TWI616496B - Resin composition for hard coat layer formation and cured product thereof - Google Patents

Abstract

The present invention provides a resin composition for forming a hard coat layer, which is provided with a hardened product having higher surface hardness and abrasion resistance while suppressing the appearance of curling.

The resin composition for forming a hard coat layer according to the present invention comprises a polyfunctional alicyclic epoxy compound (A), a polyfunctional (meth) acrylic compound (B), surface-modified inorganic particles (C), and photocationic polymerization. The initiator (D) and the photoradical polymerization initiator (E), and the content of the aforementioned (A) is 3 to 35% by weight based on the sum (100% by weight) of the contents of (A) and (B).

Description

Resin composition for hard coat layer formation and cured product thereof

The present invention relates to a resin composition for forming a hard coat layer and a cured product thereof. Moreover, this invention relates to the coating object obtained using the said resin composition for hard-coat layer formation. This application claims the benefit of filing on April 21, 2015 in Japan, Japanese Patent Application No. 2015-086412, and incorporates the contents thereof.

By attaching a protective film to a liquid crystal monitor such as a liquid crystal display, an organic EL display, or a plasma display, the following effects can be obtained: preventing the screen from being damaged, making it difficult to attach the fingerprint to the screen, or making it attached The dirt on the screen is easy to wipe off. A hard coat layer is formed on the surface of the protective film to impart scratch resistance. Then, in recent years, there are many requirements for improving the surface hardness of the liquid crystal protective film, and there is a demand for improving the performance of the hard coating.

As a means for increasing the surface hardness of a hard coating layer, it is widely used to multifunctionalize the hardening group of a hardening compound forming a hard coating layer. However, it is known that a polyfunctional hardening compound causes an increase in resin density before and after hardening, that is, hardening shrinkage. Then, the more the functionalization, the more significant the curing shrinkage becomes, and the curling property of the protective film becomes a problem.

Further, as a method for improving the scratch resistance of a hard coat layer, a method of blending inorganic particles such as alumina, silica, and titanium oxide with a hardening compound is known as a method called an organic-inorganic hybrid (Patent Document) 1).

However, when inorganic particles are dispersed in a resin to prepare a coating film, there are phenomena that inorganic particles are missing from a cured coating film (hardened coating film), or an increase in haze and brittleness are seen. This is considered to be due to poor compatibility between organic and inorganic substances. Then, as a method for improving the compatibility between organic and inorganic substances, a method using a nano filler in which the particle diameter of the inorganic particles has been reduced to a nano size is known (Patent Document 2). However, when nano-sized inorganic particles are used, the dispersion stability is lowered, and the inorganic particles are easily aggregated, making it difficult to maintain the transparency of the cured coating film. In addition, a method of using a surface-modified inorganic filler for surface-modifying an inorganic particle shell with an organic substance is also known (Patent Document 3). However, when inorganic particles that are surface-modified with organic substances are used, it may be difficult to increase the surface hardness of the hardened coating film, and the surface hardness may be reduced.

[Prior technical literature] [Patent Literature]

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

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

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

Therefore, an object of the present invention is to provide a resin composition for forming a hard coat layer, which is provided with a hardened product having a higher surface hardness and abrasion resistance while suppressing the appearance of curlability.

The term "curlability" refers to a characteristic that causes curling of the substrate when a cured film (cured coating film) is formed on the substrate. The term "low crimpability" means that it is difficult to similarly A characteristic that causes curl on a substrate.

As a result of intensive studies in order to solve the above-mentioned problems, the present inventors have found that the functional group contains a polyfunctional alicyclic epoxy compound, a polyfunctional (meth) acrylic compound, and inorganic particles having a functional group in a specific ratio. A resin composition having reactivity to the epoxy group of the aforementioned multifunctional alicyclic epoxy compound and / or the (meth) acryl group of the polyfunctional (meth) acrylic compound, if the active energy ray is irradiated, that is, It is possible to obtain a hardened product having low surface curlability (or low hardening shrinkage) while suppressing the appearance of curlability, and having higher surface hardness and abrasion resistance. The present invention has been completed based on these knowledge and insights.

That is, the present invention provides 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; The surface of the inorganic particles having two or more (meth) acrylfluorene-based polyfunctional (meth) acrylic compounds (B) and an average particle diameter (according to a dynamic light scattering method) of 0.1 to 100 nm has an epoxy group and / or The surface-modified inorganic particles (C), the photocationic polymerization initiator (D), and the photoradical polymerization initiator (E) of the reactive functional group of the (meth) acrylfluorenyl group, and the content of the aforementioned (A) Is the content of (A) and (B) And (100% by weight) 3 to 35% by weight.

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

The present invention also provides the resin composition for forming a hard coat layer, wherein (meth) acrylfluorenyl group is included 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.

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 also provides the resin composition for forming a hard coat layer, further comprising at least one selected from the following compounds having a reactive functional group with an epoxy group and / or a (meth) acrylfluorenyl group. Compounds: silicon compounds, (meth) acrylic compounds containing perfluoroalkyl groups, (meth) acrylic compounds containing silicon groups, polyether-modified (meth) acrylic compounds, silicon-modified poly (meth) acrylates , Polyether modified poly (meth) acrylate, poly (meth) acrylate containing perfluoroalkyl group, polyether modified (meth) acrylate containing perfluoroalkyl group, acryl Dimethylsiloxanes, polyether-modified polydimethylsiloxanes, polydimethylsiloxanes containing perfluoroalkyl groups, and polyether-modified polydimethylsiloxanes containing perfluoroalkyl groups alkyl.

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 having a hard coat including a cured product of the resin composition for forming a hard coat layer on an article surface. Floor.

That is, this 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-mentioned (meth) acrylfluorene-containing polyfunctional (meth) acrylic compound (B) and inorganic particles having an average particle diameter (according to a dynamic light scattering method) of 0.1 to 100 nm have an epoxy group and / or Group) a surface-modified inorganic particle (C), a photocationic polymerization initiator (D), and a photoradical polymerization initiator (E) of a reactive functional group of an acrylfluorene group, and the content of the aforementioned (A) is ( 3 to 35% by weight of the sum (100% by weight) of the contents of A) and (B).

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

[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, and 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 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) cyclohexanecarboxylic acid ester and / Or (3,4,3 ', 4'-diepoxy) bicyclohexane.

[5] The resin composition for forming a hard coat layer according to any one of [1] to [4], wherein (B) has three or more (for example, three to twelve, preferably five or more, particularly It is preferably 5 to 10) (meth) acrylfluorenyl compounds.

[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 13,000.

[7] The resin composition for forming a hard coat layer according to any one of [1] to [6], wherein the weight average molecular weight (in terms of GPC standard polystyrene conversion) of (B) is 400 to 13,000.

[8] The resin composition for forming a hard coat layer according to any one of [1] to [7], wherein (B) is dineopentaerythritol 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 silicon oxide, titanium oxide, aluminum oxide, 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 silicon oxide.

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

[12] The resin composition for forming a hard coat layer according to any one of [1] to [11], wherein the resin composition has a reactivity with an epoxy group and / or a (meth) acrylfluorenyl group in (C) The functional group is a group selected from 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] to [12], further comprising a reactive function selected from a group having an epoxy group and / or a (meth) acrylfluorenyl group. At least one of the following compounds: silicon compounds, (meth) acrylic compounds containing perfluoroalkyl groups, (meth) acrylic compounds containing silicon groups, polyether-modified (meth) acrylic acids Compounds, silicon-modified poly (meth) acrylates, polyether-modified poly (meth) acrylates, poly (meth) acrylates containing perfluoroalkyl groups, polyether-modified polyethers containing perfluoroalkyl groups ( (Meth) acrylates, acryl-modified polydimethylsiloxanes, polyether-modified polydimethylsiloxanes, polydimethylsiloxanes containing perfluoroalkyl groups, and polyether modifications Polydimethylsiloxane containing perfluoroalkyl groups.

[14] The resin composition for forming a hard coat layer according to any one of [1] to [12], further comprising a silicon-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 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 nonvolatile component contained in the resin composition %.

[17] 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) acrylfluorenyl in the total was greater than 5.0 millimoles / g.

[18] The resin composition for forming a hard coat layer according to any one of [1] to [17], wherein the content of (C) is 1 to 30 weight of the total amount of nonvolatile components contained in the resin composition %.

[19] The resin composition for forming a hard coat layer according to any one of [1] to [18], wherein the content of (C) is 5 based on 100 parts by weight of the total content of (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 content of (A) and (C) is 5 to 60% by weight of the total (100% by weight) of (A), (B), and (C).

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

[22] The resin composition for forming a hard coat layer according to any one of [1] to [21], wherein the resin composition (particularly a multifunctional (meth) acrylic acid) is contained in the resin composition relative to the radical-curable compound contained in 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], which is selected from the total of (A), (B), and (C) (100 parts by weight) The content of at least one of the following compounds [especially a silicon-modified poly (meth) acrylate containing a hydroxyl group] among the following compounds having a reactive functional group with an epoxy group and / or a (meth) acrylfluorenyl group is: 0.01 ~ 10 parts by weight: silicon compound, (meth) acrylic compound containing perfluoroalkyl group, (meth) acrylic compound containing silicon group, polyether-modified (meth) acrylic compound, silicon-modified poly (methyl) Base) acrylate, polyether modified poly (meth) acrylate, poly (meth) acrylate containing perfluoroalkyl group, polyether modified (meth) acrylate containing perfluoroalkyl group, acrylic resin Modified polydimethylsiloxane, polyether modified polydimethylsiloxane, polydimethylsiloxane containing perfluoroalkyl group, and polyether modified polyether containing polyfluoroalkyl group Methylsiloxane.

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

[25] A coating, which is provided on the surface of the article with a content such as [1] ~ [23] A hard coat layer of a cured product of a resin composition for forming a hard coat layer according to any one of the above.

[26] A coated article obtained by applying and hardening a resin composition for forming a hard coat layer according to any one of [1] to [23] on an article surface.

The resin composition for forming a hard coat layer of the present invention has the above-mentioned structure. By irradiating active energy rays, hardening having high surface hardness, excellent abrasion resistance, and low curlability (or low hardening shrinkage) can be formed. It 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) and PET (polyethylene terephthalate). In addition, the resin composition for forming a hard coat layer of the present invention can also be preferably used as a resin composition for forming a hard coat layer of a glass substrate. When used in this application, it imparts high surface hardness and excellent scratch resistance. In addition to the effect of properties, the effect of preventing the glass substrate from cracking can also be exerted.

1‧‧‧hardened film

2‧‧‧ horizontal

3‧‧‧Warpage

FIG. 1 is a schematic diagram for explaining a method for evaluating curlability in Examples.

[Form of Implementing Invention]

The resin composition (hereinafter sometimes referred to as a "resin composition") for forming a hard coat layer of the present invention contains a polyfunctional alicyclic epoxy compound (A) and a polyfunctional (meth) acrylic compound (B). Moreover, in this specification The term "(meth) acrylfluorenyl" means acrylfluorenyl and / or methacrylfluorenyl (either one or both of acrylfluorenyl and methacrylfluorenyl), in terms of (meth) acrylate etc. The same is true.

[Multifunctional alicyclic epoxy compound (A)]

The polyfunctional alicyclic epoxy compound (A) is a cation-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 alone, or two or more kinds may be used in combination.

As for the polyfunctional alicyclic epoxy compound (A), specifically, (i) it has an epoxy group (alicyclic epoxy group) composed of two adjacent carbon atoms and an oxygen atom constituting an alicyclic ring Compounds; (ii) compounds having an epoxy group directly bonded to an alicyclic ring by a single bond; (iii) compounds having an alicyclic ring and a glycidyl group; and the like.

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

In the formula (I), X represents a single bond or a linking group (a divalent group having one or more atoms). As the above-mentioned linking group, for example, a divalent hydrocarbon group, an alkenyl 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, an amido group, and And so on. Furthermore, a substituent such as an alkyl group may be bonded to one or more carbon atoms constituting a cyclohexane ring (epoxycyclohexane group) in the formula (I).

As far as the above divalent hydrocarbon group is concerned, the number of carbons is 1 to 18 Such as linear or branched chain alkylene, divalent alicyclic hydrocarbon group, and the like. As for the linear or branched alkylene group having 1 to 18 carbon atoms, for example, methylene, methylmethylene, dimethylmethylene, ethylidene, and propylene And trimethylene. For the divalent alicyclic hydrocarbon group, for example, 1,2-cyclopentyl, 1,3-cyclopentyl, cyclopentylene, 1,2-cyclohexyl, 1,3 -Cyclohexyl (including cycloalkylidene) and the like, such as cyclohexyl, 1,4-cyclohexyl, and cyclohexylene.

As for the alkenyl group in which some or all of the carbon-carbon double bonds are epoxidized (sometimes referred to as "epoxidized alkenyl group"), for example, vinylene, Propenyl, 1-butenyl, 2-butenyl, butadienylene, pentenylene, hexenylene, heptenylene, Octenylene (octenylene) and other straight-chain or branched chain carbon number of 2 to 8 carbon. In particular, as for the epoxidized alkenyl group, an alkenyl group having all carbon-carbon double bonds epoxidized is preferred, and an alkenyl group having 2 to 4 carbon atoms in which all carbon-carbon double bonds are epoxidized is more preferable. base.

As for the linking group in X, a linking group containing an oxygen atom is particularly preferred. Specifically, -CO-, -O-CO-O-, -COO-, -O-, -CONH- 2, epoxidized alkenyl groups; these groups are obtained by connecting a plurality of groups; one or more of these groups are obtained by connecting one or more of the above divalent hydrocarbon groups.

As representative examples of the compound represented by the formula (I), (3,4,3 ', 4'-diepoxy) bicyclohexane, bis (3,4-epoxy) Cyclohexylmethyl) ether, 1,2-epoxy-1,2-bis (3,4-epoxycyclohexane-1-yl) ethane, 2,2-bis (3,4-cyclo Oxycyclohexane-1-yl) propane, 1,2-bis (3,4-epoxycyclohexane-1-yl) ethane, and the following formulae (I-1) to (I-10 ) And the like. In the following formula (I-5), L is an alkylene group having 1 to 8 carbon atoms, and among them, a straight chain having 1 to 3 carbon atoms such as methylene, ethylene, propyl, and isopropyl is preferred. Shaped or branched chain alkylene. N ¹ to n ⁸ in the following formulae (I-5), (I-7), (I-9), and (I-10) each represent an integer of 1 to 30.

(I) A compound having an alicyclic epoxy group can be used, for example, commercially available products such as "Celloxide 2021P" and "Celloxide 2081" (above, manufactured by Daicel).

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

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

Examples of the compound (iii) having an alicyclic ring and a glycidyl group include a compound obtained by hydrogenating a bisphenol A type epoxy compound (hydrogenated bisphenol A type epoxy compound), and a bisphenol Compound obtained by hydrogenating F-type epoxy compound (hydrogenated bisphenol F-type epoxy compound), hydrogenated biphenol-type epoxy compound, hydrogenated novolac-type epoxy compound, hydrogenated cresol novolac-type epoxy Hydrogenated aromatic glycidyl ether ring such as compound, hydrogenated cresol novolac epoxy compound of bisphenol A, hydrogenated naphthalene epoxy compound, hydrogenated epoxy compound of epoxy compound obtained from phenol methane Oxygen compounds and so on.

The polyfunctional alicyclic epoxy compound (A) is preferably a compound having an alicyclic epoxy group in terms of obtaining a cured product with low curlability, high surface hardness, and further excellent transparency, Particularly preferred is 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate [a compound represented by the above formula (I-1), trade name "Celloxide 2021P" (Daicel (Manufactured by), etc.], and (3,4,3 ', 4'-diepoxy) bicyclohexane.

The content (blending amount) of (A) is the total amount of the nonvolatile components (components 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 even more preferably 25% by weight. The lower limit is preferably 6% by weight, particularly preferably 10% by weight, most preferably 13% by weight, and even more preferably 17% by weight.

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

By controlling the content of (A) to the above range, the effect of reducing the curlability while maintaining the abrasion resistance can be obtained. If the content of (A) exceeds the above-mentioned range, the content of the polyfunctional (meth) acrylic compound (B) to be described later will be reduced, thereby exhibiting a reverse curl property, and it will be difficult to obtain a hardened material having a low curl property. . In addition, abrasion resistance tends to decrease. On the other hand, if the content of (A) is lower than the above range, since the content of the polyfunctional (meth) acrylic compound (B) described later becomes excessive, positive curl is exhibited, and low curl is required to be obtained. Hardened materials become difficult.

[Multifunctional (meth) acrylic compound (B)]

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

The number (total) of acryl and / or methacryl groups in the polyfunctional (meth) acrylic compound (B) in the molecule is 2 or more, for example, 2 to 15 and more preferably 3 or more (For example, 3 to 12), and 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 13,000, preferably 400 to 13,000, 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 13,000, preferably 500 to 10,000, and 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 curlability 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 hardened material decreases, and it may become impossible to achieve the function of top coating (particularly hard coating) as a protective film. The weight average molecular weight is a standard polystyrene-equivalent molecular weight measured by the GPC method.

As for the polyfunctional (meth) acrylic compound (B), for example, aliphatic (meth) acrylate (straight or branched chain aliphatic (meth) acrylate), alicyclic Non-aromatic (meth) acrylates such as (meth) acrylates; aromatic (meth) acrylates and the like. In the present invention, among them, from the viewpoint of non-coloring properties of the cured material, non-aromatic (meth) acrylates are preferred, and aliphatic (meth) acrylates are particularly preferred.

Specifically, the polyfunctional (meth) acrylic compound (B) may be, for example, 2-hydroxy-3- (meth) acryloxypropyl (meth) acrylate, tricyclodecane Alkanedimethanol di (meth) acrylate, glycerol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (methyl) Base) 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- (meth) acryloxyethoxy) phenyl] fluorene, 2,2-bis [4-((meth) propylene Ethoxy diethoxy) phenyl] propane, and bifunctional (meth) acrylates of such derivatives; ethoxylated isotricyanate tri (meth) acrylate, ε-hexane Lactone modified ginseng (2- (meth) acryloxyethyl) isocyanurate, glycerol tri (meth) acrylate , Ethoxylated glycerol tri (meth) acrylate, propoxylated glycerol tri (meth) acrylate, neopentyl tetraol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate Ester, tri (meth) acrylate of 3 mol ethylene oxide adduct of trimethylolpropane, tri (meth) acrylate of 3 mol ethylene oxide adduct of trimethylolpropane, tri (meth) acrylate Tri (meth) acrylate of 6 mol ethylene oxide adduct of methylolpropane, tri (meth) acrylate, di-trihydroxy of 6 mol ethylene oxide adduct of trimethylolpropane Methylpropane tetra (meth) acrylate, ethoxylated neopentaerythritol tetra (meth) acrylate, neopentaerythritol tetra (meth) acrylate, dinepentaerythritol poly (meth) acrylic acid Esters (for example, dipentaerythritol hexa (meth) acrylate, hexa (meth) acrylate of caprolactone adducts of dipentaerythritol, etc.), and derivatives thereof, polyesters ( (Meth) acrylate, polyether (meth) acrylate, acryl (meth) acrylate, urethane (meth) acrylate, epoxy (meth) ) Acrylate, polydiene ( Polyalkadiene (meth) acrylate (e.g. polybutadiene (meth) acrylate, etc.), melamine (meth) acrylate, polyacetal (meth) acrylate, etc. Polyfunctional (meth) acrylates and the like.

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

(Meth) acrylfluorenyl (for example, (meth) contained in polyfunctional (meth) acrylic compound (B)) in the total amount of (A), (B), and (C) contained in the resin composition of the present invention Concentration of acryl), for example, more than 5.0 millimoles / g (for example, more than 5.0 millimoles / g, and less than 10.0 millimoles / g), 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. The upper limit of the (meth) acrylfluorene group concentration is preferably 9.5 millimoles / g, more preferably 9.0 millimoles / g, even more preferably 8.5 millimoles / g, and particularly preferably 8.0 millimoles. / g, most preferably 7.5 millimoles / g.

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

The content (blending 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 content of (A) and (B). % By weight, particularly preferably 65 to 87% by weight, most preferably 68 to 83% by weight, and particularly preferably 73 to 83% by weight.

By controlling the content of (B) to the above range, the effect of reducing the curlability while maintaining the abrasion resistance can be obtained. If the content of (B) is out of the above range, the content of the aforementioned polyfunctional alicyclic epoxy compound (A) will decrease, and the positive curl property will be exhibited, and it will be difficult to obtain a cured product with low curl property. On the other hand, if the content of (B) is lower than the above range, since the content of the aforementioned polyfunctional alicyclic epoxy compound (A) becomes excessive, it exhibits a reverse curl property, and a low curl property hardening is required. Things become difficult. In addition, abrasion resistance tends to decrease.

[Surface-modified inorganic particles (C)]

The surface-modified inorganic particle (C) in the present invention is an epoxy group and / or a polyfunctional (meth) acrylic acid having a surface having an epoxy group with a polyfunctional alicyclic epoxy compound (A). Reactive functional group of (meth) acrylfluorenyl group of enoic acid compound (B) (i.e., functional group having reactivity with epoxy group, functional group having reactivity with (meth) acryl group), or Epoxy and (meth) acrylfluorenyl have reactive functional groups). In the present invention, the surface-modified inorganic particles (C) have excellent compatibility with organic substances because of having the above-mentioned reactive functional group. Moreover, it is excellent in dispersibility, and can prevent aggregation of inorganic particles. Then, in the present invention, when the surface-modified inorganic particle (C) has a reactive functional group with an epoxy group, it will be combined with the aforementioned polyfunctional alicyclic epoxy compound (A); in the present invention, when the surface When the modified inorganic particle (C) has a reactive functional group with a (meth) acrylfluorenyl group, it is bound to the aforementioned multifunctional (meth) acrylic compound (B); and in the present invention, the surface modified inorganic particle (C) When it has a reactive functional group with an epoxy group and a (meth) acrylfluorenyl group, it is bound to the above-mentioned polyfunctional alicyclic epoxy compound (A) and the polyfunctional (meth) acrylic compound (B Because of this, the inorganic particles are not damaged from the hardened material and can provide excellent scratch resistance to the hardened material. Furthermore, it is possible to prevent the haze from increasing in the hardened material and to generate brittleness. The surface-modified inorganic particles (C) may be used alone or in combination of two or more.

The inorganic particles include transparent inorganic particles such as silicon oxide, titanium oxide, aluminum oxide, and zirconia. In the present invention, among them, the point that the coloration of the cured product can be suppressed, and the curable compound (that is, the polyfunctional alicyclic epoxy compound (A) and the polyfunctional (meth) acrylic compound (B)) are not hindered. It is preferably silicon oxide because it is hardened without decomposing the aforementioned hardening compound and its polymer.

The average particle diameter (based on the dynamic light scattering method) of the inorganic particles is 0.1 to 100 nm, preferably 1 to 50 nm, and particularly preferably 3 to 20 nm. Average grain If the diameter exceeds the above range, the transparency tends to decrease. On the other hand, if the average particle diameter is less than the above range, scratch resistance tends to be difficult to obtain.

As for the aforementioned reactive functional groups with epoxy groups and / or (meth) acrylfluorenyl groups, for example, (meth) acrylfluorenyl groups, glycidyl ether groups, alicyclic epoxy groups, and oxa groups Cyclobutane, vinyl ether, thiirane group, vinyl, hydroxyl, and the like. In the present invention, among them, in order to improve the scratch resistance of the polyfunctional alicyclic epoxy compound (A), a group having excellent reactivity with an epoxy group is preferred, and a hydroxyl group and a glycidyl ether are particularly preferred. And alicyclic epoxy (for example, epoxycyclohexane).

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

The content (mixing amount) of (C) is the total amount of the non-volatile components (components 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 Particularly preferred is 4-20% by weight, and the best is 5-15% by weight.

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

In addition, 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 foregoing (A), (B), and (C), and the upper limit is preferably 55% by weight, particularly preferably It is 50% by weight, and most preferably 40% by weight. The lower limit is preferably 10% by weight, particularly preferably 15% by weight, most preferably 20% by weight, and even more preferably 25% by weight.

If it contains (C) in the said range, it is preferable that the hardened | cured material which has abrasion resistance, high hardness, and low curling property is obtained. If the content of (C) is less than the above range, the scratch resistance tends to decrease. On the other hand, if 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 an epoxy group of the polyfunctional alicyclic epoxy compound (A) as the surface-modified inorganic particles (C), the resin is prepared. In the case of the composition, the polyfunctional alicyclic epoxy compound (A) and the surface-modified inorganic particles (C) can be added separately and prepared by mixing. When the content of) is large, haze tends to be easily generated. In general, 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 necessary. Since a large amount is blended, when the blending amount of the solvent is set to be low, the amount that the surface-modified inorganic particles (C) can be added is considerably limited. Therefore, it is preferable to use a product obtained by reacting a surface-modified inorganic particle (C) with an epoxy-reactive functional group (for example, a hydroxyl group) with an epoxy group of the polyfunctional alicyclic epoxy compound (A), Or the surface-modified inorganic particles (C) are dispersed in a 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 a solvent The oxygen compound (A) is mixed and the solvent is removed. For a product obtained by reacting a polyfunctional alicyclic epoxy compound (A) with a surface-modified inorganic particle (C), for example, a trade name "NANOPOX C620" (manufactured by EVONIC) can be suitably used. Also, make it have In the case where the surface-modified inorganic particles (C) of the epoxy-based reactive functional group are dispersed in the polyfunctional alicyclic epoxy compound (A) without a solvent, for example, "Y10C-JFS" ( Admatechs (shares) system) and so on.

[Photocationic polymerization initiator (D)]

The photocationic polymerization initiator is a compound that generates an acid by irradiation with light, and a compound that initiates a hardening reaction of a cation-curable compound contained in the resin composition, and includes a cationic portion that absorbs light and an anion portion that becomes an acid generation source.

Examples of the photocationic polymerization initiator include a diazonium salt-based compound, a sulfonium salt-based compound, a sulfonium salt-based compound, a sulfonium salt-based compound, a selenium salt-based compound, Salt-based compounds, ammonium-based compounds, bromine-based compounds, and the like.

In the present invention, among them, a sulfonium salt-based compound is preferably used because a cured product having excellent curability can be formed. As a cationic part of a sulfonium salt-based compound, for example, (4-hydroxyphenyl) methylbenzylsulfonium ion, triphenylsulfonium ion, diphenyl [4- (phenylthio) phenyl] Arsenic ions (especially triarylsulfonium ions) such as sulfonium ions, 4- (4-biphenylthio) phenyl-4-biphenylphenylsulfonium ions, and tri-p-tolylsulfonium ions.

As for the anion part of the photocationic polymerization initiator, for example, [(Y) _s B (Phf) _4-s ] ^- (wherein Y represents a phenyl group or a biphenyl group. Phf represents a hydrogen atom. by at least one selected from a perfluoroalkyl group, at least one substituted phenyl .s perfluoroalkoxy group, a halogen atom and an integer of 0 to ^{_{3), BF 4 -, [(}} Rf) t PF _6-t] ^- (formula, Rf represents 80% or more hydrogen atoms substituted with fluorine atoms .t alkyl group represents an integer of 0 to ^{_{5), AsF 6 -, SbF 6}} -, SbF 5 OH - , etc. .

As for the photocationic polymerization initiator in the present invention, for example, (4-hydroxyphenyl) methylbenzylsulfonium (pentafluorophenyl) borate, 4- (4-biphenyl) Thio) phenyl-4-biphenylphenylsulfonium (pentafluorophenyl) borate, 4- (phenylthio) phenyldiphenylsulfonylphenyl (pentafluorophenyl) borate, [ 4- (4-biphenylthio) phenyl] -4-biphenylphenyl, phenylphenyl (pentafluorophenyl) borate, diphenyl [4- (phenylthio) phenyl], Ginseng (pentafluoroethyl) trifluorophosphate, diphenyl [4- (phenylthio) phenyl], (pentafluorophenyl) borate, diphenyl [4- (phenylthio) phenyl ] 鋶 Hexafluorophosphate, 4- (4-biphenylthio) phenyl-4-biphenylphenyl, ginseng (pentafluoroethyl) trifluorophosphate, bis [4- (diphenylsulfonium) Phenyl) phenyl] sulfide phenyl ginseng (pentafluorophenyl) borate, [4- (2-thioxanthone thio) phenyl] phenyl-2-thioxanthone phenyl phenyl (5 Fluorophenyl) borate, 4- (phenylthio) phenyldiphenylsulfonium hexafluoroantimonate; trade names "CYRACURE UVI-6970", "CYRACURE UVI-6974", "CYRACURE UVI-6990", " CYRACURE UVI-950 "(above, manufactured by Union Carbide, USA);" Irgac ure250 "," Irgacure261 "," Irgacure264 "(above, made by BASF);" CG-24-61 "(made by Ciba-Geigy);" Optomer SP-150 "," Optomer SP-151 "," Optomer SP -170 "," Optomer SP-171 "(above, ADEKA (stock) system);" DAICAT II "(Daicel (stock) system);" UVAC1590 "," UVAC1591 "(above, Daicel-Cytech (stock) system) ; "CI-2064", "CI-2639", "CI-2624", "CI-2481", "CI-2734", "CI-2855", "CI-2823", "CI-2758", ""CIT-1682" (above, manufactured by Soda Co., Ltd.); "PI-2074" (manufactured by Rhodia Corporation, (pentafluorophenyl) borate Formamyl cumene sulfonium salt); "FFC509" (manufactured by 3M); "BBI-102", "BBI-101", "BBI-103", "MPI-103", "TPS-103", "MDS-103", "DTS-103", "NAT-103", "NDS-103" (above, made by Midori Chemical Co., Ltd.); "CD-1010", "CD-1011", "CD-1012" (Above, manufactured by Sartomer, USA); "CPI-100P", "CPI-101A" (above, manufactured by San-Apro), and other commercially available products. These can be used individually by 1 type or in combination of 2 or more types.

The content of the photocationic polymerization initiator (D) in the resin composition of the present invention is 100 parts by weight with respect to 100 parts by weight of the cationic curable compound (especially 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, and particularly preferably 2 to 4 parts by weight. If the content of the photocationic polymerization initiator (D) is lower than the above range, there is a possibility that the curing failure may be caused. On the other hand, when the content of the photocationic polymerization initiator (D) exceeds the above range, the cured product tends to be easily colored.

[Photo radical polymerization initiator (E)]

The photo-radical polymerization initiator is a compound that generates radicals by irradiation of light, and initiates a curing reaction of the radical-curable compound contained in the resin composition. For example, benzophenone and acetophenone may be mentioned. Acetophenone benzyl, benzyl dimethyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, dimethoxyacetophenone, dimethoxyphenyl Acetophenone, diethoxyacetophenone, diphenyl disulfite, methyl o-benzoyl benzoate, ethyl 4-dimethylamino benzoate (made by Nippon Kayaku Co., Ltd., Trade name "Kayacure EPA", etc.), 2,4-diethylthioxanthone (made by Nippon Kayaku Co., Ltd., trade name "Kayacure DETX", etc.), 2-methyl-1 -[4- (methyl) phenyl] -2- Porphyrinacetone-1 (made by Ciba-Geigy (stock), trade name "Irgacure907", etc.), 1-hydroxycyclohexylphenyl ketone (made by Ciba-Geigy (stock), trade name "Irgacure184", etc.), 2-two Methylamino-2- (4- 2-amino-2-benzyl-1-phenylalkane compounds such as benzamyl-1-phenylpropane, tetrakis (tertiary butylperoxycarbonyl) benzophenone, benzyl Amine derivatives such as 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 4,4'-bis (diethylamino) benzophenone, 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", etc.) Compound, 2,6-bis (trichloromethyl) -4- (4-methoxynaphthalene-1-yl) -1,3,5-tris Isohalomethylated tris Compound, 2-trichloromethyl-5- (2-benzofuran-2-yl-vinyl) -1,3,4- Halomethyl Diazole compounds and the like. These can be used individually by 1 type or in combination of 2 or more types.

Content of the photo-radical polymerization initiator (E) in the resin composition of the present invention with respect to 100 parts by weight of a radical-curable compound (particularly a 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, and particularly preferably 1.5 to 3.5 parts by weight. If the content of the photo-radical polymerization initiator (E) is less than the above range, there is a possibility of causing hardening failure. On the other hand, if the content of the photo radical polymerization initiator (E) exceeds the above range, the cured product tends to be easily colored.

[Other hardening compounds]

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

The ratio of the total content of the polyfunctional alicyclic epoxy compound (A) and the polyfunctional (meth) acrylic compound (B) to 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. 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. If the ratio of the total content of the polyfunctional alicyclic epoxy compound (A) to the polyfunctional (meth) acrylic compound (B) is lower than the above range, it is necessary to obtain a combination of low curlability, 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 other than the above as long as the effect of the present invention is not impaired. In the present invention, it is preferable to contain one or two or more kinds of compounds that impart lubricity in order to obtain a hardened material that is more excellent in abrasion resistance.

Examples of the aforementioned lubricity-imparting compound include a silane compound, a (meth) acrylic compound containing a perfluoroalkyl group, a (meth) acrylic compound containing a silicon group, and a polyether-modified (meth) Acrylic compounds, silicon-modified poly (meth) acrylates, polyether-modified poly (meth) acrylates, poly (meth) acrylates containing perfluoroalkyl groups, and polyethers containing perfluoroalkyl groups (Meth) acrylic ester Methylsiloxanes, polyether-modified polydimethylsiloxanes, polydimethylsiloxanes containing perfluoroalkyl groups, polyether-modified polydimethylsiloxanes containing perfluoroalkyl groups, etc. . It is preferable that the said compound has a reactive functional group with an epoxy group and / or a (meth) acryl fluorenyl group (The thing similar to the example in the surface modification inorganic particle (C) is mentioned).

Examples of the silane compound include triethylsilane, tertiary butyldimethylsilane, and the like.

As for the aforementioned (meth) acrylic compound containing a perfluoroalkyl group, for example, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-penta Fluoropropyl (meth) acrylate, 2- (perfluorobutyl) ethyl (meth) acrylate, 2- (perfluorooctyl) ethyl (meth) acrylate, and the like.

As for the aforementioned silicon-containing (meth) acrylic compound, for example, trimethylsilyl (meth) acrylate, triisopropylsilyl (meth) acrylate, tri (n-butyl) ) Silyl (meth) acrylate, triisobutylsilyl (meth) acrylate, tricyclohexylsilyl (meth) acrylate, triphenylsilyl (meth) acrylate, etc.

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

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

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

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

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

The aforementioned polyether-modified polydimethylsiloxane, a polydimethylsiloxane containing a perfluoroalkyl group, and a polyether-modified polydimethylsiloxane containing a perfluoroalkyl group, except for poly (methyl It is the same as described above when the acrylate) is changed to a system other than polydimethylsiloxane.

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

In the present invention, it is particularly preferable to use a compound containing a hydroxyl group having particularly excellent reactivity with the epoxy group of the polyfunctional alicyclic epoxy compound (A) (for example, a silicon-modified poly (meth) acrylic acid containing a hydroxyl group) Ester, etc.), and the hydroxyl value is preferably, for example, 5 to 150 mgKOH / g.

The amount of the compound that imparts lubricity to the total (100 parts by weight) of (A), (B), and (C) contained in the resin composition of the present invention (when two or more kinds are included, the total amount) For example, it is 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, and particularly preferably 0.1 to 3 parts by weight.

For the resin composition of the present invention, in addition, solvents (for example, butyl acetate, methyl ethyl ketone, etc.), polyols, hardening aids, organosiloxane compounds, metal oxide particles, rubber particles, and antifoaming agents can also be used. , Silane coupling agent, filler, plasticizer, leveling agent, antistatic agent, release agent, surfactant, flame retardant, colorant, antioxidant , UV absorber, ion adsorbent, fluorescent and other commonly used additives. With respect to the resin composition (100% by weight) of the present invention, the content of these additives can be appropriately set, for example, in a range of 0 to 40% by weight, preferably 1 to 25% by weight.

The resin composition of the present invention can be prepared by stirring / mixing the above-mentioned respective components in a heated state as necessary. In addition, the resin composition of the present invention may be used as a one-liquid-type composition in which those obtained by mixing the components in advance are used as they are, or they may be divided into two or more components, for example. A mixture of two or more components) is a multi-liquid system (for example, a two-liquid system) composition that is mixed and used at a specified ratio before use. The above-mentioned stirring / mixing method is not particularly limited. For example, various mixers such as a dissolver, a homogenizer, a kneader, a roll, a bead mill, and a self-revolving stirring device can be used. Mixed means. After stirring / mixing, defoaming can also be performed under vacuum.

<Composition for Hard Coating>

By curing the resin composition of the present invention, it is possible to obtain a cured product having low curlability and excellent surface hardness and abrasion resistance. Therefore, the resin composition of the present invention can be preferably used as a composition for hard coating (hard coating agent).

<Painting>

The resin composition of the present invention is applied and hardened on the surface of an object (such as a base material or a film made of a metal or a resin (for example, plastic such as TAC and PET)), which is an object (a coating object). This gives a coating. The resin composition of the present invention is excellent in hardenability (hardening speed). The hardened material is low in curl and has excellent surface hardness and abrasion resistance. Therefore, the coating is excellent in both productivity and quality.

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

The resin composition of the present invention can be used in coating agents (particularly for hard coating applications), inks, adhesives, sealants, sealants, resists, composite materials, transparent substrates, transparent films or sheets, and optical materials. (E.g., optical lenses, etc.), optical shaping materials, electronic materials (e.g., electronic paper, touch panels, solar cell substrates, optical waveguides, light guide plates, holographic memories, etc.), mechanical component materials, electrical component materials, automobiles Various applications such as component materials, civil construction materials, molding materials, plastic forming materials, and solvents (for example, reactive diluents).

[Example]

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

Example 1

[Preparation of resin composition]

The ingredients were mixed at the blending ratio (unit: part by weight) shown in the table, and they were stirred and defoamed using a self-revolving stirring device (trade name "THINKY MIXERAR-250", manufactured by Thinky) to obtain a resin.组合 物。 Composition.

[Production of hardened film]

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

Then, after drying at 80 ° C. for 1 minute, ultraviolet rays were irradiated under a condition of an irradiation amount of about 1000 mJ / cm ² in a state where the nitrogen-filled closed container was placed, and curing was performed.

The laminated body (cured film) having the structure of "PET substrate / cured material (cured coating film)" obtained in this manner was used as a sample for pencil hardness evaluation and abrasion resistance evaluation.

Further, a test piece having a square shape of 10 cm on one side was cut out from the laminated body (cured film) having the structure of "PET substrate / cured material (cured coating film)" obtained as described above. With respect to the test piece, the film thickness at the measurement points shown by the numbers 1 to 5 circled in FIG. 1 (1a) was measured. At all the measurement points, the cured coating film thicknesses of the film thickness of the PET base material (pre-measured film thickness) minus the film thickness at the measurement points were 20 μm ± 2 μm, respectively, and they were considered acceptable, and they were used as curls. Sample for sexual evaluation. When it failed, a bar coater was changed, and the coating, drying, and hardening steps were repeated until the film thickness at the measurement point became acceptable, and a sample for curling evaluation was produced.

Examples 2 to 10, Comparative Examples 1 to 8

A resin composition and a cured product (sample) thereof were obtained in the same manner as in Example 1 except that the blending amounts of the components were changed as shown in the table. In Examples and Comparative Examples other than Example 1 and Comparative Example 2, post-curing (heating at 80 ° C. for 2 hours) was performed after ultraviolet irradiation.

<Evaluation>

The hardened | cured material (sample) of the resin composition obtained by the Example and the comparative example was performed the following evaluation test.

[Pencil hardness]

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

The pencil hardness of the cured coating film was evaluated in accordance with JIS K5600. The evaluation was performed by visual inspection, and the cured coating film on the PET substrate was scratched with a pencil, and those with a flaw on the surface or the substrate were regarded as NG (defective). To be specific, iteratively proceed: the evaluation is performed with a pencil of a certain hardness, and when there is no flaw, the operation of the previous level of hardness pencil is performed. If a flaw is confirmed, the hardness of the next level is re-evaluated . If a flaw is not confirmed, a pencil with a higher hardness is used. When the reproducibility is confirmed twice or more, the hardest pencil hardness that does not impart a flaw is set to the pencil hardness of the cured coating film. The evaluation result is Expressed as the hardness of the pencil core. The evaluation conditions are as follows.

Evaluation pencil: "Pencil for pencil hardness test" made by Mitsubishi Pencil

Load: 750gf

Scratching distance: 50mm or more

Scratching angle: 45 °

Measurement environment: 23 ℃, 50% RH

The sample (cured film) used in the test was obtained by using a constant temperature and humidity machine at 23 ° C. and 50% RH for 24 hours to adjust humidity.

[Curlability]

As shown in FIG. 1 (1b), for the samples for evaluation of curlability obtained in the examples and comparative examples, the warpage of the four corners when placed on a horizontal plane was measured, and the average value was taken as the warpage of the cured film. . The larger the amount of warping, it is considered that the hardening shrinks or the hardening expands. Furthermore, the warpage at the time of hardening shrinkage (when the surface of the hardened film that is in contact with the horizontal plane in FIG. 1 (1b) and the hardened coating film is on the opposite side) is set to a positive value. When the surface in contact with the horizontal plane of FIG. 1 (1b) is the hardened coating film side), the warpage is shown in the table as a negative value.

[Scratch resistance]

For the hardened films (thickness of about 20 μm) obtained in the examples and comparative examples, the coated surface was reciprocated 20 times, 200 times with a load of 500 g / cm ² or 1 kg / cm ² using steel wool of # 0000 Scratching was performed 1,000 times, and abrasion resistance was evaluated. The evaluation system for abrasion resistance is as follows.

A: 1000 times without scratches

B: There are no scars after 200 round trips, and there are slight scars after 1000 round trips

C: There are no scars after 200 round trips, and there are slight scars or slight turbidity after 1000 round trips

D: There are no scars after 200 round trips, and there are clear scars or clear turbidity after 1000 round trips

E: There are no scars after 20 round trips, and there are slight scars after 200 round trips

F: There are no scars after 20 round trips, and there are slight scars or slight turbidity after 200 round trips

G: There are no scars for 20 round trips, and there are clear scars or clear turbidity for 200 round trips

H: Minor scars after 20 round trips

I: Slight scars or turbidity after 20 round trips

The abbreviations in Tables 1 and 2 represent the following compounds.

NANOPOX C620: Compound obtained by reacting hydroxyl-containing silica (average particle diameter of silica: 10 nm) (40 parts by weight) with Celloxide 2021P (60 parts by weight), trade name "NANOPOX C620", manufactured by EVONIC Corporation

Y10C-JFS: A mixture of Celloxide 2021P (80.5 parts by weight) and alicyclic epoxy-containing silica (average particle size of silica: 10nm) (19.5 parts by weight), trade name "Y10C-JFS", Admatechs (stock) system

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

A-9550: Dinepentaerythritol polyacrylate, molecular weight: about 554, hydroxyl value: about 56 mgKOH / g, manufactured by Shin Nakamura Chemical Co., Ltd.

A-TMM-3L-N: neopentaerythritol triacrylate, molecular weight: 246, hydroxyl value: about 112 mgKOH / g, manufactured by Shin Nakamura Chemical Co., Ltd.

DPHA: Dinepentaerythritol hexaacrylate, molecular weight: 578, trade name "DPHA", manufactured by Daicel-Allnex (stock)

Y10C-MFK: methyl ethyl ketone dispersion (silica concentration: 30% by weight) containing glycidyl ether-containing silica (silica average particle diameter: 10 nm), trade name "Y10C-MFK", manufactured by Admatechs

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

Irgacure 184: 1-hydroxycyclohexylphenyl ketone

BYK-SILCLEAN 3700: Silicon-modified polyacrylic acid containing hydroxyl groups Ester, hydroxyl value: about 30 mgKOH / g, trade name "BYK-SILCLEAN 3700", manufactured by BYK Chemie Japan

[Industrial availability]

The resin composition for forming a hard coat layer of the present invention can form a hardened product having high surface hardness, excellent abrasion resistance, and low curl by irradiating active energy rays, and can be suitably used in plastic films and Use for forming a hard coat layer on the surface of a glass substrate.

Claims (9)

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 or more (formaldehydes) in one molecule. (Meth) acrylfluorene-based polyfunctional (meth) acrylic compound (B), inorganic particles having an average particle diameter (according to a dynamic light scattering method) of 0.1 to 100 nm, have an epoxy group and / or (meth) propylene Surface-modified inorganic particles (C), photocationic polymerization initiator (D), and photoradical polymerization initiator (E) of the fluorene-based reactive functional group, and the content of the aforementioned (A) is (A) and (B) The sum (100% by weight) of 3 to 35% by weight. The resin composition for forming a hard coat layer according to claim 1, wherein the content of the (C) is 5 to 40 parts by weight based on 100 parts by weight of the total content of the (A) and (B). The resin composition for forming a hard coat layer according to claim 1, wherein the (meth) acrylfluorenyl 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. The resin composition for forming a hard coat layer according to claim 2, wherein the (meth) acrylfluorenyl 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. The resin composition for forming a hard coat layer according to any one of claims 1 to 4, wherein the inorganic particles in the surface-modified inorganic particles (C) are silicon oxide. The resin composition for forming a hard coat layer according to any one of claims 1 to 4, further comprising a compound selected from the following compounds having a reactive functional group with an epoxy group and / or a (meth) acrylfluorenyl group. At least one compound: silicon compounds, (meth) acrylic compounds containing perfluoroalkyl groups, containing Silicon-based (meth) acrylic compounds, polyether-modified (meth) acrylic compounds, silicon-modified poly (meth) acrylates, polyether-modified poly (meth) acrylates, Poly (meth) acrylates, polyether-modified (meth) acrylates containing perfluoroalkyl groups, acryl-modified polydimethylsiloxanes, polyether-modified polydimethylsiloxanes, Polydimethylsiloxane containing a perfluoroalkyl group and polydimethylsiloxane modified with a polyether containing a polyether. The resin composition for forming a hard coat layer according to claim 5, further comprising at least one compound selected from the following compounds having a reactive functional group with an epoxy group and / or a (meth) acrylfluorenyl group: Silicon compound, (meth) acrylic compound containing perfluoroalkyl group, (meth) acrylic compound containing silicon group, polyether modified (meth) acrylic compound, silicon modified poly (meth) acrylate, poly Ether-modified poly (meth) acrylate, poly (meth) acrylate containing perfluoroalkyl group, polyether-modified (meth) acrylate containing perfluoroalkyl group, acryl-modified polydimethylene Siloxane, polyether-modified polydimethylsiloxane, polydimethylsiloxane containing a perfluoroalkyl group, and polyethermodified polydimethylsiloxane containing a perfluoroalkyl group. A hardened product of a resin composition for forming a hard coat layer according to any one of claims 1 to 7. A coated article having a hard coat layer comprising a cured product of a resin composition for forming a hard coat layer according to any one of claims 1 to 7 on the surface of an article.