KR101751372B1 - Photocurable resin composition and cured film thereof - Google Patents

Abstract

A photo-curable resin composition capable of forming a hard coat layer having improved blocking resistance without lowering transparency and having excellent printability, and a cured film thereof.
(Meth) acrylate equivalent weight of 100 to 800 g / eq, a weight average molecular weight of 10,000 to 200,000, a glass transition point of 50 to 110 占 폚, and a photopolymerizable group and a hydroxyl group (B) having an average particle diameter of 10 nm to 500 nm, organic particles (C) having an average particle diameter of 10 nm to 500 nm, and a (meth) acrylic polymer And a photopolymerizable polyfunctional compound (D) having at least two photopolymerizable groups.

Description

TECHNICAL FIELD [0001] The present invention relates to a photocurable resin composition and a cured film thereof,

The present invention relates to a photo-curable resin composition and a cured film thereof suitably used for forming a hard coat layer.

BACKGROUND ART Conventionally, information terminal apparatuses such as a mobile phone, a portable information terminal (PDA), a portable game machine, a digital camera, a personal computer, and a television are known. Recently, in such an information terminal apparatus, a touch panel is mounted on the front surface of a display panel. The touch panel can input necessary information such as data information to the information terminal device by pressing the surface panel with a finger or a pen.

Examples of the classification of the touch panel include an optical method, an ultrasonic method, a capacitance method, and a resistive film method. In a capacitive touch panel, a laminated film having a transparent substrate and a transparent conductive layer having a pattern shape such as a stripe pattern provided on the transparent substrate is used.

If a transparent substrate surface is scratched, transparency is lowered. Therefore, a hard coat layer is formed by applying a coating agent to the surface of the transparent substrate, and a transparent conductive layer is provided on the hard coat layer. When the adhesion between the hard coat layer and the transparent conductive layer is low, the transparent conductive layer is provided on the hard coat layer through the adhesive layer. According to the hard coat layer, it is possible to impart scratch resistance to the surface of the transparent substrate. In such a hard coat layer, it is necessary to have high transparency in order to secure the visibility of the touch panel.

BACKGROUND ART Conventionally, various studies have been made on a coating agent used for forming a hard coat layer. Patent Document 1 discloses a photopolymerizable composition comprising (A) 3 to 40 mass% of an acrylic resin, (B) 0.1 to 5 mass% of a polyoxyethylene-polyoxypropylene block copolymer, and (C) Discloses a photocurable hydrophilic coating agent containing a resin component containing 55 to 95 mass% of a functional compound.

Patent Document 2 discloses a reaction product (A) comprising an addition reaction of a carboxyl group-containing (meth) acrylic compound (a2) with a polymer obtained by polymerizing a polymerization component (a1) containing a vinyl compound having an epoxy group in a molecule, B), a phosphoric acid compound (C) containing one or two vinyl groups in the molecule, and a polyfunctional (meth) acrylic compound (D).

Patent Document 3 discloses an optical sheet having a functional layer on at least one surface of a transparent substrate and a functional layer in which transparent inorganic particles and / or translucent organic particles are dispersed in a transparent resin.

International Publication No. 2011/013497 specification Japanese Patent Application Laid-Open No. 2009-286972 Japanese Patent Application Laid-Open No. 2010-66549

The hard coat layer formed using the photocurable hydrophilic coating agent of Patent Document 1 has low blocking resistance. Therefore, when the transparent substrate having the hard coat layer is rolled up or stored in the form of a roll, the transparent substrates are hardly peeled off from each other.

The active energy ray-curable resin composition of Patent Document 2 contains colloidal silica as inorganic particles. The surface of the hard coat layer formed by using the active energy ray-curable resin composition has irregularities formed by the inorganic particles, thereby imparting anti-blocking properties to the hard coat layer. However, the use of only the inorganic particles not only makes it impossible to sufficiently improve the blocking resistance of the hard coat layer, but also lowers the transparency of the hard coat layer.

In the optical sheet of Patent Document 3, concaves and convexes are formed on the surface of the functional layer by translucent inorganic particles and / or light-transmitting organic particles. However, such unevenness is formed in order to impart antiglare property to the optical sheet. For this purpose, translucent inorganic particles and translucent organic particles having a large particle diameter are used. Use of such translucent inorganic particles and translucent organic particles lowers the transparency of the functional layer.

The formation of the transparent conductive layer or the adhesive layer on the hard coat layer can be performed by applying an ink such as a composition containing a conductive paste or an adhesive to the hard coat layer. However, since the hard coat layer has low wettability with the ink, when the ink is applied onto the hard coat layer, the hard coat layer splashes the ink. Therefore, the ink can not be printed with high precision, and a transparent conductive layer or an adhesive layer having a desired pattern shape and uniform thickness can not be formed on the hard coat layer. Therefore, it is also necessary to improve the printability of the hard coat layer.

Therefore, an object of the present invention is to provide a photo-curable resin composition capable of forming a hard coat layer having improved blocking resistance without deteriorating transparency and having excellent printability.

The photo-curable resin composition of the present invention is a photo-

(Meth) acrylate equivalent weight of 100 to 800 g / eq, a weight average molecular weight of 10,000 to 200,000, a glass transition point of 50 to 110 占 폚, and a photopolymerizable group and a hydroxyl group (Meth) acryl-based polymer (A)

An inorganic particle (B) having an average particle diameter of 10 nm to 500 nm,

(C) having an average particle diameter of 10 nm to 500 nm,

(D) having at least two photopolymerizable groups in one molecule, and the photopolymerizable polyfunctional compound

Based on the total weight of the (meth) acrylic polymer (A), the inorganic particles (B), the organic particles (C), and the photopolymerizable polyfunctional compound (D)

The content of the (meth) acrylic polymer (A) is 10 to 40% by weight,

, The content of the inorganic particles (B) is 5 to 40% by weight,

The content of the organic particles (C) is 0.5 to 10% by weight,

The content of the photopolymerizable polyfunctional compound (D) is 20 to 70% by weight.

The (meth) acrylic polymer (A) preferably contains an alkyl (meth) acrylate component in an amount of 10 to 90% by weight.

The inorganic particles (B) are preferably at least one of metal particles and metal oxide particles.

The organic particles (C) are preferably (meth) acrylic resin particles.

It is preferable that the photocurable resin composition contains a photopolymerization initiator.

Further, the cured film of the present invention is characterized in that the photo-curable resin composition is cured.

(Effects of the Invention)

According to the photocurable resin composition of the present invention, it is possible to form a hard coat layer having improved blocking resistance without deteriorating transparency and having excellent printability.

[Photocurable resin composition]

The photocurable resin composition of the present invention is a composition comprising a (meth) acrylic polymer (A), an inorganic particle (B), and an organic particle (C) each having a photopolymerizable group and a hydroxyl group in a side chain and at least two photopolymerizable groups And a photopolymerizable polyfunctional compound (D).

[(Meth) acryl-based polymer (A)]

The photo-curing resin composition of the present invention contains at least one (meth) acryl-based polymer (A) having a photopolymerizable group and a hydroxyl group in its side chain. By using the (meth) acrylic polymer (A), a hard coat layer having excellent transparency can be formed. Further, the (meth) acrylic polymer (A) can be subjected to radical polymerization by a photopolymerizable polyfunctional compound (D) and a photopolymerizable group to form a crosslinked structure. Thus, a hard coat layer having high hardness and excellent in scratch resistance can be formed.

The (meth) acrylic polymer (A) should have at least one photopolymerizable group and at least one hydroxyl group in the side chain, and the (meth) acrylic polymer (A) preferably has two or more photopolymerizable groups and a hydroxyl group in the side chain. In the present invention, (meth) acryl means acryl or methacryl.

The photopolymerizable group of the (meth) acrylic polymer (A) may have a photopolymerizable group of a photopolymerizable polyfunctional compound (D) to be described later and a radically polymerizable ethylenically unsaturated double bond. Examples of the photopolymerizable group include an acryloyl group, a methacryloyl group, a styryl group, a vinyl group, and an allyl group, and an acryloyl group and a methacryloyl group are preferable.

As the (meth) acrylic polymer (A), the following (meth) acrylic polymers (A1) to (A3) are preferably used.

(I ') obtained by radical polymerization of a monomer composition (I) containing a radically polymerizable monomer having a glycidyl group and an alkyl (meth) acrylate not having a glycidyl group, if necessary, (A1) obtained by adding a compound having a carboxyl group and a photopolymerizable group to a (meth) acrylic polymer;

(II ') obtained by radical polymerization of a monomer composition (II) containing a radically polymerizable monomer having a hydroxyl group and an alkyl (meth) acrylate having no hydroxyl group, as the case requires, (Meth) acryl-based polymer (A2) obtained by adding a compound having a cyano group; And

(III ') having a carboxyl group obtained by radical polymerization of a monomer composition (III) containing a radically polymerizable monomer having a carboxyl group and an alkyl (meth) acrylate having no carboxyl group if necessary, (Meth) acrylic polymer (A3) obtained by adding a compound having a photopolymerizable group.

The (meth) acrylic polymers (A1) to (A3) can be produced, for example, by the following methods (1) to (3).

(1) a monomer composition (I) containing a radically polymerizable monomer having a glycidyl group and an alkyl (meth) acrylate having no glycidyl group, if necessary, is subjected to radical polymerization in the presence of a radical polymerization initiator, (Meth) acrylic polymer (A1) by adding a compound having a carboxyl group and a photopolymerizable group to the polymer (I '), and a step of obtaining a (meth) acrylic polymer

(II) a radically polymerizable monomer having a hydroxyl group, and optionally a monomer composition (II) containing an alkyl (meth) acrylate having no hydroxyl group, in the presence of a radical polymerization initiator, (A2) by adding a compound having an isocyanate group and a photopolymerizable group to the polymer (II '), and a step of obtaining a (meth) acrylic polymer (A2)

(III) a radically polymerizable monomer having a carboxyl group and, if necessary, a monomer composition (III) containing an alkyl (meth) acrylate having no carboxyl group, in the presence of a radical polymerization initiator, (Meth) acrylic polymer (A3) by adding a compound having a glycidyl group and a photopolymerizable group to the polymer (III ').

A specific example of the production process (1) of the (meth) acrylic polymer (A1) will be described below. (I) containing a radically polymerizable monomer having a glycidyl group and an alkyl (meth) acrylate having no glycidyl group, if necessary, is subjected to radical polymerization in a reaction vessel in the presence of a radical polymerization initiator, To prepare a polymer (I ') having a silyl group. Then, a compound having a carboxyl group and a photopolymerizable group, and, if necessary, a catalyst are added to the reaction vessel. If necessary, polymerization inhibitors such as p-methoxyphenol and hydroquinone (HQ) may be added to the reaction vessel. Thereafter, the reaction solution is allowed to react for 6 to 12 hours while controlling the reaction liquid to be at 30 to 150 占 폚 while blowing oxygen into the reaction vessel if necessary, whereby a (meth) acrylic polymer having a photopolymerizable group and a hydroxyl group (A1) can be produced.

Examples of the radically polymerizable monomer having a glycidyl group include glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and allyl glycidyl ether. (Meth) acrylate. Further, the radically polymerizable monomers having a glycidyl group may be used alone, or two or more kinds thereof may be used in combination. Further, (meth) acrylate means acrylate or methacrylate.

The content of the radically polymerizable monomer having a glycidyl group in the monomer composition (I) is preferably from 10 to 90% by weight, and more preferably from 20 to 80% by weight. By setting the content of the radically polymerizable monomer having a glycidyl group to the lower limit value or more, it is possible to form a hard coat layer having high crosslinking density and excellent hardness. By controlling the content of the radically polymerizable monomer having a glycidyl group to be not more than the upper limit value, it is possible to suppress gelation in the synthesis of the (meth) acrylic polymer.

The monomer composition (I) preferably contains an alkyl (meth) acrylate having no glycidyl group. It is preferable that the alkyl (meth) acrylate not having a glycidyl group does not have a hydroxyl group. Examples of such alkyl (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, (Meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (Meth) acrylate, and the like. Among them, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate and butyl (meth) acrylate are preferable, and methyl (meth) acrylate is more preferable. The alkyl (meth) acrylate may be used singly or in combination of two or more.

The content of the alkyl (meth) acrylate having no glycidyl group in the monomer composition (I) is preferably from 10 to 90% by weight, and more preferably from 20 to 80% by weight. When the content of the alkyl (meth) acrylate having no glycidyl group is set to the lower limit value or more, the gelation during the synthesis of the (meth) acrylic polymer can be suppressed. By setting the content of the alkyl (meth) acrylate having no glycidyl group to the upper limit value or less, a hard coat layer having a high crosslinking density and excellent hardness can be formed.

The monomer composition (I) may contain an alkyl (meth) acrylate having a hydroxyl group. By using an alkyl (meth) acrylate having a hydroxyl group, the hydroxyl value of the (meth) acrylic polymer (A1) can be adjusted. Examples of the alkyl (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) (Meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl Acrylate, and 12-hydroxylauryl (meth) acrylate. Among them, 2-hydroxyethyl (meth) acrylate is preferable. The alkyl (meth) acrylate having a hydroxyl group may be used singly or in combination of two or more.

The content of the alkyl (meth) acrylate having a hydroxyl group in the monomer composition (I) is preferably 80% by weight or less, more preferably 60% by weight or less. By controlling the content of the alkyl (meth) acrylate having a hydroxyl group to be not more than the upper limit value, deterioration of transparency of the hard coat layer due to aggregation of the inorganic particles (B) and the organic particles (C) can be suppressed.

The monomer composition (I) may contain (meth) acrylate having an alicyclic group. Examples of the (meth) acrylate having an alicyclic group include cyclohexyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (Meth) acrylate, chloropentadienyl (meth) acrylate, isobonyl (meth) acrylate, and tricyclodecanyl (meth) acrylate.

The content of the (meth) acrylate having an alicyclic group in the monomer composition (I) is preferably 80% by weight or less, and more preferably 60% by weight or less. By controlling the content of the (meth) acrylate having an alicyclic group to be not more than the upper limit, the lowering of the molecular weight of the (meth) acrylic polymer (A1) is suppressed and thereby the hard coat layer having excellent blocking resistance and transparency is formed .

A compound having a carboxyl group and a photopolymerizable group is added to the polymer (I ') having a glycidyl group. Examples of the compound having a carboxyl group and a photopolymerizable group include an ethylenically unsaturated carboxylic acid or an anhydride thereof. Specific examples include acrylic acid, methacrylic acid, omega -carboxy-polycaprolactone monoacrylate, and phthalic acid monohydroxyethyl acrylate, and acrylic acid and methacrylic acid are preferable. The compounds having a carboxyl group and a photopolymerizable group may be used alone or in combination of two or more. The carboxyl group possessed by these compounds and the glycidyl group of the polymer (I ') react with each other to form an ester bond, and a new hydroxyl group can be produced. At the same time, the photopolymerizable group can be introduced. Thus, a (meth) acrylic polymer (A1) having a photopolymerizable group and a hydroxyl group in its side chain is obtained.

When a compound having a carboxyl group and a photopolymerizable group is added to the polymer (I ') having a glycidyl group, the ratio of the carboxyl group and the glycidyl group to the glycidyl group in the radically polymerizable monomer having a glycidyl group used in the production of the polymer (I' The molar ratio of the carboxyl group (mole number of carboxyl group / mole number of glycidyl group) in the compound having a photopolymerizable group is preferably from 0.3 to 1.5, more preferably from 0.5 to 1.2, and particularly preferably 1.0. When the molar ratio is too low, the photopolymerizable group in the side chain is decreased, and the hardness of the hard coat layer may be lowered. If the molar ratio is excessively high, unreacted acid remains, and the water resistance of the hard coat layer may be lowered. Further, as described above, the glycidyl group reacts with the carboxyl group to form an ester bond, and also generates a hydroxyl group. Therefore, the hydroxyl value of the (meth) acrylic polymer (A1) can be adjusted by adjusting the molar ratio.

An example of a more specific production method for the production method (2) of the (meth) acrylic polymer (A2) will be described. (II) containing a hydroxyl group-containing radical polymerizable monomer and, if necessary, an alkyl (meth) acrylate having no hydroxyl group, in a reaction vessel in the presence of a radical polymerization initiator to obtain a polymer having a hydroxyl group II '). Then, a compound having an isocyanate group and a photopolymerizable group, and, if necessary, a catalyst are added to the reaction vessel. If necessary, polymerization inhibitors such as p-methoxyphenol and hydroquinone (HQ) may be added to the reaction vessel. Thereafter, the reaction solution is allowed to react for 6 to 12 hours while controlling the reaction liquid to be at 30 to 150 占 폚 while blowing oxygen into the reaction vessel if necessary, whereby a (meth) acrylic polymer having a photopolymerizable group and a hydroxyl group (A2) can be produced.

Examples of the radically polymerizable monomer having a hydroxyl group include alkyl (meth) acrylates having a hydroxyl group, acrylic acid N-hydroxymethylamide, methacrylic acid N-hydroxymethylamide, 4-hydroxymethylcyclohexyl (meth) (Meth) acrylate having a hydroxyl group is preferable, and alkyl (meth) acrylate having a hydroxyl group in the alkyl group is more preferable. Examples of the alkyl (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) (Meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl Acrylate, and 12-hydroxylauryl (meth) acrylate. The radically polymerizable monomer having a hydroxyl group may be used singly or two or more kinds thereof may be used in combination.

As the radically polymerizable monomer having a hydroxyl group, 2-hydroxyethyl (meth) acrylate is preferable, and 2-hydroxyethyl methacrylate (2-HEMA) is more preferable. By using a radically polymerizable monomer having a hydroxyl group, the hydroxyl value of the (meth) acrylic polymer (A2) can be easily adjusted.

The content of the radically polymerizable monomer having a hydroxyl group in the monomer composition (II) is preferably from 10 to 90% by weight, and more preferably from 20 to 80% by weight. By setting the content of the radically polymerizable monomer having a hydroxyl group to the lower limit value or more, a hard coat layer having a high crosslinking density and excellent hardness can be formed. The inorganic particles (B) and the organic particles (C) are highly dispersed by setting the content of the radically polymerizable monomer having a hydroxyl group to the lower limit value or more, thereby improving the transparency and printing property of the hard coat layer . On the other hand, by setting the content of the radically polymerizable monomer having a hydroxyl group to be not more than the upper limit value, deterioration of transparency of the hard coat layer due to agglomeration of the inorganic particles (B) and the organic particles (C) can be suppressed.

It is preferable that the monomer composition (II) further contains an alkyl (meth) acrylate having no hydroxyl group. Specific examples of the alkyl (meth) acrylate not having a hydroxyl group include the same alkyl (meth) acrylates having no glycidyl group in the above-mentioned method (1). Among these, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth) acrylate are preferable.

The content of the alkyl (meth) acrylate having no hydroxyl group in the monomer composition (II) is preferably from 10 to 90% by weight, and more preferably from 20 to 80% by weight. When the content of the alkyl (meth) acrylate having no hydroxyl group is set to the lower limit value or more, deterioration of transparency of the hard coat layer due to agglomeration of the inorganic particles (B) and the organic particles (C) can be suppressed. On the other hand, by setting the content of the alkyl (meth) acrylate having no hydroxyl group to the upper limit value or less, the inorganic particles (B) and the organic particles (C) are highly dispersed to improve the transparency and printability of the hard coat layer . By setting the content of the alkyl (meth) acrylate having no hydroxyl group to the upper limit value or less, a hard coat layer having a high crosslinking density and excellent hardness can be formed.

The monomer composition (II) may contain (meth) acrylate having an alicyclic group. Specific examples of the (meth) acrylate having an alicyclic group include the same as those of the (meth) acrylate having an alicyclic group in the above-mentioned method (1).

The content of the (meth) acrylate having an alicyclic group in the monomer composition (II) is preferably 80% by weight or less, and more preferably 60% by weight or less. By lowering the content of the (meth) acrylate having an alicyclic group to the upper limit value or less, the lowering of the molecular weight of the (meth) acrylic polymer (A2) is suppressed and thereby the hard coat layer having excellent blocking resistance and transparency is formed .

A compound having an isocyanate group and a photopolymerizable group is added to the polymer (II '). By adding a compound having an isocyanate group and a photopolymerizable group to a part of the hydroxyl groups of the polymer (II '), a (meth) acrylic polymer (A2) having a hydroxyl group and a photopolymerizable group in the side chain is obtained.

Examples of the compound having an isocyanate group and a photopolymerizable group include 2-isocyanatoethyl methacrylate (for example, trade name "CALENSE MOI" manufactured by Showa Denko K.K.), 1,1- Acryloyloxymethyl) ethyl isocyanate (for example, trade name "CALENZ BEI" manufactured by Showa Denko K.K.), 2-isocyanatoethyl acrylate [for example, available from Showa Denko K.K. , (Meth) acryloyl isocyanate in which the (meth) acryloyl group is bonded to an isocyanate group through an alkylene group having 2 to 6 carbon atoms, and derivatives thereof. Examples of the (meth) acryloyl isocyanate include 2-methacryloyloxyethyl isocyanate and the like.

As the derivative, for example, (meth) acrylate having an isocyanate group masked with a block group can be given. Specific examples thereof include methacrylic acid 2- (O- [1'-methylpropylideneamino] carboxyamino) ethyl [for example, trade name "CALENSE MOI-BM" manufactured by Showa Denko Co., [(3,5-dimethylpyrazolyl) carbonylamino] ethyl methacrylate [for example, trade name "CALENS MOI-BP" manufactured by Showa Denko Co., Ltd.] and the like. The compounds having an isocyanate group and a photopolymerizable group may be used alone, or two or more of them may be used in combination. Among them, 2-isocyanatoethyl methacrylate is preferable.

In the addition of the compound having an isocyanate group and a photopolymerizable group to the polymer (II ') having a hydroxyl group, the ratio of the number of moles of the hydroxyl group (-OH) in the radically polymerizable monomer having a hydroxyl group used in the production of the polymer (II' The ratio (-NCO / -OH) of the number of moles of the group (-NCO) is preferably 0.05 to 0.9, more preferably 0.1 to 0.9. The hydroxyl value of the (meth) acrylic polymer (A2) can also be adjusted by adjusting the molar ratio.

An example of a more specific production method for the production method (3) of the (meth) acrylic polymer (A3) will be described. (III ') by radical polymerization in the presence of a radical polymerization initiator in the presence of a radically polymerizable monomer having a carboxyl group and, if necessary, an alkyl (meth) acrylate having no carboxyl group, . Then, a compound having a glycidyl group and a photopolymerizable group, and, if necessary, a catalyst are added to the reaction vessel. If necessary, polymerization inhibitors such as p-methoxyphenol and hydroquinone (HQ) may be added to the reaction vessel. Thereafter, the reaction solution is allowed to react for 6 to 12 hours while controlling the reaction liquid to be at 30 to 150 占 폚 while blowing oxygen into the reaction vessel if necessary, whereby a (meth) acrylic polymer having a photopolymerizable group and a hydroxyl group (A3) can be produced.

Examples of the radically polymerizable monomer having a carboxyl group used in the method (3) include an ethylenically unsaturated carboxylic acid or an anhydride thereof. Specifically,?,? - unsaturated carboxylic acids or salts thereof such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, and fumaric acid; ω-carboxy-polycaprolactone monoacrylate, phthalic acid monohydroxyethyl acrylate, and the like, and acrylic acid and methacrylic acid are preferable. Further, the radical polymerizable monomer having a carboxyl group may be used alone, or two or more kinds thereof may be used in combination.

The content of the radically polymerizable monomer having a carboxyl group in the monomer composition (III) is preferably from 10 to 90% by weight, and more preferably from 20 to 80% by weight. By setting the content of the radically polymerizable monomer having a carboxyl group to the lower limit value or more, a hard coat layer having a high crosslinking density and an excellent hardness can be formed. In addition, gelation at the time of synthesis of the (meth) acrylic polymer can be suppressed by setting the content of the radically polymerizable monomer having a carboxyl group to the upper limit value or less.

The monomer composition (III) preferably further contains an alkyl (meth) acrylate having no carboxyl group. Specific examples of the alkyl (meth) acrylate having no carboxyl group include the same alkyl (meth) acrylates having no glycidyl group in the above-mentioned method (1).

The content of the alkyl (meth) acrylate having no carboxyl group in the monomer composition (III) is preferably from 10 to 90% by weight, and more preferably from 20 to 80% by weight. By setting the content of the alkyl (meth) acrylate having no carboxyl group to the lower limit value or more, the gelation in the synthesis of the (meth) acrylic polymer can be suppressed. By setting the content of the alkyl (meth) acrylate having no carboxyl group to the upper limit value or less, a hard coat layer having a high crosslinking density and excellent hardness can be formed.

The monomer composition (III) may contain an alkyl (meth) acrylate having a hydroxyl group. Specific examples of the alkyl (meth) acrylate having a hydroxyl group include the same alkyl (meth) acrylates having a hydroxyl group in the above-mentioned method (1). By using an alkyl (meth) acrylate having a hydroxyl group, the hydroxyl value of the (meth) acrylic polymer (A3) can be adjusted.

The content of the alkyl (meth) acrylate having a hydroxyl group in the monomer composition (III) is preferably 90% by weight or less, more preferably 80% by weight or less, particularly preferably 10 to 90% by weight, % By weight is most preferred. By setting the content of the alkyl (meth) acrylate having a hydroxyl group to the lower limit value or more, the inorganic particles (B) and the organic particles (C) can be highly dispersed to improve the transparency and printability of the hard coat layer. On the other hand, by lowering the content of the alkyl (meth) acrylate having a hydroxyl group to the upper limit value or less, deterioration of transparency of the hard coat layer due to aggregation of the inorganic particles (B) and the organic particles (C) can be suppressed.

The monomer composition (III) may contain (meth) acrylate having an alicyclic group. Specific examples of the (meth) acrylate having an alicyclic group include the same as those of the (meth) acrylate having an alicyclic group in the above-mentioned method (1).

The content of the (meth) acrylate having an alicyclic group in the monomer composition (III) is preferably 80% by weight or less, and more preferably 60% by weight or less. By lowering the content of the (meth) acrylate having an alicyclic group to the upper limit value or less, the lowering of the molecular weight of the (meth) acrylic polymer (A3) is suppressed, thereby forming a hard coat layer excellent in blocking resistance and transparency .

A compound having a glycidyl group and a photopolymerizable group is added to the polymer (III '). The carboxyl group of the polymer (III ') and the glycidyl group of the compound react with each other to form an ester bond, and a new hydroxyl group can be produced. At the same time, the photopolymerizable group can be introduced. Thus, a (meth) acryl-based polymer (A3) having a photopolymerizable group such as a vinyl group and a hydroxyl group in the side chain is obtained.

Specific examples of the compound having a glycidyl group and a photopolymerizable group include glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and allyl glycidyl ether. Glycidyl (meth) acrylate is preferred. The compounds having a glycidyl group and a photopolymerizable group may be used alone or in combination of two or more.

When a compound having a glycidyl group and a photopolymerizable group is added to the polymer (III ') having a glycidyl group, the glycidyl group and the glycidyl group for the carboxyl group in the radically polymerizable monomer having a carboxyl group used for preparing the polymer (III' The molar ratio of the glycidyl group (mole number of glycidyl group / mole number of carboxyl group) in the compound having a photopolymerizable group is preferably from 0.3 to 1.5, more preferably from 0.5 to 1.2, still more preferably 1.0. As described above, the glycidyl group reacts with the carboxyl group to form an ester bond, and also forms a hydroxyl group. Therefore, the hydroxyl value of the (meth) acrylic polymer (A3) can be adjusted by adjusting the molar ratio.

In the above methods (1) to (3), the monomer composition (I), (II) or (III) is subjected to radical polymerization in the presence of a radical polymerization initiator. As the radical polymerization initiator, those generally used in radical polymerization are used. Examples of the radical polymerization initiator include organic peroxides such as benzoyl peroxide, lauroyl peroxide, caproyl peroxide, t-hexyl peroxyneodecanate and t-butyl peroxy pivalate; Azobis-isobutyronitrile, 2,2-azobis-2,4-dimethylvaleronitrile, 2,2-azobis-4-methoxy-2,4-dimethylvaleronitrile, azo Azo compounds such as bis-2-methylbutyronitrile (trade name " ABN-E ", manufactured by Nihon Hydrazine Coatings Co., Ltd.) and azo compounds are preferable. The radical polymerization initiator may be used alone or in combination of two or more.

As the polymerization methods of the monomer compositions (I), (II) and (III), a general method is used, but emulsion polymerization (including suspension polymerization) and solution polymerization are preferred.

In emulsion polymerization and solution polymerization, the monomer composition (I), (II) or (III) is polymerized in a solvent. The solvent is not particularly limited as long as it is stable with respect to each of the monomers described above, and examples thereof include petroleum hydrocarbon solvents such as hexane and mineral spirit; Aromatic hydrocarbon solvents such as benzene, toluene and xylene; Ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, and cyclohexanone; Ester solvents such as methyl acetate, ethyl acetate, butyl acetate,? -Butyrolactone and propylene glycol monomethyl ether acetate; And aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone and pyridine. The solvent may be used alone, or two or more solvents may be used in combination. The mixing ratio of the solvent is not particularly limited and is suitably set according to the purpose and use.

Commercially available products may also be used as the solvent. Specific examples of the petroleum hydrocarbon solvent include Shin-Nippon Seki Chemical Co., Ltd., AF Solvent No. 4 to No. 7. Examples of the aromatic hydrocarbon solvents include Shin-Nippon Seki KK Ink Solvent No. 0, and Exxon Chemical Solvesso 100, 150, 200 and the like.

In the above-mentioned methods (1) to (3), it is preferable to add a catalyst in each reactor. Examples of the catalyst include dibutyltin dilaurate, dioctyltin laurate, dioctyltin dilaurate, triphenylphosphine, and bismuth-based catalysts.

The hydroxyl group value of the (meth) acrylic polymer (A) is limited to 10 to 350 mgKOH / g, but is preferably 30 to 330 mgKOH / g, more preferably 50 to 300 mgKOH / g. (Meth) acrylic polymer (A) having a hydroxyl value of at least the lower limit value, the hard coat layer can provide excellent printability. The inorganic particles B and the organic particles C can be highly dispersed by the (meth) acrylic polymer (A) having a hydroxyl value within the above range, ) Can be suppressed from lowering the transparency of the hard coat layer. The hydroxyl value of the (meth) acryl-based polymer (A) can be measured by the method described in the following Examples.

The (meth) acrylic equivalent of the (meth) acrylic polymer (A) is limited to 100 to 800 g / eq, but is preferably 200 to 700 g / eq, more preferably 300 to 600 g / eq. (A) having a (meth) acrylic equivalent of not more than the upper limit value can form a hard coat layer having a high hardness. The (meth) acrylic polymer (A) having a (meth) acryl equivalent in the above range can highly disperse the inorganic particles (B) and the organic particles (C) The deterioration of the transparency of the hard coat layer due to the addition of the particles (C) can be suppressed.

The (meth) acrylic equivalent of the (meth) acrylic polymer (A) means the number of grams of the (meth) acrylic polymer (A) per mole of the (meth) acryloyl group of the (meth) acrylic polymer .

(Meth) acrylic equivalent of the (meth) acrylic polymer (A) can be calculated from the monomer composition which is the raw material of the (meth) acrylic polymer (A) by the following formula (I).

[Wherein,

(G) of the monomer used for the raw material of the (meth) acrylic polymer (A) is referred to as " W &

(A) in the synthesis of the (meth) acrylic polymer (A), the number of moles of the monomer optionally selected from the monomers used for introducing the (meth) acryloyl group as the side chain Mol) is referred to as " M ", and the number of (meth) acryloyl groups per molecule of the monomer selected arbitrarily is referred to as "

The number of monomer species used for introducing a (meth) acryloyl group as a side chain in the main chain of the finally obtained (meth) acrylic polymer (A) in the synthesis of the (meth) acrylic polymer (A) It is said.]

The weight average molecular weight of the (meth) acrylic polymer (A) is limited to 10,000 to 200,000, but is preferably 30,000 to 170,000, more preferably 50,000 to 150,000, and particularly preferably 65,000 to 150,000. The (meth) acryl-based polymer (A) having a weight average molecular weight within the above range can disperse the inorganic particles (B) and the organic particles (C) in a highly dispersed state to form a hard-coded layer excellent in blocking resistance and transparency.

The weight-average molecular weight of the (meth) acrylic polymer (A) can be measured by polystyrene conversion using a gel permeation chromatograph (GPC). The measurement of the weight average molecular weight using GPC can be carried out specifically as follows. First, the molecular weight distribution of the (meth) acrylic polymer (A) is measured by a gel permeation chromatograph (GPC) equipped with a differential refractive index detector (RID) to obtain a chromatogram (chart). From this chromatogram, the weight average molecular weight of the (meth) acrylic polymer (A) can be calculated using standard polystyrene as a calibration curve. The weight average molecular weight of the (meth) acrylic polymer (A) can be measured by the method described in the following Examples.

The glass transition point (Tg) of the (meth) acrylic polymer (A) is limited to 50 to 110 占 폚, but is preferably 55 to 107 占 폚, more preferably 60 to 105 占 폚. (Meth) acrylic polymer (A) having a glass transition point of at least the lower limit value can form a hard coat layer having high hardness and excellent scratch resistance and blocking resistance. Further, according to the (meth) acrylic polymer (A) having a glass transition point within the above range, the inorganic particles (B) and the organic particles (C) can be highly dispersed to form a hard-coded layer excellent in blocking resistance and transparency . The glass transition point of the (meth) acrylic polymer (A) can be calculated by the formula of Fox.

The (meth) acrylic polymer (A) preferably contains 10 to 90% by weight of an alkyl (meth) acrylate component as a monomer component. The (meth) acrylic polymer (A) is obtained by radical polymerization of a monomer composition containing 10 to 90% by weight of an alkyl (meth) acrylate. According to the alkyl (meth) acrylate component, the organic particles (C) can be highly dispersed, whereby the transparency of the hard coat layer can be improved.

The alkyl (meth) acrylate used as the monomer component preferably has no glycidyl group or hydroxyl group. Specific examples of the alkyl (meth) acrylate include ethyl (meth) acrylate, methyl (meth) acrylate, n-butyl (meth) acrylate, hexyl acrylate, (Meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate and dodecyl (meth) acrylate. Among them, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate and butyl (meth) acrylate are preferable, and methyl (meth) acrylate is more preferable. According to the methyl (meth) acrylate, not only the organic particles (C) can be highly dispersed, but also a hard coat layer having high hardness can be formed.

The content of the alkyl (meth) acrylate component in the (meth) acrylic polymer (A) is preferably 10 to 90 wt%, more preferably 20 to 80 wt%, particularly preferably 30 to 80 wt% Most preferably from 40 to 70% by weight. That is, the content of the alkyl (meth) acrylate in the monomer composition is preferably 10 to 90% by weight, more preferably 20 to 80% by weight, particularly preferably 30 to 80% Is most preferable. When the content of the alkyl (meth) acrylate component is within the above range, a hard coat layer having excellent transparency and hardness can be formed.

The content of the (meth) acrylic polymer (A) in the photocurable resin composition is preferably such that the total amount of the (meth) acrylic polymer (A), the inorganic particles (B), the organic particles (C), and the photopolymerizable polyfunctional compound But is preferably 12 to 37% by weight, and more preferably 15 to 35% by weight. (B) and the organic particles (C) can be highly dispersed by setting the content of the (meth) acrylic polymer (A) to be not less than the lower limit value described above, thereby forming a hard-coded layer excellent in blocking resistance and transparency can do. By setting the content of the (meth) acrylic polymer (A) to the upper limit value or less, high hardness of the hard coat layer can be secured.

[Inorganic Particles (B)]

The photocurable resin composition of the present invention contains at least one kind of inorganic particles (B). According to the inorganic particles (B), a hard coat layer having high hardness and excellent scratch resistance and blocking resistance can be formed. On the surface of the inorganic particles (B), a polar group such as a hydroxyl group is often present. The above-mentioned (meth) acrylic polymer (A) having a predetermined hydroxyl value also has a hydroxyl group in the side chain. Therefore, the polarity of the inorganic particles (B) and the (meth) acrylic polymer (A) are close to each other, and electrostatic repulsion is suppressed. Therefore, it is possible to highly disperse the inorganic particles (B) by using the (meth) acrylic polymer (A), thereby suppressing the deterioration of the transparency of the hard coat layer by the addition of the inorganic particles The scratch resistance and blocking resistance of the layer can be improved. Further, the mechanism is presumed by the present inventors, and thus the present invention is not limited to the above mechanism.

Examples of the inorganic particles (B) include metal particles, metal oxide particles, metal sulfate particles, metal silicate particles, metal phosphate particles, metal carbonate particles, metal hydroxide particles, and fluorine compound particles. Among them, metal particles and metal oxide particles are preferable, and metal oxide particles are more preferable. The metal particles and the metal oxide particles are close to the polarity of the (meth) acrylic polymer (A) and can be highly dispersed by the (meth) acrylic polymer (A). The inorganic particles (B) may be used alone, or two or more kinds thereof may be used in combination.

Examples of metals included in the metal particles include Si, Ti, Mg, Ca, Zr, Sn, Sb, As, Zn, Nb, In and Al. Examples of the metal oxide contained in the metal oxide particles include oxides of metals such as Si, Ti, Mg, Ca, Zr, Sn, Sb, As, Zn, Nb, In and Al. Specific examples of the metal oxide particles include silicon oxide particles, titanium oxide particles, aluminum oxide particles, tin oxide particles, indium oxide particles, ITO particles, zinc oxide particles, zirconium oxide particles and magnesium oxide particles. Further, fine particles of a hetero-element-doped metal oxide doped with a hetero element such as Ab, Sn, F, P, Al or the like can be mentioned for these metal oxide particles.

As the inorganic particles (B), silicon oxide particles, aluminum oxide particles, zirconium oxide particles, and titanium oxide particles are preferable, and silicon oxide particles are more preferable.

The inorganic particles (B) may be inorganic particles dispersed in a colloidal form. The inorganic particles (B) may be surface-treated by a known method.

The shape of the inorganic particles (B) is not particularly limited, and examples thereof include bulk, spherical, hollow, porous, rod, plate, fibrous, and irregular shapes. (B) having different shapes may be used in combination.

The average particle diameter of the inorganic particles (B) is limited to 10 nm to 500 nm, preferably 10 nm to 400 nm, and more preferably 10 nm to 200 nm. It is difficult to highly disperse the inorganic particles (B) having an average particle diameter lower than the lower limit value, which may lower the transparency and antiblocking property of the hard coat layer. In addition, in the inorganic particles (B) having an average particle diameter exceeding the upper limit value, there is a fear of lowering the transparency, hardness, blocking resistance and printability of the hard coat layer. In the photocurable resin composition, the inorganic particles (B) exist as agglomerated particles such as primary particles or secondary particles. Therefore, the average particle diameter of the inorganic particles (B) is a value measured by a measuring method described later.

The average particle diameter of the inorganic particles (B) can be measured in the following manner. First, the photo-curing resin composition is diluted with methyl isobutyl ketone to obtain a diluted solution. The concentration of the inorganic particles (B) in the diluent is 0.1 to 1% by weight. Subsequently, the volume particle size distribution of the inorganic particles (B) was measured by a laser diffraction / scattering type particle size distribution analyzer (Nanotrac UPA-EX150 manufactured by Nikkiso Co., Ltd.) using a diluent, and the cumulative cumulative volume particle size distribution And the value of 50% can be calculated as the average particle diameter of the inorganic particles (B). Specific measurement conditions are as follows. The measured value of the average particle diameter of the inorganic particles obtained by the following measurement conditions is taken as the average particle diameter of the inorganic particles (B).

Number of measurements: 1 time

Measurement time: 180 seconds

Measuring temperature: 23 ° C

Measurement solvent: methyl isobutyl ketone

CI value: 0.4-0.8

Particle permeability: permeation

Sensitivity: Standard

Filter: Stand: Norm

Nano-range correction: invalid

The content of the inorganic particles (B) in the photo-curing resin composition is preferably in the range of 1 to 20 parts by weight based on the total weight of the (meth) acrylic polymer (A), the inorganic particles (B), the organic particles (C), and the photopolymerizable polyfunctional compound But is preferably 6 to 35% by weight, more preferably 7 to 30% by weight. If the content of the inorganic particles (B) is less than the above lower limit value, there is a possibility that excellent blocking resistance can not be imparted to the hard coat layer. If the content of the inorganic particles (B) exceeds the upper limit value, the transparency and printability of the hard coat layer may deteriorate. If the content of the inorganic particles (B) exceeds the upper limit value, the hard coat layer becomes too hard and cracks may easily occur.

[Organic Particles (C)]

The photocurable resin composition of the present invention contains at least one kind of organic particles (C). In the present invention, by using the inorganic particles (B) and the organic particles (C) in combination in the presence of the (meth) acrylic polymer (A), the printability of the hard coat layer can be improved. The mechanism by which such an effect is obtained is not clear, but can be estimated as follows. Further, the following mechanism is assumed by the present inventors, and therefore the present invention is not limited to the following mechanism.

As described above, the inorganic particles (B) can be highly dispersed by the hydroxyl groups of the (meth) acrylic polymer (A), but the majority of the hydroxyl groups of the (meth) acrylic polymer Is present toward the inside of the hard coat layer. The organic particles C have hydrophobicity and the hydroxyl groups which do not contribute to the dispersion of the inorganic particles B in the hydroxyl groups of the (meth) acrylic polymer (A) due to the hydrophobicity of the organic particles (C) It can be present toward the outside. Therefore, by using the inorganic particles (B) and the organic particles (C) in combination in the presence of the (meth) acrylic polymer (A), the number of hydroxyl groups present on the surface of the hard coat layer toward the outside can be increased. Such a hard coat layer has a large number of hydroxyl groups on the surface thereof, so that the wettability with respect to the ink is improved, whereby it is possible to perform printing with high precision without splashing the ink.

Examples of the organic particles (C) include particles containing a synthetic resin. Examples of the synthetic resin include polyamide resins, polyamideimide resins, polyacetal resins, (meth) acrylic resins, melamine resins, (meth) acryl-styrene copolymers, polycarbonate resins, styrene resins, Based resin, a fluororesin, a polyester resin, a cross-linked (meth) acrylic resin, a cross-linked polystyrene-based resin, a cross-linked polyurethane-based resin, and an epoxy resin. The organic particles (C) may be used singly or in combination of two or more.

Among them, as the organic particles (C), (meth) acrylic resin particles are preferable, and polyalkyl (meth) acrylate particles are more preferable. (Meth) acrylic resin particles have low polarity, a large number of hydroxyl groups of the (meth) acrylic polymer (A) can be present on the surface of the hard coat layer. (Meth) acrylate particles, polyethyl (meth) acrylate particles, polypropyl (meth) acrylate particles, polybutyl (meth) acrylate particles, polypentyl (Meth) acrylate particles, polyhexyl (meth) acrylate particles, polyhexyl (meth) acrylate particles, polyhexyl (meth) acrylate particles, polyhexyl (Meth) acrylate particles, polybenzyl (meth) acrylate particles, and polydicyclopentadienyl (meth) acrylate particles. Among them, polymethyl (meth) acrylate particles are preferred.

The average particle diameter of the organic particles (C) is limited to 10 nm to 500 nm, preferably 10 nm to 400 nm, and more preferably 50 nm to 300 nm. The organic particles (C) having an average particle diameter within the above range are highly dispersed, and a hydroxyl group which does not contribute to the dispersion of the inorganic particles (B) in the hydroxyl groups of the (meth) acrylic polymer . Thus, a hard coat layer having a large number of hydroxyl groups on its surface can be formed. In addition, the organic particles (C) having an average particle diameter exceeding the upper limit value may lower the transparency and hardness of the hard coat layer.

The average particle diameter of the organic particles (C) can be measured in the same manner as the above-mentioned method of measuring the average particle diameter of the inorganic particles (B). Further, in the photo-curing resin composition, the organic particles (C) exist as agglomerated particles such as primary particles or secondary particles. Therefore, the average particle diameter of the organic particles (C) is a value measured by the same method as the above-mentioned method of measuring the average particle diameter of the inorganic particles (B). The concentration of the organic particles (C) in the diluted solution is 0.1 to 1% by weight.

The content of the organic particles (C) in the photo-curable resin composition is preferably such that the total weight of the (meth) acrylic polymer (A), the inorganic particles (B), the organic particles (C), and the photopolymerizable polyfunctional compound But is preferably from 0.7 to 9% by weight, more preferably from 1 to 8% by weight. By setting the content of the organic particles (C) to the lower limit value or more, a hard coat layer having excellent blocking resistance and printability can be formed. By setting the content of the organic particles (C) to the upper limit value or less, excellent transparency of the hard coat layer can be ensured.

[Photopolymerizable polyfunctional compound (D)]

The photocurable resin composition of the present invention contains at least one photopolymerizable polyfunctional compound (D) having two or more photopolymerizable groups in one molecule. The photopolymerizable polyfunctional compound (D) can be subjected to radical polymerization with the (meth) acrylic polymer (A). Thereby, the photopolymerizable polyfunctional compound (D) can cross-link molecular chains of the (meth) acrylic polymer (A) to form a dense network structure. The inorganic particles (B) and the organic particles (C) can be introduced into such a dense mesh structure, whereby the inorganic particles (B) and the organic particles (C) Can be formed. Such a hard coat layer is excellent in transparency, blocking resistance and printing property because the inorganic particles (B) and the organic particles (C) are highly dispersed.

The photopolymerizable group contained in the photopolymerizable polyfunctional compound (D) is not particularly limited as long as it has a photopolymerizable group of the (meth) acrylic polymer (A) and an ethylenically unsaturated double bond capable of radical polymerization, and an acryloyl group, a methacryloyl group, A vinyl group, and an allyl group, and an acryloyl group and a methacryloyl group are preferable.

Examples of the photopolymerizable polyfunctional compound (D) having two photopolymerizable groups in one molecule include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di Alkylene glycol di (meth) acrylate; (Meth) acrylates such as diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate and tripropylene glycol di Rate; Acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, dicyclopentadienedi (meth) acrylate, neopentyl Glycol adipate di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, dicyclopentanyl di (meth) acrylate; (Meth) acrylate, ethylene oxide modified di (meth) acrylate, allylated cyclohexyldi (meth) acrylate, bisphenol AEO added diacrylate, caprolactone modified dicyclopentenyl di (Meth) acrylate or an alkylene oxide modified product thereof, divinylbenzene, butanediol-1,4-divinyl ether, cyclohexanedimethanol divinyl ether, diethylene glycol divinyl ether, Dipropylene glycol divinyl ether, dipropylene glycol divinyl ether, hexanediol divinyl ether, triethylene glycol divinyl ether, phenylglycidyl ether acrylate hexamethylene diisocyanate urethane oligomer [manufactured by Kyoeisha Chemical Co., Ltd. Trade name " AH-600 "), phenylglycidyl ether acrylate, toluene diisocyanate urethane oligomer (manufactured by Kyoeisha Chemical Co., The trade name can be given the "AT-600"] and the like. The photopolymerizable polyfunctional compound (D) may be used singly or in combination of two or more.

Examples of the photopolymerizable polyfunctional compound (D) having three photopolymerizable groups in one molecule include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri , Tris (acryloxyethyl) isocyanurate, and tri (meth) acrylates of an alkylene oxide modified product thereof and an isocyanuric acid alkylene oxide modified product.

Examples of the photopolymerizable polyfunctional compound (D) having four photopolymerizable groups in one molecule include ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, and alkylene oxide modified products thereof .

Examples of the photopolymerizable polyfunctional compound (D) having 5 photopolymerizable groups in one molecule include dipentaerythritol penta (meth) acrylate or an alkylene oxide modified product thereof.

Examples of the photopolymerizable polyfunctional compound (D) having six photopolymerizable groups in one molecule include dipentaerythritol hexa (metha) acrylate, pentaerythritol triacrylate hexamethylene diisocyanate urethane oligomer (available from Kyoeisha Chemical Co., (UA-306H), caprolactone-modified dipentaerythritol hexa (meth) acrylate, and alkylene oxide-modified products thereof.

As the photopolymerizable polyfunctional compound (D), an oligomer having two or more photopolymerizable groups in one molecule is preferable. Examples of the oligomer include urethane (meth) acrylate, polyester (meth) acrylate, and epoxy (meth) acrylate. Of these, urethane (meth) acrylate oligomers are more preferable. The urethane (meth) acrylate oligomer is obtained by reacting an isocyanate-terminated urethane prepolymer obtained by reacting a polyol and a polyisocyanate with a (meth) acrylate monomer having at least one hydroxyl group in one molecule.

Examples of the urethane (meth) acrylate oligomer include phenylglycidyl ether acrylate hexamethylene diisocyanate urethane oligomer, phenyl glycidyl ether acrylate toluene diisocyanate urethane oligomer, and pentaerythritol triacrylate hexamethylene diisocyanate urethane oligomer. .

The number of photopolymerizable groups contained in one molecule of the photopolymerizable polyfunctional compound (D) is preferably from 3 to 20, more preferably from 4 to 20, and particularly preferably from 5 to 15. The photopolymerizable polyfunctional compound (D) having the number of photopolymerizable groups within the above range can form a dense crosslinked structure, thereby providing a hard coat layer excellent in transparency, hardness, blocking resistance and printability .

The content of the photopolymerizable polyfunctional compound (D) in the photocurable resin composition is preferably such that the sum of the (meth) acrylic polymer (A), the inorganic particles (B), the organic particles (C), and the photopolymerizable polyfunctional compound But is preferably from 23 to 65% by weight, and more preferably from 25 to 60% by weight. By setting the content of the photopolymerizable polyfunctional compound (D) to the lower limit value or more, excellent hardness of the hard coat layer can be secured. When the content of the photopolymerizable polyfunctional compound (D) is made not more than the upper limit value, the inorganic particles (B) and the organic particles (C) are highly dispersed, A coat layer can be formed.

(Photopolymerization initiator)

It is preferable that the photocurable resin composition of the present invention further comprises a photopolymerization initiator. As the photopolymerization initiator, for example, a benzoin ether photopolymerization initiator, a benzophenone photopolymerization initiator, a thioxanthone photopolymerization initiator, an alkylphenon photopolymerization initiator, an acylphosphine oxide photopolymerization initiator, a titanocene photopolymerization initiator, Initiators, diazodiphenylamine photopolymerization initiators, naphthoquinone diazosulfonic acid photopolymerization initiators, dimethylaminobenzoic acid photopolymerization initiators, and the like. The photopolymerization initiator may be used alone, or two or more thereof may be used in combination.

Examples of the benzoin ether photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

Examples of the benzophenone-based photopolymerization initiator include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenylsulfide, 2,4,6- .

Examples of the thioxanthone photopolymerization initiator include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4- .

Examples of the alkylphenon-based photopolymerization initiator include 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1,2-diphenylethane- Hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- Methyl-l- (4-methylthiophenyl) - < / RTI > 2-dimethylamino-1- (4-morpholinophenyl) -butanone-l, 2- (dimethylamino) -2 - [(4-methylphenyl) ) Methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone.

Examples of the acylphosphine oxide photopolymerization initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide.

Examples of the titanocene photopolymerization initiator include bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H- Titanium, and the like.

Examples of the oxime ester photopolymerization initiator include 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone- 1- [ Oxo-2-phenylacetoxyethoxy] ethyl ester, oxy-phenyl-acetic acid 2- [2- Phenyl-acetic acid 2- (2-hydroxyethoxy) ethyl ester and the like.

The content of the photopolymerization initiator in the photocurable resin composition is preferably 0.1 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, and particularly preferably 1 to 5 parts by weight per 100 parts by weight of the (meth) acrylic polymer (A) . By setting the content of the photopolymerization initiator to the lower limit value or more, the photocuring property of the photocurable resin composition can be sufficiently promoted. Further, by setting the content of the photopolymerization initiator to the upper limit value or less, it is possible to suppress the hardness of the hard coat layer caused by the decomposition product of the photopolymerization initiator from lowering.

(Photopolymerizable monofunctional compound)

The photocurable resin composition of the present invention may contain a photopolymerizable monofunctional compound having one photopolymerizable group in one molecule. The photopolymerizable monofunctional compound is used to adjust the viscosity of the photocurable resin composition and to improve the dryness of the photocurable resin composition by increasing the solid concentration.

Examples of the photopolymerizable monofunctional compound include aliphatic (meth) acrylates, alicyclic (meth) acrylates, aromatic (meth) acrylates, ether (meth) acrylates, vinyl monomers, Amides and the like. In the present invention, (meth) acrylamide means acrylamide or methacrylamide.

Examples of the photopolymerizable monofunctional compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl (meth) acrylate, lauryl (meth) (Meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, isooctyl (meth) acrylate, isomyristyl (Meth) acrylate, 2-ethylhexyl-carbitol (meth) acrylate, neopentyl glycol benzoate (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, ECH-modified phenoxy ) Acrylate, phenoxyethyl (meth) acrylate, para-cumylphenol ethylene oxide-modified (meth) acrylate, vinylpyrrolidone, vinylcaprolactam and acryloylmorpholine.

(Surfactants)

The photocurable resin composition of the present invention may contain a surfactant. By using a surfactant, the printability of the hard coat layer can be improved.

Examples of the surfactant include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants. It is preferable that the surfactant has a functional group having active hydrogen. Examples of the functional group having an active hydrogen include a hydroxyl group, a carboxyl group, an amino group, and an amide group.

As the anionic surfactant, there may be mentioned, for example, castor oil monosulfate, castor oil monophosphate, sorbitan fatty acid ester sulfate, sorbitan fatty acid ester phosphate, polyoxyalkylene glycerin ether monosulfate, polyoxyalkylene glycerin ether monophosphate, And a fluoroalkyl ester phosphate.

Examples of the cationic surfactant include a dialkanolamine salt, a polyoxyalkylene alkylamine ether salt, a polyoxyalkylene alkylammonium salt, and a polyoxyalkylene dialkanolamine ether salt.

Examples of the nonionic surfactant include polyoxyethylene polyoxypropylene block polymer, sorbitan fatty acid ester, polyoxyalkylene sorbitan fatty acid ester, polyglycerin fatty acid ester, and the like.

Examples of the amphoteric surfactant include N, N-di (beta -hydroxyalkyl) N-hydroxyethyl-N-carboxyalkylammonium betaine, N, N-di (polyoxyethylene) - sulfoalkylammonium betaine, and perfluoroalkylbetaine.

(Silane coupling agent)

The photocurable resin composition of the present invention may contain a silane coupling agent. By using a silane coupling agent, the printability of the hard coat layer can be improved.

Examples of the silane coupling agent include epoxy group-containing silane coupling agents such as glycidoxypropyltrimethoxysilane and glycidoxypropyltriethoxysilane; Amino group-containing silane coupling agents such as aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, and aminopropyltriethoxysilane; A mercapto group-containing silane coupling agent such as mercaptopropyltrimethoxysilane; A urethane group-containing silane coupling agent such as ureido propyl triethoxysilane; And isocyanate group-containing silane coupling agents such as isocyanatepropyltriethoxysilane.

The photocurable resin composition of the present invention may contain a solvent. By using a solvent, the viscosity of the photo-curable resin composition can be adjusted, thereby improving the handling property and the coatability of the photo-curable resin composition. The solvent is not particularly limited and the same solvents as those used for the polymerization of the monomer composition in the emulsion polymerization and solution polymerization described above may be mentioned.

The photo-curable resin composition of the present invention may contain other additives if necessary within the range not impairing its physical properties. Other additives include, for example, antioxidants, light stabilizers, heat stabilizers, antistatic agents, antifoaming agents and the like.

The photocurable composition of the present invention is preferably used to form a cured film on one side of a substrate. The cured film obtained by curing the photo-curing composition has excellent transparency, hardness, scratch resistance, blocking resistance, and printability. Therefore, such a cured film can be used as a hard coat layer.

As a method of forming a cured film of the photo-curable resin composition, there is a method of applying a photo-curable resin composition to at least one surface of a base material and a method of obtaining a cured film by photo-curing the applied photo- do. Examples of the active energy ray include ultraviolet rays, electron rays, alpha rays, beta rays, and gamma rays, but ultraviolet rays and electron beams are preferable. When an active energy ray is irradiated to a photocurable resin composition not containing a photopolymerization initiator, an electron beam is preferably used as an active energy ray.

The irradiation with ultraviolet rays can be performed using an ultraviolet irradiation apparatus having a light source such as a xenon lamp, a high-pressure mercury lamp, and a metal halide lamp. When a high-pressure mercury lamp is used as the light source, it is preferable to irradiate ultraviolet light by transporting the substrate coated with the photo-curable resin composition to the high-pressure mercury lamp 1 at a conveying speed of 5 to 50 m / min. At this time, the light amount of the high-pressure mercury lamp is preferably 80 to 160 W / cm.

When the electron beam is used as the light source, the substrate coated with the photo-curable resin composition is preferably transported at an electron beam accelerating device having an acceleration voltage of 10 to 300 kV at a transport speed of 5 to 50 m / min to irradiate an electron beam .

The material of the base material is not particularly limited, and examples thereof include polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polycarbonate resins, polyacrylic resins, styrene resins, ABS resins, triacetylcellulose, Synthetic resins such as olefin resins, inorganic materials such as glass, and metals such as stainless steel, steel and aluminum.

Examples of the method of applying the photocurable resin composition to a substrate include a coating method using a dip coating method, a spray coating method, a roll coating method, a doctor blade method, a screen printing method, etc., a casting method using a bar coater, .

The thickness of the coating film after drying of the photocurable resin composition applied on the substrate is not particularly limited, but is preferably 2 to 90 占 퐉, more preferably 5 to 50 占 퐉.

The applied photo-curable resin composition may be heated before light irradiation to remove the solvent and the like contained in the photo-curable resin composition.

The cured film of the photo-curing resin composition has improved physical properties such as hardness, scratch resistance, blocking resistance, transparency and printability by using the inorganic particles (B) and the organic particles (C) in combination as described above. Originally, when the inorganic particles and the organic particles have different refractive indices and are used in combination with the inorganic particles and the organic particles, the inorganic particles and the organic particles easily aggregate due to the electrostatic repulsion between them. As a result, the combined use of the inorganic particles and the organic particles lowers the transparency of the cured film. However, in the present invention, the inorganic particles (B) and the organic particles (C) are highly dispersed using the (meth) acrylic polymer (A) Can be greatly reduced.

The cured film of the photo-curing resin composition has excellent transparency. The haze of the cured film of the photocurable resin composition is preferably 1.0% or less, more preferably 0.8% or less. The haze of the cured film is a value measured in accordance with JIS K 7136 (2000).

The cured film of the photocurable resin composition has excellent hardness. The hardness of the cured film of the photocurable resin composition is preferably a pencil hardness of H or more, more preferably 2H or more. The pencil hardness refers to a value measured by a pencil hardness test according to JIS K 5600-5-4 (1999).

The cured film of the photo-curing resin composition has a low dynamic friction coefficient and excellent blocking resistance. The coefficient of dynamic friction of the cured film of the photo-curable resin composition is preferably 0.6 N or less, more preferably 0.5 N or less. The coefficient of dynamic friction is a value measured in accordance with JIS K 7125 (1999).

The cured film of the photo-curable resin composition has excellent wettability with respect to ink, and printability is improved. The wet tension of the surface of the cured film of the photo-curable resin composition is preferably 35 dyn / cm or more, more preferably 40 dyn / cm or more. The wetting strength of the surface of the cured film of the photo-curing resin composition is measured in accordance with JIS K 6768 (1999).

The thickness of the cured film of the photo-curable resin composition is preferably 2 to 90 占 퐉, more preferably 5 to 50 占 퐉, from the viewpoint of obtaining a cured film excellent in hardness, scratch resistance, blocking resistance and printability.

The cured film of the photocurable resin composition of the present invention is preferably used as a hard coat layer in order to protect the substrate surface. It is preferable that functional layers other than the hard coat layer are laminated and integrated on the cured film. Since the cured film of the photo-curing resin composition has excellent printability, a functional layer having a desired pattern shape and uniform thickness can be formed on the cured film.

Examples of the functional layer include an electromagnetic wave shielding layer, a heat ray reflective layer, an ultraviolet shielding layer, a gas barrier layer, an antireflection layer, a conductive layer, a hard coat protective layer, an antiglare layer, an adhesive layer and an antistatic layer. These functional layers can be formed by a known method.

For example, a conductive laminated film in which a transparent conductive layer is laminated and integrated on a cured film of a photo-curable resin composition is preferably used for a touch panel. Since the cured film of the photo-curable resin composition of the present invention has excellent transparency as well as printability, it is possible to form a transparent conductive layer having a fine pattern shape and excellent transparency on the cured film, It is possible to provide a conductive laminated film which is difficult to be visually recognized and has high transmittance of visible light.

The conductive laminated film includes a transparent substrate, a cured film of a photo-curable resin composition laminated and integrated on one surface of the transparent substrate, and a transparent conductive layer laminated and integrated on one surface of the cured film.

The transparent substrate includes a transparent synthetic resin. Examples of the transparent synthetic resin include a polyester resin, an acetate resin, a polyether sulfone resin, a polycarbonate resin, a polyamide resin, a polyimide resin, a polyolefin resin, a (meth) acrylic resin, a polyvinyl chloride resin, Polyvinylidene chloride resins, polystyrene resins, polyvinyl alcohol resins, polyarylate resins, polyphenylene sulfide resins, and the like. The thickness of the transparent substrate is preferably 2 to 200 mu m, more preferably 2 to 100 mu m.

The transparent conductive layer may be laminated and integrated on the cured film of the photo-curing resin composition through the adhesive layer. The adhesive layer contains a known adhesive. As the adhesive, for example, an acrylic adhesive, a silicone adhesive, a polyester adhesive and the like are used. By applying a composition containing an adhesive on the cured film, an adhesive layer having a uniform thickness can be formed.

Examples of the constituent material of the transparent conductive layer include at least one selected from the group consisting of indium, tin, zinc, gallium, antimony, titanium, silicon, zirconium, magnesium, aluminum, gold, silver, copper, palladium, and tungsten Of an oxide of a metal. The transparent conductive layer has a pattern shape such as a stripe shape depending on the application in which the conductive laminated film is used.

As a method for forming the transparent conductive layer, a known method is used. For example, a method of printing a conductive paste is preferable. The cured film of the photo-curable resin composition has a high polarity because a large number of hydroxyl groups exist on the surface as described above. Thus, the cured film of the photo-curable resin composition and the transparent conductive layer can be firmly laminated and integrated. Therefore, the method of forming the transparent conductive layer is not limited to the printing method, and a vapor deposition method, a sputtering method, and the like are also preferably used.

The conductive laminated film is preferably used for a capacitive touch panel. The touch panel is not particularly limited, but is provided on the front surface of the display panel of the information terminal apparatus. Examples of the information terminal apparatus include a cellular phone, a portable information terminal (PDA), a portable game machine, a digital camera, a personal computer, a television, and the like.

Example

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

(Conducting Synthesis Examples 1 to 9 and Comparative Synthesis Examples 1 to 8)

Synthesis of (meth) acrylic polymer

400 parts by weight of methyl isobutyl ketone (MIBK) as a solvent was supplied into the reaction vessel, and the mixture was heated to 90 占 폚 and held.

(MMA), isobornyl methacrylate (IBXMA), glycidyl methacrylate (GMA), 2-hydroxyethyl methacrylate (2-HEMA), butyl acrylate (BA) Azobis-2-methylbutyronitrile (ABN-E) as a polymerization initiator was mixed in the amounts shown in Tables 1 and 2 to obtain a monomer composition.

Then, the monomer composition was slowly added dropwise to the reaction vessel over a period of 2 hours, and the mixture was allowed to stand over 4 hours, followed by heating at 120 占 폚 for 1 hour to obtain a polymer by radical polymerization.

Subsequently, the polymer was cooled to 60 DEG C, and then acrylic acid (AA), 2-isocyanatoethyl methacrylate (MOI), paramethoxyphenol (MQ) as a polymerization inhibitor and triphenylphosphine TPP) and dibutyltin dilaurate (DBTDL) were mixed in the amounts shown in Tables 1 and 2, respectively, to obtain a mixture. Thereafter, the mixture was heated to 110 DEG C over 8 hours while oxygen was blown into the reaction vessel to add acrylic acid (AA) or 2-isocyanatoethyl methacrylate (MOI) to the polymer, (Meth) acrylic polymer having a photopolymerizable group and a hydroxyl group.

The (meth) acrylic equivalent, the weight average molecular weight, and the glass transition point of the obtained (meth) acryl-based polymer were measured in the following manner. The results are shown in Tables 1 and 2.

(Hydroxyl group)

The hydroxyl value of the (meth) acryl-based polymer is measured according to 4.2 B of JIS K 1557-1: 2007 (ISO 14900: 2001) "Plastics - Test method for polyurethane raw material polyol - Part 1: did. The hydroxyl value of the (meth) acryl-based polymer means the hydroxyl value of the solid content.

[(Meth) acryl equivalent]

The (meth) acrylic equivalent of the (meth) acrylic polymer was calculated from the monomer composition as the raw material of the (meth) acrylic polymer by the above formula (I).

(Weight average molecular weight)

A 0.2 mg sample was taken from a (meth) acrylic polymer, dissolved in 10 milliliters of tetrahydrofuran, and the molecular weight distribution of the sample was measured by gel permeation chromatography (GPC) equipped with a differential refractive index detector (RID) A chromatogram (chart) was obtained.

Then, the weight average molecular weight and number average molecular weight of the sample were calculated from the obtained chromatogram (chart) using standard polystyrene as a calibration curve. The measurement apparatus and measurement conditions are shown below.

Data processing apparatus: product name HLC-8220GPC (manufactured by Tosoh Corporation)

Differential Refractive Index Detector: RI detector embedded in HLC-8220GPC

Column: Product name TSKgel GMH _XL (made by Tosoh Corporation) 3

Mobile phase: tetrahydrofuran

Column flow rate: 0.5 mL / min

Injection volume: 20 μL

Measuring temperature: 40 ° C

Standard polystyrene molecular weight: 1250, 3250, 9200, 28500, 68000, 165000, 475000, 950000, 1900000

(Glass transition point)

The glass transition point of the (meth) acrylic polymer was calculated by Fox's formula.

(Examples 1 to 25 and Comparative Examples 1 to 20)

The silicon oxide particles (B1) having an average particle diameter (MD) of 10 nm, the silicon oxide particles (B2) having an average particle diameter of 100 nm as the inorganic particles (B) (B3) having a mean particle diameter of 100 nm, titanium oxide particles (B4) having an average particle diameter of 100 nm, zirconium oxide particles (B5) having an average particle diameter of 100 nm, and silicon oxide particles , Polymethyl methacrylate (PMMA) particles (C1) having an average particle diameter of 20 nm as the organic particles (C), polymethylmethacrylate (PMMA) particles (C2) having an average particle diameter of 100 nm, Polymethyl methacrylate (PMMA) particles (C3) having a diameter of 400 nm, styrene type resin particles (C4) having an average particle diameter of 100 nm, melamine resin particles (C5) having an average particle diameter of 100 nm, Polymethyl methacrylate (PMMA) particles (C6) having a particle size of 1000 nm, a pentaerythritol triacrylate Acrylate hexamethylene diisocyanate urethane oligomer a, and methyl isobutyl ketone [trade name: "UA-306H" of the T Ischia Kagaku Co., Ltd.] and uniformly mixed to prepare a pre-mixed solution.

The (meth) acrylic polymer prepared in Examples 1 to 9 and Comparative Synthesis Examples 1 to 8 was slowly added dropwise to the preliminary mixed solution over a period of 10 minutes so that the blend amount shown in Tables 3 to 7 was obtained in terms of solid content. After completion of the dropwise addition, the premix solution was stirred at 30 占 폚 for 30 to 60 minutes.

Then, 2-hydroxy-2-methyl-1-phenyl-propan-1-one (product name "DAROCUR 1173" manufactured by BASF) as a photopolymerization initiator was added to the preliminary mixed solution in the amounts shown in Tables 3 to 7, To obtain a photo-curable resin composition. The average particle diameters of the inorganic particles (B1) to (B6) and the organic particles (C1) to (C6) in the obtained photo-curable resin composition were measured by the measurement method described above. Was the same as the average particle diameter of the inorganic particles (B1) to (B6) and the organic particles (C1) to (C6) used for preparing the preliminary mixed solution.

The photo-curable resin composition was applied on a polyethylene terephthalate (PET) film using a bar coater so that the dry film thickness was 5 mu m. Thereafter, the photo-curing resin composition was heated at 80 占 폚 for 2 minutes to remove the solvent. Then, the photo-curable resin composition was irradiated with ultraviolet rays at a cumulative light quantity of 500 mJ / cm2 using a high-pressure mercury lamp (light amount 120 W / cm) The photo-curing resin composition was photo-cured to form a cured film (thickness: 5 m).

[evaluation]

The appearance of the cured film, pencil hardness, haze, blocking resistance, and printability were evaluated according to the following procedures. The results are shown in the formulations shown in Tables 3 to 7.

(Exterior)

The appearance of the cured film was evaluated in accordance with the test method of 4.4 " Appearance of Coating Film " of JIS K 5600-1-1. In Tables 3 to 7, " right " and " column "

Right: The cured film was colorless transparent and had no cracks.

Heat: At least one of occurrence of cloudiness and generation of cracks occurred in the cured film.

(Pencil hardness)

The pencil hardness of the cured film was measured by a pencil hardness test according to JIS K 5600-5-4 (1999).

(Hayes)

The haze (%) of the cured film was measured by a haze meter according to JIS K 7136 (2000).

(Blocking resistance)

Two PET films on which a cured film was formed were prepared. These PET films were stacked so that the cured films were opposed to each other to obtain a laminate. The laminate was heated at 80 占 폚 for 12 hours while applying a load of 5 kg onto this laminate. Thereafter, one PET film was stretched in a direction parallel to the surface of the cured film at a tensile speed of 10 mm / min, and the coefficient of dynamic friction (N) at that time was measured in accordance with JIS K 7125 (1999).

(Printability)

The printability of the cured film was evaluated by measuring the wet tension (dyn / cm) on the surface of the cured film in accordance with JIS K 6768 (1999).

(Industrial availability)

According to the present invention, it is possible to provide a photo-curing resin composition capable of forming a hard coat layer having improved blocking resistance without deteriorating transparency and also having excellent printability.

Claims (6)

(Meth) acrylate equivalent weight of 100 to 800 g / eq, a weight average molecular weight of 10,000 to 200,000, a glass transition point of 50 to 110 占 폚, and a photopolymerizable group and a hydroxyl group (Meth) acryl-based polymer (A)
An inorganic particle (B) having an average particle diameter of 10 nm to 500 nm,
(C) having an average particle diameter of 10 nm to 500 nm,
(D) having at least two photopolymerizable groups in one molecule, and the photopolymerizable polyfunctional compound
Based on the total weight of the (meth) acrylic polymer (A), the inorganic particles (B), the organic particles (C), and the photopolymerizable polyfunctional compound (D)
The content of the (meth) acrylic polymer (A) is 10 to 40% by weight,
, The content of the inorganic particles (B) is 5 to 40% by weight,
The content of the organic particles (C) is 0.5 to 10% by weight,
Wherein the content of the photopolymerizable polyfunctional compound (D) is 20 to 70% by weight. The method according to claim 1,
Wherein the (meth) acrylic polymer (A) contains 10 to 90% by weight of an alkyl (meth) acrylate component. The method according to claim 1,
Wherein the inorganic particles (B) are at least one of metal particles and metal oxide particles. The method according to claim 1,
Wherein the organic particles (C) are (meth) acrylic resin particles. The method according to claim 1,
A photopolymerization initiator, and a photopolymerization initiator. A cured film formed by curing the photo-curable resin composition according to claim 1.