurement environment: 23 ° C, 50% RH

In addition, the sample (hardened film) used for the test was obtained by using a constant temperature and humidity machine of 23° C. and 50% RH for 24 hours.

[curlability]

With respect to the samples for evaluation of the curling property obtained in the examples and the comparative examples, as shown in Fig. 1 (1b), the warpage at the four corners when placed in the horizontal plane was measured, and the average value was made into the amount of warpage of the cured film. . A person with a large amount of warpage is considered to have a hardening shrinkage or a hardening expansion. In addition, when the hardening shrinkage occurs (when the surface of the cured film which is in contact with the horizontal plane of FIG. 1 (1b) and the hardened coating film are opposite sides), the warpage is positive, and hardening expansion occurs (hardened film) The warp of the surface in contact with the horizontal plane of Fig. 1 (1b) is a negative value and is shown in the table.

[scratch resistance]

With respect to the cured film obtained by the examples and the comparative examples (film thickness: about 20 μm), the coated surface was wound 20 times, 200 times, and back and forth with a load of 500 g/cm ² or 1 kg/cm ² using steel wool of #0000. The scratch was performed 1000 times, and the scratch resistance was evaluated. Furthermore, the evaluation of the scratch resistance is as follows.

A: 1000 rounds without scratches

B: 200 rounds without scratches, and 1000 rounds with tiny scars

C: 200 rounds without scratches, and 1000 rounds with mild scars or mild turbidity

D: 200 rounds without scratches, and 1000 rounds with clear scars or clear turbidity

E: 20 rounds without scratches, and 200 rounds with tiny scars

F: 20 rounds without scars, and 200 rounds with mild scars or mild turbidity

G: 20 rounds without scratches, and 200 rounds with clear scars or clear turbidity

H: 20 rounds with tiny scars

I: 20 rounds with mild scars or mild turbidity

Further, the abbreviations in Tables 1 and 2 indicate the following compounds.

NANOPOX C620: a compound obtained by reacting a hydroxyl group-containing cerium oxide (an average particle diameter of cerium oxide: 10 nm) (40 parts by weight) against Celloxide 2021P (60 parts by weight), trade name "NANOPOX C620", manufactured by EVONIC Co., Ltd.

Y10C-JFS: a mixture of Celloxide 2021P (80.5 parts by weight) and an alicyclic epoxy group containing cerium oxide (an average particle diameter of cerium oxide: 10 nm) (19.5 parts by weight), trade name "Y10C-JFS", Admatechs (shares) system

Celloxide 2021P: 3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexanecarboxylate, trade name "Celloxide 2021P", manufactured by Daicel Co., Ltd.

A-9550: dipentaerythritol polyacrylate, molecular weight: about 554, hydroxyl value: about 56 mg KOH / g, Xinzhongcun Chemical Co., Ltd.

A-TMM-3L-N: neopentyl alcohol triacrylate, molecular weight: 246, hydroxyl value: about 112 mg KOH / g, Xinzhongcun Chemical Co., Ltd.

DPHA: dipentaerythritol hexaacrylate, molecular weight: 578, trade name "DPHA", made by Daicel-Allnex

Y10C-MFK: a methyl ethyl ketone dispersion containing a glycidyl ether group (an average particle diameter of cerium oxide: 10 nm) (concentration of cerium oxide: 30% by weight), trade name "Y10C-MFK", manufactured by Admatechs Co., Ltd.

CPI-210S: diphenyl[4-(phenylthio)phenyl]indole (pentafluoroethyl)trifluorophosphate, trade name "CPI-210S", manufactured by San-Apro

Irgacure 184: 1-hydroxycyclohexyl phenyl ketone

BYK-SILCLEAN 3700: Hydrazine-modified polyacrylic acid containing hydroxyl groups Ester, hydroxyl value: about 30mgKOH / g, the trade name "BYK-SILCLEAN 3700", BYK Chemie Japan (share) system

[Industrial availability]

The resin composition for forming a hard coat layer of the present invention can form a cured product having high surface hardness and excellent scratch resistance and low curling property by irradiation with an active energy ray, and can be suitably used for a plastic film and The use of a surface of a glass substrate to form a hard coat layer.

Claims (7)

A resin composition for forming a hard coat layer, which comprises a polyfunctional alicyclic epoxy compound (A) having an alicyclic structure and two or more epoxy groups in one molecule, and having two or more in one molecule (A) a polyfunctional (meth)acrylic compound (B) having an acrylonitrile group and an inorganic particle having an average particle diameter (based on dynamic light scattering method) of 0.1 to 100 nm having an epoxy group and/or (meth) propylene a surface-modified inorganic particle (C) having a reactive functional group of a mercapto group, a photocationic polymerization initiator (D), and a photoradical polymerization initiator (E), and the content of the above (A) is (A) and (B) 3 to 35% by weight of the sum of the contents (100% by weight). The resin composition for forming a hard coat layer of claim 1, wherein the content of the above (C) is 5 to 40 parts by weight based on 100 parts by weight of the total of the above (A) and (B). The resin composition for forming a hard coat layer according to claim 1 or 2, wherein (meth)acrylic acid is contained in the total amount of (A), (B), and (C) contained in the resin composition for forming a hard coat layer. The concentration of the base is greater than 5.0 millimoles per gram. 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 cerium oxide. The resin composition for forming a hard coat layer according to any one of claims 1 to 4, which further contains a compound selected from the following compounds having a reactive functional group with an epoxy group and/or a (meth) acrylonitrile group; At least one compound: a ruthenium compound, a (meth)acrylic compound containing a perfluoroalkyl group, a (meth)acrylic compound containing a mercapto group, a polyether modified (meth)acrylic compound, and a ruthenium modified poly(A) Acrylate, polyether modified poly(meth)acrylate, poly(meth)acrylate containing perfluoroalkyl group, containing perfluoro Alkyl polyether modified (meth) acrylate, propylene fluorenyl modified polydimethyl siloxane, polyether modified polydimethyl siloxane, polydimethyl fluorene containing perfluoroalkyl The oxane and the polyether modify the polydimethyl siloxane containing a perfluoroalkyl group. A cured product of a resin composition for forming a hard coat layer according to any one of claims 1 to 5. A coating material comprising a hard coat layer containing a cured product of a resin composition for forming a hard coat layer according to any one of claims 1 to 5, on the surface of the article.