JP5981750B2 - Hard coat resin composition, cured product thereof, and method for producing cured product - Google Patents

Description

  The present invention relates to a hard coat resin composition having a high refractive index and hardness, a cured product thereof (such as a cured film), and a method for producing the cured product.

  As a material having a high refractive index and a hard coat property or scratch resistance as an optical material application such as optical overcoat agent, hard coat agent, antireflection film, spectacle lens, optical fiber, optical waveguide, hologram, etc. A curable resin composition containing a monomer having a 9,9-bisphenoxyfluorene skeleton has been proposed.

  For example, JP-A-2007-84815 (Patent Document 1) discloses a hard coat layer used in an optical laminate, and a monomer having a 9,9-bisphenoxyfluorene skeleton having at least one functional group, A hard coat layer containing a trifunctional or higher functional urethane (meth) acrylate and / or a trifunctional or higher functional (meth) acrylate resin and a permeable solvent is disclosed. In this document, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) are given as specific examples of tri- or higher functional (meth) acrylate resins. ) Acrylate, dipentaerythritol tetra (meth) acrylate, isocyanuric acid-modified tri (meth) acrylate, and the like. In the examples, curable resin compositions containing 9,9-bis [4- (2-acryloyloxyethoxy) phenylfluorene, dipentaerythritol hexaacrylate and polyethylene glycol diacrylate are described.

  JP-A 2007-58111 (Patent Document 2) discloses a hard coat layer used in an optical laminate, and a monomer having a 9,9-bisphenoxyfluorene skeleton having at least one functional group; A hard coat layer containing a monomer containing at least two or more sulfur atoms, a trifunctional or higher functional urethane (meth) acrylate and / or a trifunctional or higher functional (meth) acrylate resin, and a penetrating solvent is disclosed. This document also describes dipentaerythritol hexa (meth) acrylate and the like as specific examples of trifunctional or higher functional (meth) acrylate resins.

  However, in these curable resin compositions, the hardness of the cured product is low, and when it is laminated on a substrate film, it is easily curled by curing shrinkage and has low adhesion. Furthermore, the composition of Patent Document 2 is intensely colored, has low transparency, is easily gelled, and has low storage stability.

JP 2007-84815 A (Claims, paragraph [0017], Examples) JP 2007-58111 A (claims, paragraph [0018], examples)

  Accordingly, an object of the present invention is to provide a hard coat resin composition having a high hardness and refractive index of a cured product, a cured product thereof, and a method for producing the cured product.

  Another object of the present invention is to provide a hard coat resin composition having a high hardness even if it is thin, a cured product thereof, and a method for producing the cured product.

  Still another object of the present invention is to provide a hard coat resin composition capable of suppressing curling even when laminated on a base film and improving adhesion, a cured product thereof, and a method for producing the cured product.

  Another object of the present invention is to provide a hard coat resin composition having high transparency and excellent handling properties, a cured product thereof, and a method for producing the cured product.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that a fluorene-containing (meth) acrylate having at least one (meth) acryloyl group in the molecule and having a 9,9-bisarylfluorene skeleton, The present inventors have found that the hardness and refractive index of a cured product can be improved by combining with a polyfunctional (meth) acrylate having 10 or more (meth) acryloyl groups in the molecule.

  That is, the hard coat resin composition of the present invention includes a fluorene-containing (meth) acrylate having at least one (meth) acryloyl group in the molecule and having a 9,9-bisarylfluorene skeleton, And a polyfunctional (meth) acrylate having 10 or more (meth) acryloyl groups. The polyfunctional (meth) acrylate may have 50 to 200 (meth) acryloyl groups in the molecule. The weight average molecular weight of the polyfunctional (meth) acrylate may be about 10,000 to 30,000. The polyfunctional (meth) acrylate may be a (branched) (meth) acrylate having a polyhydric alcohol as a nucleus. The polyfunctional (meth) acrylate may be a polyfunctional (meth) acrylate obtained by condensing a poly (meth) acrylate of a polyhydric alcohol having 4 to 8 methylol groups with a crosslinking agent.

  The fluorene-containing (meth) acrylate may be a compound represented by the following formula (1).

(In the formula, the rings Ar are the same or different and are aromatic hydrocarbon rings; A is the same or different and an alkylene group; R ¹ is the same or different and represents a hydrogen atom or a methyl group; and R ² is the same or different and is a halogen atom. , An alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, a cycloalkyloxy group, an aryloxy group, an aralkyloxy group, an acyl group, a nitro group, a cyano group, or a substituted amino group, and R ³ is the same or Differently represents a halogen atom, a cyano group or an alkyl group, n is 0 or an integer of 1 to 10, m is an integer of 1 to 3, q is an integer of 0 or 1 to 3, and r is an integer of 0 or 1 to 3. Indicates)
In the formula (1), m may be 1.

  About 30-100 weight part may be sufficient as the ratio of the said polyfunctional (meth) acrylate with respect to 100 weight part of fluorene containing (meth) acrylate.

  The hard coat resin composition of the present invention may further contain a monofunctional (meth) acrylate having one (meth) acryloyl group in the molecule. The ratio of the monofunctional (meth) acrylate may be about 10 to 100 parts by weight with respect to 100 parts by weight of the fluorene-containing (meth) acrylate.

  The manufacturing method of the hardened | cured material which provides active energy to the said hard-coat resin composition, and hardens | cures is also contained in this invention. In this method, after applying a hard coat resin composition on a light-transmitting substrate, it may be cured by irradiation with actinic rays.

  The cured product obtained by the manufacturing method is also included in the present invention. The cured product may have a refractive index of 1.57 or more, and a pencil hardness of 10 μm in thickness may be 2H or more.

  In the present invention, a fluorene-containing (meth) acrylate having at least one (meth) acryloyl group in the molecule and having a 9,9-bisarylfluorene skeleton, and 10 or more (meth) acryloyl groups in the molecule. Since the polyfunctional (meth) acrylate is combined, the hardness and refractive index of the cured product can be improved, and in particular, the hardness can be improved even with a thin wall. Furthermore, curling can be suppressed and adhesion can be improved even when laminated on a base film. Moreover, transparency can be improved and handling property can also be improved by adding monofunctional (meth) acrylate.

[Hard coat resin composition]
The hard coat resin composition of the present invention comprises a fluorene-containing (meth) acrylate having at least one (meth) acryloyl group in the molecule and having a 9,9-bisarylfluorene skeleton, and 10 or more in the molecule. And a polyfunctional (meth) acrylate having a (meth) acryloyl group.

(Fluorene-containing (meth) acrylate)
The fluorene-containing (meth) acrylate (curable monomer) may have a 9,9-bisarylfluorene skeleton and have at least one (meth) acryloyl group, but is polymerizable (curable). From the viewpoint, (meth) acrylate having two or more (meth) acryloyl groups is preferable. Such a compound can be represented by the formula (1).

In the formula (1), examples of the aromatic hydrocarbon ring represented by Ar include C _6-14 aromatic hydrocarbon rings such as a benzene ring, a naphthalene ring, an anthracene ring, a biphenyl ring, and an indene ring. Preferred Ar is a benzene ring or a naphthalene ring.

Examples of the alkylene group represented by A include linear or branched C _2-6 alkylene groups such as ethylene group, propylene group, trimethylene group and tetramethylene group. A may be different types of alkylene groups, and the type of alkylene group A may be different depending on the number of coefficients n. A preferable alkylene group is a _C2-4 alkylene group, particularly a _C2-3 alkylene group (ethylene group, propylene group), and is usually an ethylene group in many cases. The repeating number n of the oxyalkylene unit is 0 or an integer of 1 to 10, usually 1 to 7, preferably 1 to 5 (for example, 1 to 3), more preferably an integer of about 1 or 2. Good.

R ¹ may be either a hydrogen atom or a methyl group, but is preferably a hydrogen atom from the viewpoint of curability.

  The coefficient m is an integer of 1 to 3, for example, an integer of 1 or 2 (particularly 1). The coefficient q represents an integer of 0 or 1 to 3, and is usually 0 to 3 (for example, 0 or 1). The coefficient r represents 0 or an integer of 1 to 3, and is usually 0 or 1. In addition, the (meth) acryloyl group can be substituted at any position of the ring Ar. For example, when the ring Ar is a benzene ring, it is usually in the 3-position or 4-position, and the ring Ar is naphthalene. In the case of a ring, it is often the 5-position, 6-position, 7-position or 8-position.

Examples of the halogen atom represented by R ² include a fluorine atom and a chlorine atom. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a t-butyl group. Examples thereof include linear or branched C _1-8 alkyl groups (particularly, C _1-6 alkyl groups). Examples of the cycloalkyl group include C _5-10 cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group. Examples of the aryl group include a phenyl group, an alkylphenyl group (tolyl group, xylyl group, t-butyl group). A C _6-10 aryl group such as a naphthyl group, and the like, and examples of the aralkyl group include a C _6-10 aryl-C _1-4 alkyl group such as a benzyl group and a phenethyl group. As an alkoxy group, _C1-8 alkoxy groups (especially _C1-6 alkoxy group), such as a methoxy group, an ethoxy group, a propoxy group, n-butoxy group, an isobutoxy group, t-butoxy group, etc. can be illustrated, for example. Examples of the cycloalkyloxy group include C _5-10 cycloalkyloxy groups such as a cyclohexyloxy group, and examples of the aryloxy group include C _6-10 aryloxy groups such as a phenoxy group, and an aralkyloxy group. Examples thereof include C _6-10 aryl-C _1-4 alkyloxy groups such as a benzyloxy group. Examples of the acyl group include C _1-6 acyl groups such as an acetyl group, and examples of the substituted amino group include a dialkylamino group. Preferred substituents R ² are C _1-4 alkyl groups (particularly methyl group) such as methyl group and ethyl group, C _1-4 alkoxy groups (particularly methoxy group) such as phenyl group, methoxy group and ethoxy group. . The substitution position of R ² is not particularly limited. For example, when the ring Ar is a benzene ring, usually, the 2-position or the 3-position is often present, and when the ring Ar is a naphthalene ring, 4- In many cases, the position is 5-position, 6-position or 7-position.

Examples of the halogen atom represented by R ³ include a fluorine atom and a chlorine atom, and examples of the alkyl group include linear or branched C _1-8 alkyl groups such as a methyl group and an ethyl group (particularly, C _{1 -6} alkyl group) and the like. A preferred alkyl group is a methyl group.

As a typical compound represented by the formula (1), for example, 9,9-bis [(meth) acryloyloxyphenyl] such as 9,9-bis [4-((meth) acryloyloxy) phenyl] fluorene 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, 9,9-bis [4- (2- (meth) acryloyloxypropoxy) phenyl] fluorene, etc. 9-bis [((meth) acryloyloxy C _2-4 alkoxy) phenyl] fluorenes; 9,9-bis [3-methyl-4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, 9,9 -Bis [3-methyl-4- (2- (meth) acryloyloxypropoxy) phenyl] fluorene, 9,9-bis [3,5-dimethyl- 9,9-bis [mono or diC _1-4 alkyl- (2- (meth) acryloyloxy C _2-4 alkoxy) phenyl] fluorene such as 4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene; 9,9-bis [3,4-di (2- (meth) acryloyloxyethoxy) phenyl] fluorene, 9,9-bis [3,5-di (2- (meth) acryloyloxyethoxy) phenyl] fluorene, etc. Roh 9,9-bis [di (2- (meth) acryloyloxy _{C 2-4} alkoxy) phenyl] fluorenes; 9,9-bis [3,4,5-tris (2- (meth) acryloyloxy ethoxy) 9,9-bis [tri (2- (meth) acryloyloxy _{C 2-4} alkoxy) phenyl] fluorene such as phenyl] fluorene; these reduction In the compound, a compound (9,9-bis [(meth) acryloyloxy C) in which the C _2-4 alkoxy group represented by AO is substituted with a poly (C _2-4 alkoxy) group (diethoxy, triethoxy group, etc.) _2-4 alkoxy) phenyl] fluorenes; 9,9-bis [4- (2- (2- (meth) acryloyloxyethoxy) ethoxy) phenyl] fluorene, 9,9-bis [3,5-dimethyl-4 - (2- (2- (meth) acryloyloxy ethoxy) ethoxy) phenyl] 9,9-bis fluorene [((meth) acryloyloxy _{C 2-4} alkoxy _{C 2-4} alkoxy) phenyl] fluorenes, etc.) In these compounds, a compound in which a phenyl group is further substituted on a ring Ar which is a phenyl group to form a biphenyl group (9,9- The [3-phenyl-4- (2- (meth) acryloyloxy ethoxy) phenyl] fluorene such as 9,9-bis [phenyl - (meth) acryloyloxy _{C 2-4} alkoxyphenyl] fluorenes, etc.); these Compound (9,9-bis [5 or 6- (2- (meth) acryloyloxyethoxy) -2-naphthyl)] fluorene, 9,9-bis [5 or 6- (wherein ring Ar is a naphthyl group in the compound Examples include 9,9-bis [((meth) acryloyloxy C _2-4 alkoxy) naphthyl] fluorenes) such as 2- (meth) acryloyloxyethoxy) -1 or 2-naphthyl)] fluorene.

(Multifunctional (meth) acrylate)
The polyfunctional (meth) acrylate (curable monomer) is mainly blended to improve the hardness of the hard coat resin composition, and has 10 or more (meth) acryloyl groups in the molecule. Furthermore, when polyfunctional (meth) acrylate is blended, curling can be suppressed even when laminated on a substrate film, and adhesion can be improved.

  The number of (meth) acryloyl groups in the molecule of the polyfunctional (meth) acrylate may be 10 or more (for example, 10 to 300), for example, 30 to 250, preferably 40 to 220, and more preferably 50 to It is about 200 (particularly 80 to 150). If the number of (meth) acryloyl groups is too small, the hardness cannot be improved. Conversely, if the number is too large, handling properties and the like are lowered.

  Polyfunctional (meth) acrylates only need to have 10 or more (meth) acryloyl groups in the molecule, but low molecular weight compounds are used as cores because they can improve not only hardness but also adhesion and curl suppression. Is preferably a multi-branched (meth) acrylate having a side chain extending radially or in the form of a network, for example, a (meth) acrylate having a multi-branched structure with a polyhydric alcohol as a nucleus. Good.

  As the polyhydric alcohol, usually, an aliphatic polyhydric alcohol (3 to 8 valent aliphatic alcohol or the like) is used. For example, an aliphatic trihydric alcohol (for example, glycerin, trimethylolethane, trimethylolpropane or the like), Aliphatic tetrahydric alcohol (eg, threitol, erythritol, pentaerythritol, etc.), aliphatic pentahydric alcohol (eg, arabitol, ribitol, xylitol, etc.), aliphatic hexahydric alcohol (eg, dipentaerythritol, sorbitol, mannitol, Galactitol, etc.), aliphatic octahydric alcohols (eg, tripentaerythritol, etc.). These polyhydric alcohols can be used alone or in combination of two or more.

  Among these polyhydric alcohols, a polyhydric alcohol having a plurality of methylol groups (for example, 3 to 10 methylol groups) from the viewpoint of easily forming a multi-branched structure and introducing a large number of (meth) acryloyl groups, for example, , Trimethylolethane, trimethylolpropane, pentaerythritol, or oligomers thereof are preferred, and polyhydric alcohols having 4 to 8 methylol groups such as pentaerythritol or oligomers thereof (for example, diesters) are preferred because they easily branch in three dimensions. Polyhydric alcohols having 5-7 methylol groups such as pentaerythritol are particularly preferred.

The hyperbranched (meth) acrylate can form these polyhydric alcohols as nuclei. For example, a reactive group (carboxyl group) with a hydroxyl group with respect to the polyhydric alcohol (particularly dipentaerythritol) as a nucleus. , Epoxy groups, etc.) and dendrimers in which a (meth) acryloyl group is introduced at the end (hydroxy end) of a side chain that is branched and extended by adding a hydrocarbon compound having a plurality of hydroxyl groups, poly (meth) of polyhydric alcohol An acrylate (for example, a polymer obtained by condensing an alkane polyol poly (meth) acrylate such as dipentaerythritol hexaacrylate into a three-dimensional network by addition reaction using a cross-linking agent . Among these, may be used. polyhydric alcohol poly (meth) acrylate with a crosslinker 3D network As the cross-linking agent, for example, a compound having a plurality of reactive groups (for example, about 2 to 10, preferably about 3 to 8, more preferably about 4 to 6) with respect to the polymerizable group (for example, And polyvalent thiols).

  The weight average molecular weight of polyfunctional (meth) acrylate can be selected from the range of about 800-50000, for example, For example, 1000-45000 (for example, 3000-40000), Preferably it is 5000-35000, More preferably, it is 10,000-30000 ( In particular, it is about 15000 to 25000). If the molecular weight is too large, the hardness and handling properties decrease, and if it is too small, the hardness cannot be improved. The weight average molecular weight can be measured by gel permeation chromatography (reference resin: polystyrene, eluent: 10% by volume acetic acid tetrahydrofuran solution) using HLC-8220GPC (manufactured by Tosoh Corporation).

  The acid value of the polyfunctional (meth) acrylate may be, for example, 1.0 mgKOH / g or less, for example, 0.5 mgKOH / g or less (for example, about 0.01 to 0.5 mgKOH / g) Also good.

  The refractive index of the polyfunctional (meth) acrylate (the refractive index of the polyfunctional (meth) acrylate alone before curing) may be, for example, 1.4 or more, for example, 1.4 to 1.6, preferably It may be about 1.41 to 1.58, more preferably about 1.42 to 1.55. Furthermore, from the viewpoint of improving the refractive index of the cured product, the refractive index of the polyfunctional (meth) acrylate may be 1.45 or more, for example, 1.45 to 1.6, preferably 1.47 to It may be about 1.55, more preferably about 1.48 to 1.53.

  The ratio of the polyfunctional (meth) acrylate can be selected from a range of about 10 to 200 parts by weight with respect to 100 parts by weight of the fluorene-containing (meth) acrylate, for example, 20 to 150 parts by weight, preferably 30 to 100 parts by weight. More preferably, it is about 40 to 90 parts by weight (particularly 45 to 80 parts by weight). When the ratio of the polyfunctional (meth) acrylate is too small, the hardness is lowered, and the adhesion to the base film and the curl suppressing effect are lowered. On the other hand, in the blending system of fluorene-containing (meth) acrylate and polyfunctional (meth) acrylate, if the ratio of polyfunctional (meth) acrylate is too large, not only the refractive index decreases, but also surprisingly, the hardness ( In particular, the hardness of a thin film of about 10 μm is also reduced. Therefore, as a ratio having both of these effects, the ratio of the polyfunctional (meth) acrylate is 40 to 80 parts by weight, preferably 50 to 75 parts by weight, more preferably 55 to 100 parts by weight of the fluorene-containing (meth) acrylate. About 70 parts by weight (particularly 60 to 70 parts by weight) may be used.

(Monofunctional (meth) acrylate)
Monofunctional (meth) acrylate (diluted monomer) is formulated to improve the handleability of the hard coat resin composition and adjust the hardness of the cured product, and has one (meth) acryloyl group in the molecule. doing. The monofunctional (meth) acrylate can be classified into an aliphatic monomer, a monomer containing an aliphatic hydrocarbon ring, a monomer containing an aromatic ring, and the like depending on the kind of skeleton that is ester-bonded to the (meth) acryloyl group.

Examples of the aliphatic monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, t-butyl (meth) acrylate, and isobutyl (meth). C _1- such as acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, etc. ₂₄ alkyl (meth) acrylate; hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxy _{C 2-10} alkyl, such as hydroxybutyl (meth) acrylate (Meth) acrylate; and alkoxyalkyl (meth) acrylates such as methoxyethyl (meth) acrylate.

  Examples of the monomer containing an aliphatic hydrocarbon ring include cycloalkyl (meth) acrylates such as cyclohexyl (meth) acrylate; dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentadi Examples include bridged cyclic (meth) acrylates such as enyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, and dicyclopentenyloxyethyl (meth) acrylate. It is done.

  Examples of the monomer containing an aromatic ring include aralkyl (meth) acrylates such as benzyl (meth) acrylate; phenoxyalkyl (meth) acrylates such as phenoxyethyl (meth) acrylate; phenylphenoxyethyl (meth) acrylate, and the like. Phenylphenoxyalkyl (meth) acrylate; Phenoxy (poly) alkoxyalkyl (meth) acrylate such as phenoxy (poly) ethoxyethyl (meth) acrylate; Alkylphenoxy (poly) alkoxy such as nonylphenoxy (poly) ethoxyethyl (meth) acrylate Alkyl (meth) acrylates; phenylphenoxy (poly) alkoxyalkyl (meth) acrylates such as phenylphenoxy (poly) ethoxyethyl (meth) acrylate ; Phenyl thio-alkyl (meth) acrylates such as phenyl thio (meth) acrylate.

As other monomers, unsaturated polyvalent carboxylic acids such as (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid or their anhydrides, carboxyl group-containing compounds such as half esters thereof, sulfonic acid group-containing compounds Glycidyl (meth) acrylate; nitrogen atom-containing (meth) acrylate such as dimethylamino (meth) acrylate, (meth) acrylamide, (meth) acryloylmorpholine; cyclic ether-containing (meth) such as tetrahydrofurfuryl (meth) acrylate Acrylate; fluoro C _1-10 alkyl (meth) acrylates such as trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, hexafluoroisopropyl (meth) acrylate; (meth) acryloyloxyethyl acetate Examples thereof include phosphoric acid group-containing compounds such as cide phosphate.

  These monofunctional (meth) acrylates can be used alone or in combination of two or more. Among these, an aliphatic monomer, a monomer containing an aliphatic hydrocarbon ring, and a monomer containing an aromatic ring are widely used, and these monomers may be properly used according to applications. For example, from the viewpoint of improving the refractive index, a monomer containing an aromatic ring may be used, and from the viewpoint of improving handleability and hardness, an aliphatic monomer or a monomer containing an aliphatic hydrocarbon ring is used. Also good.

  The refractive index of the monofunctional (meth) acrylate (the refractive index of the monofunctional (meth) acrylate alone before curing) may be, for example, 1.4 or more, for example, 1.4 to 1.6, preferably It may be about 1.41 to 1.58, more preferably about 1.42 to 1.55. Furthermore, from the point which improves the refractive index of hardened | cured material, the refractive index of monofunctional (meth) acrylate may be 1.5 or more, for example, 1.5-1.6, Preferably 1.5- It may be about 1.55, more preferably about 1.5 to 1.53.

Examples of the monofunctional (meth) acrylate having a refractive index of 1.5 or more include monomers containing an aromatic ring, for example, aralkyl (meth) acrylates such as benzyl (meth) acrylate; phenoxy such as phenoxyethyl (meth) acrylate Alkyl (meth) acrylates; phenoxyaralkyl (meth) acrylates such as phenoxybenzyl (meth) acrylate; phenylphenoxyalkyl (meth) acrylates such as phenylphenoxyethyl (meth) acrylate; phenylphenoxy (poly) ethoxyethyl (meth) Phenylphenoxy (poly) alkoxyalkyl (meth) acrylates such as acrylate; phenylthioalkyl (meth) acrylates such as phenylthioethyl (meth) acrylate, etc. Among these, phenoxyalkyl (meth) acrylates such as phenoxyethyl (meth) acrylate, and C _6-10 aryl-C ₁₋ such as benzyl (meth) acrylate, because the refractive index can be improved without impairing handling properties. Particularly preferred are phenylthio C _1-4 alkyl (meth) acrylates such as _4- alkyl (meth) acrylates and phenylthioethyl (meth) acrylate.

  The viscosity of the monofunctional (meth) acrylate is not particularly limited, and the viscosity at 25 ° C. can be selected from a range of about 200 mPa · s or less. For example, the viscosity is 100 mPa · s or less (for example, 0.01 to 100 mPa · s), Preferably, it may be 50 mPa · s or less (for example, 0.1 to 50 mPa · s), and more preferably 30 mPa · s or less (for example, 0.3 to 30 mPa · s).

  The hard coat resin composition of the present invention can improve the handling property without using a solvent by blending a monofunctional (meth) acrylate. For example, the viscosity of the hard coat resin composition is 25 ° C. In, for example, it can be adjusted to 100000 mPa · s or less, preferably 50000 mPa · s or less, more preferably 30000 mPa · s or less.

  The proportion of the monofunctional (meth) acrylate may be 200 parts by weight or less (for example, 0 to 200 parts by weight), for example, 1 to 150 parts by weight, preferably 100 parts by weight of the fluorene-containing (meth) acrylate. Is about 10 to 100 parts by weight, more preferably about 20 to 80 parts by weight (particularly 30 to 50 parts by weight).

  The proportion of monofunctional (meth) acrylate may be 500 parts by weight or less (for example, 0 to 500 parts by weight), for example, 1 to 200 parts by weight, preferably 100 parts by weight of polyfunctional (meth) acrylate. Is about 20 to 100 parts by weight, more preferably about 40 to 80 parts by weight (particularly 50 to 60 parts by weight).

  If the proportion of monofunctional (meth) acrylate is too large, the hardness decreases. In the present invention, in addition to the fluorene-containing (meth) acrylate and the polyfunctional (meth) acrylate, the monofunctional (meth) acrylate is blended in the above range, thereby improving the handling property while maintaining a high refractive index and hardness. it can.

(Other curable monomers)
The hard coat resin composition of the present invention may further contain another curable monomer in order to improve handling properties. Other curable monomers include monofunctional curable monomers and polyfunctional curable monomers.

  Other monofunctional curable monomers (diluting monomers) include, for example, allyl group-containing dilution monomers (allyl alcohol, etc.), vinyl group-containing dilution monomers (styrene monomers, N-vinyl pyrrolidone, vinyl ethers, etc.), etc. Can be mentioned.

The polyfunctional curable monomer may be any monomer having 9 or less (meth) acryloyl groups in the molecule, and examples of the bifunctional curable monomer include ethylene glycol di (meth) acrylate and propylene glycol di (meth). Alkane diols such as acrylate, 1,3-propanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate Di (meth) acrylates; diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polypropylene glycol di (meth) Polyalkylene glycol di (meth) acrylates such as acrylate; 2,2-bis (4- (meth) acryloyloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxyethoxyphenyl) propane, Di (meth) acrylates of C _2-4 alkylene oxide adducts of bisphenols (such as bisphenol A) such as 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane; tricyclodecane dimethanol di Examples thereof include bridged cyclic (meth) acrylates such as (meth) acrylate.

Examples of the trifunctional or higher polyfunctional curable monomer include trimethylolpropane tri (meth) acrylate, glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol penta. Alkane polyols such as (meth) acrylate and dipentaerythritol hexa (meth) acrylate; poly (meth) acrylates; alkane polyols such as trimethylolpropane and glycerol; tri (meth) acrylates of C _2-4 alkylene oxide adducts; Examples include tri (meth) acrylates having a triazine ring such as (2-hydroxyethyl) isocyanurate tri (meth) acrylate.

  Furthermore, the polyfunctional curable monomer is produced by a reaction of a polyfunctional oligomer having a (meth) acryloyl group, for example, a polyvalent carboxylic acid, a polyol, (meth) acrylic acid and / or hydroxyalkyl (meth) acrylate. Polyester (meth) acrylates; (meth) acrylic for epoxy compounds having a plurality of epoxy groups (polyhydric alcohol type, polyvalent carboxylic acid type, bisphenol type such as bisphenol A, F, and S, and epoxy resin such as novolac type) Epoxy (meth) acrylates with ring-opening addition of acid; polyurethane (meth) acrylates produced by reaction of polyisocyanate and polyol, and having oligomers with terminal isocyanate groups reacted with hydroxyalkyl (meth) acrylate included. In addition, an oligomer having a hydroxyl group (for example, epoxy (meth) acrylate having a hydroxyl group generated by a ring-opening reaction) reacts with a reactive compound having a carboxyl group or an acid anhydride group (for example, an acid anhydride). And a carboxyl group or the like may be introduced.

  Furthermore, as a polyfunctional curable monomer, another polyfunctional curable monomer, for example, a polyfunctional curable monomer having an ethylenically unsaturated bond other than a (meth) acryloyl group, for example, a compound having an allyl group such as diallyl phthalate Etc.

  These other curable monomers can be used alone or in combination of two or more. Among these, curable monomers having 4 to 9 (for example, 4 to 8) (meth) acryloyl groups in the molecule, in particular, 5 to 7 from the viewpoint that the handleability can be improved while maintaining the hardness. A curable monomer having two (meth) acryloyl groups (for example, dipentaerythritol hexa (meth) acrylate) is preferable.

  The ratio of the other curable monomer may be, for example, 200 parts by weight or less with respect to 100 parts by weight of the fluorene-containing (meth) acrylate, for example, 1 to 200 parts by weight, preferably 10 to 150 parts by weight, Preferably it is about 30-100 weight part (especially 50-80 weight part).

(Polymerization initiator)
The hard coat resin composition of the present invention may contain a polymerization initiator, and such a polymerization initiator may be a thermal polymerization initiator (thermal radical generator) or a photopolymerization initiator (photo radical). Generator). A preferred polymerization initiator is a photopolymerization initiator.

  Examples of the photopolymerization initiator or photo radical generator include benzoins (benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether); acetophenones (acetophenone, p- Dimethylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-phenyl-2-hydroxy-acetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, etc .; propiophenones (p-dimethylaminopropiophenone, -Hydroxy-2-methyl-propiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, etc.); butyrylphenones [1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy 2-methyl-1-propan-1-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl-propane- 1-one etc.]; aminoacetophenones [2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane- 1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-dimethylamino-2-methyl 1-phenylpropan-1-one, 2-diethylamino-2-methyl-1-phenylpropan-1-one, 2-methyl-2-morpholino-1-phenylpropan-1-one, 2-dimethylamino- 2-methyl-1- (4-methylphenyl) propan-1-one, 1- (4-butylphenyl) -2-dimethylamino-2-methylpropan-1-one, 2-dimethylamino-1- (4 -Methoxyphenyl) -2-methylpropan-1-one, 2-dimethylamino-2-methyl-1- (4-methylthiophenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4 -Dimethylaminophenyl) -butan-1-one etc.]; ketals (acetophenone dimethyl ketal, benzyl dimethyl ketal etc.); thioxanthenes ( (Thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, etc.); anthraquinones (2-ethylanthraquinone, 1-chloroanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, etc.); ) Xanthones (thioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone); acridines (1,3-bis- (9-acridinyl) propane, 1,7-bis- (9-acridinyl) heptane, 1,5-bis- (9-acridinyl) pentane, etc.); triazines (2,4,6-tris (trichloromethyl) -s-triazine, 2- ( 4-methoxyphenyl) -4,6-bis (trichloro) Methyl) -s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, etc.); sulfides (benzyl diphenyl sulfide, etc.); acylphosphine oxides ( 2,4,6-trimethylbenzoyldiphenylphosphine oxide); titanocene photopolymerization initiators; oxime esters and the like. These photopolymerization initiators can be used alone or in combination of two or more.

  In addition, a photoinitiator can be obtained as a commercial item, for example, a brand name "Irgacure" "Darocur" (Ciba Japan Co., Ltd. product), a brand name "Syracure" (made by Union Carbide), etc.

  Examples of thermal polymerization initiators include dialkyl peroxides (di-t-butyl peroxide, dicumyl peroxide, etc.), diacyl peroxides [dialkanoyl peroxide (such as lauroyl peroxide), and dialoyl peroxide (benzoyl peroxide). Oxide, benzoyl toluyl peroxide, toluyl peroxide, etc.)], peracid esters (percarboxylic acid alkyl esters such as t-butyl peracetate, t-butyl peroxyoctate, t-butyl peroxybenzoate, etc.), Organic peroxides such as ketone peroxides, peroxycarbonates, peroxyketals; azonitrile compounds [2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (isobutyro) Nitrile) 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), etc.], azoamide compound {2,2′-azobis {2-methyl -N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide} and the like}, azoamidine compounds {2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, etc.}, azoalkane compounds [2,2′-azobis (2,4,4-trimethylpentane), 4,4′-azobis (4-cyano) Azo compounds, etc.], and azo compounds having an oxime skeleton [2,2′-azobis (2-methylpropionamidooxime, etc.)]. You may use a thermal-polymerization initiator individually or in combination of 2 or more types.

  The ratio of the polymerization initiator (particularly the photopolymerizable initiator) is, for example, 0.1 to 20 parts by weight, preferably 0.5 to 15 parts by weight, based on 100 parts by weight of the total amount of the curable monomer and the monofunctional diluent. Part, more preferably about 1 to 10 parts by weight (particularly 2 to 7 parts by weight).

  In addition, you may combine a photoinitiator with a photosensitizer. Examples of the photosensitizer include conventional components such as tertiary amines [for example, trialkylamine, trialkanolamine (such as triethanolamine), ethyl N, N-dimethylaminobenzoate, N, N-dimethyl. Dialkylaminobenzoic acid alkyl esters such as amyl aminobenzoic acid, bis (dialkylamino) benzophenones such as 4,4-bis (dimethylamino) benzophenone (Michler's ketone), 4,4′-diethylaminobenzophenone], triphenylphosphine, etc. Examples include phosphine, toluidines such as N, N-dimethyltoluidine, anthracene such as 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, and 2-ethyl-9,10-diethoxyanthracene. It is done. The photosensitizers may be used alone or in combination of two or more.

  The amount of the photosensitizer used is, for example, 0.1 to 150 parts by weight, preferably 1 to 100 parts by weight, more preferably 5 to 75 parts by weight (particularly 10 parts by weight) with respect to 100 parts by weight of the photopolymerization initiator. (About 50 parts by weight).

(Other additives)
The hard coat resin composition of the present invention may contain a solvent as a non-reactive diluent in order to improve handling properties. Examples of the solvent include hydrocarbons (toluene, xylene, etc.), halogenated solvents (methylene chloride, chloroform, etc.), alcohols (ethanol, isopropanol, etc.), ethers (dialkyl ethers such as diethyl ether, cyclic rings such as tetrahydrofuran, etc. Ethers, etc.), ketones (acetone, methyl ethyl ketone, etc.), esters (methyl acetate, ethyl acetate, butyl acetate, etc.), cellosolves (methyl cellosolve, ethyl cellosolve, butyl cellosolve, etc., C _1-4 alkyl cellosolves, propylene glycol mono C _1-4 propylene glycol monomethyl ethers such as alkyl ethers), C _1-4 alkyl cellosolve acetate, such as cellosolve acetates (ethyl cellosolve acetate, propylene Recall propylene glycol mono C _1-4 alkyl ether acetates such as monomethyl ether acetate), carbitol (methyl carbitol, ethyl carbitol, propyl carbitol, C _1-4 alkyl carbitols such as butyl carbitol, etc.) Etc. These solvents can be used alone or in combination of two or more. Among these solvents, cellosolves and cellosolve acetates (for example, propylene glycol mono C _1-4 alkyl ether acetates such as propylene glycol monomethyl ether acetate) are widely used.

  The proportion of the solvent can be selected, for example, from a range of about 100 to 1000 parts by weight with respect to 100 parts by weight of the fluorene-containing (meth) acrylate, for example, 20 to 800 parts by weight, preferably 30 to 500 parts by weight, more preferably About 50 to 400 parts by weight (particularly 100 to 300 parts by weight).

  The hard coat resin composition of the present invention further comprises conventional additives such as resin components, solvents, thermal polymerization inhibitors (hydroquinone, hydroquinone monoethyl ether, etc.), antifoaming agents, coating property improvers, thickeners. , Lubricants, stabilizers (antioxidants, heat stabilizers, light stabilizers, etc.), plasticizers, surfactants, dissolution promoters, colorants, fillers, antistatic agents, silane coupling agents, leveling agents, dispersions An agent, a dispersion aid, and the like may be included. The additives may be used alone or in combination of two or more.

  In addition, the hard-coat resin composition of this invention can be prepared by a conventional method, for example, mixing each component and filtering with a filter if needed.

(Characteristics of hard coat resin composition)
The hard coat resin composition of the present invention is excellent in curability (especially photocurability) and has high refractive properties. For example, the refractive index of the hard coat resin composition (or the solid content of the resin composition) can be selected from a range of, for example, 1.5 or more at 25 ° C. and 589 nm, preferably 1.50 to 1.70, More preferably, it is about 1.51-1.60, More preferably, it is about 1.53-1.58 (especially 1.54-1.57).

  Moreover, in this invention, although it has a high refractive index and hardness, the hard coat property resin composition excellent in handling property can be obtained. Therefore, the hard coat resin composition of the present invention may be usually liquid at normal temperature (for example, 15 to 25 ° C.).

[Cured product]
The hard coat resin composition of the present invention is easily cured by applying active energy. Therefore, the hard coat resin composition of the present invention is useful for forming a cured product using thermal energy and / or light energy (particularly, light energy) as active energy. The hard coat resin composition of the present invention is often excellent in photocurability and can be cured by applying at least light energy. The cured product may have a three-dimensional structure and is usually a cured film in many cases. The cured film may be a film pattern (particularly a thin film pattern). The cured film can be formed by applying the resin composition to a base material or a substrate and drying it if necessary, and then heating or exposing to an actinic ray. Then, it can be formed by selectively exposing and developing the generated latent image pattern.

  The base material or the substrate can be selected depending on the application, and may be a porous material such as wood, a metal such as aluminum or copper, a ceramic such as glass or quartz, a plastic such as polymethyl methacrylate or polycarbonate. Since the hard coat resin composition of the present invention has a high refractive index and high transparency, it is suitable for optical applications, and among these substrates, it is laminated on a transparent film by coating on the transparent film. It may be used as a body. As a transparent film, it is excellent in transparency and has excellent adhesion with a hard coat resin composition. For example, a cyclic olefin resin, a styrene resin, a (meth) acrylic resin (polymethyl methacrylate, etc.), A transparent film composed of acrylonitrile-based resin, polyester-based resin, polyamide-based resin, cellulose ester (such as triacetyl cellulose) is preferable. The thickness of a transparent film can be selected according to a use, for example, 1-1000 micrometers, Preferably it is 10-500 micrometers, More preferably, about 30-300 micrometers may be sufficient.

  The coating method is not particularly limited. For example, flow coating method, spin coating method, spray coating method, screen printing method, casting method, bar coating method, curtain coating method, roll coating method, gravure coating method, dipping method, slit method. It may be.

  The hard coat resin composition may be applied and then dried (for example, dried at about 40 to 150 ° C.). Although the thickness of a coating film changes with uses, it can select from the range of about 0.01-1000 micrometers, for example, it is 1-500 micrometers, Preferably it is 3-300 micrometers, More preferably, it is about 5-200 micrometers, but hardening of this invention Even if the object is thin, it has a high hardness, so it may be, for example, about 1 to 50 μm, preferably 3 to 30 μm, more preferably about 5 to 20 μm (particularly 8 to 15 μm).

  In addition, the said resin composition is normally liquid at normal temperature, and when such a liquid resin composition is used, a coating film can be formed, without passing through the process of melting a resin composition.

  When the coating film is cured by heating, the heating temperature may be, for example, 60 to 200 ° C. (for example, 80 to 180 ° C.), preferably about 100 to 150 ° C. Since the resin composition of this invention is excellent in photopolymerizability, it can also obtain hardened | cured material by irradiation of actinic light, without heating.

In the exposure step, the entire surface may be exposed depending on the application, or a patterned latent image may be formed by selective exposure using a photomask or the like. For exposure, radiation (gamma rays, X-rays, etc.), ultraviolet rays, visible rays, etc. can be used, and usually ultraviolet rays are often used. As the light source, for example, in the case of ultraviolet rays, a deep UV lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a halogen lamp, a laser light source (light source such as helium-cadmium laser or excimer laser), etc. Can be used. Irradiation light amount (irradiation energy) varies depending on the thickness of the coating film, for example, be selected from 50~10000mJ / cm ² in the range of about, 75~5000mJ / cm ^2, more preferably 100~3000mJ / cm ² (e.g., 100 to 2000 mJ / cm ² ).

  If necessary, heat treatment (after-cure or post-bake) may be performed after exposure. The heating temperature may be, for example, about 60 to 200 ° C, preferably about 100 to 150 ° C.

  When a pattern-like latent image is formed, a developed coating pattern can be formed by developing the latent image pattern. Developers include water, alkaline aqueous solutions (eg, tetramethylammonium hydroxide aqueous solution, sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, etc.), acidic aqueous solutions, hydrophilic solvents (eg, alcohols such as methanol, ethanol, isopropanol, Ketones such as acetone, ethers such as dioxane and tetrahydrofuran, cellosolves, cellosolve acetates, etc.), and mixtures thereof. The development can be performed using immersion, washing, spraying or spray development.

  The cured product obtained by the above method is excellent in optical characteristics, and the refractive index of the cured product is, for example, 1.5 or more (for example, 1.50 to 1.8) at 25 ° C. and 589 nm, preferably May be about 1.53 to 1.7, more preferably about 1.54 to 1.65 (especially 1.55 to 1.6), and 1.56 or more (for example, 1.56 to 1. 6) Especially, it may be about 1.57 or more (for example, 1.57 to 1.59).

  The cured product has a high hardness, and the pencil hardness may be H or higher (for example, H to 5H), preferably 2H or higher (for example, 2H to 4H). The pencil hardness of 10 μm may be H or more (for example, H to 4H), preferably 2H or more (for example, 2H to 3H). That is, the cured product of the present invention can achieve both a refractive index of 1.57 or more and a pencil hardness of 10 μm in thickness of 2H or more.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In the following Examples and Comparative Examples, the properties and evaluation of the hard coat resin composition and the cured product were measured as follows. Further, the hard coat resin composition was prepared as follows.

[Refractive index]
A multi-wavelength Abbe refractometer (manufactured by Atago, DR-M2 <circulating constant temperature water bath 60-C3 use>) was used, and the refractive index at 589 nm was measured while maintaining a temperature of 25 ° C.

[Pencil hardness]
A cured film produced on a 100 μm thick polyethylene terephthalate (PET) film (“A4300” manufactured by Toyobo Co., Ltd.) was placed on a pencil hardness meter (“HEIDON-14” manufactured by Shinto Kagaku Co., Ltd.), and various pencils Was pressed at an angle of 45 degrees while applying a weight of 750 g, moved on the cured film at a speed of 1 mm / second, and the pencil hardness was measured by visually confirming the presence or absence of scratches on the cured film. .

[Adhesion 1]
In accordance with JIS K5600-5-6, on a PET film (A4300), a cured film with a film thickness of 20 to 25 μm was prepared, and after cutting 100 squares in a grid pattern with a specified cutting tool, Peeling was performed using cellophane tape.

[Adhesion 2]
Qualitative evaluation of ease of peeling and difficulty of peeling when a cured film having a film thickness of 20 to 25 μm is prepared on a cellulose triacetate film (“TAC100” manufactured by Fuji Film Co., Ltd.) The following criteria were evaluated.

○… Difficult to peel ×… Easy to peel [Curl]
After making a cured film of 20 to 25 μm on a PET film (A4300), it was cut into a 6 cm × 6 cm square shape, and the average height (mm) of the four corners when placed on a flat desk is as follows: It was evaluated with.

○: 14 mm or less Δ: Exceeding 14 mm but the opposing apex angles do not contact X: The opposing apex angles come into contact and become cylindrical.

[Handling]
As the handling property in the absence of a solvent, the viscosity of the hard coat resin composition at 25 ° C. was measured. The viscosity is an optional rotor (01: 1 ° 34 × R24, 07) according to the measured viscosity using a TV-22 viscometer (cone plate type, “TVE-22L” manufactured by Toki Sangyo Co., Ltd.). It was measured at 1.0 to 20 rpm (selected according to viscosity) at 3 ° × R7.7).

[Components of Hard Coat Resin Composition and Abbreviations in Table]
Fluorene-containing acrylate (EA-0200): “Ogsol EA-0200” manufactured by Osaka Gas Chemical Co., Ltd.
Multi-branch network type polyacrylate (STAR-501): “STAR-501” manufactured by Osaka Organic Chemical Industry Co., Ltd., weight average molecular weight 16000-24000, average functional group number 100-120, refractive index 1.499, 25 ° C. viscosity 150 ˜250 Pa · s, diluent: dipentaerythritol hexaacrylate, solid content of about 50% by weight
Multi-branched dendrimer type polyester acrylate (V # 1000): “ V # 1000” manufactured by Osaka Organic Chemical Industry Co., Ltd., weight average molecular weight 1000 to 2000, refractive index 1.478, 25 ° C. viscosity 0.4 to 0.7 Pa · s
Dipentaerythritol hexaacrylate (DPHA-2C): “KAYARAD DPHA-2C” manufactured by Nippon Kayaku Co., Ltd., hexafunctional benzyl acrylate (BZA): “FA-BZA” manufactured by Hitachi Chemical Co., Ltd.
Propylene glycol monomethyl ether acetate (PGMEA): “Propylene glycol 1-monomethyl ether 2-acetate” manufactured by Tokyo Chemical Industry Co., Ltd.
Photopolymerization initiator (Irgacure 184): “IRGACURE 184” manufactured by Ciba Japan Co., Ltd.

Examples 1-8, Reference Examples 1-2, and Comparative Examples 1-7
The components shown in Table 1 were sufficiently mixed in a shaker at the ratio (parts by weight) shown in Table 1 to prepare a hard coat resin composition. The hard coat resin composition is applied to one side of a polyethylene terephthalate film (film thickness: 100 μm) and irradiated with ultraviolet rays having an integrated light quantity of 500 mJ / cm ² with a carbon arc ultraviolet ray irradiator. Two kinds of laminated films having a thickness of the dough layer) of about 10 μm and about 100 μm were obtained.

  As is clear from the results in Tables 1 and 2, the resin compositions of the examples have excellent adhesion, high transparency, and curling is suppressed. On the other hand, the resin composition of the comparative example cannot achieve both adhesion, hardness, and curl suppression.

  Furthermore, with respect to the solventless resin compositions of Examples 4 and 6 to 8, the handling property was evaluated. As a result, the viscosity of the resin composition of Example 4 was 100,000 mPa · s or more. The viscosity of 6-8 resin compositions was 10,000-20,000 mPa · s, and was excellent in handling properties even without solvent.

The hard coat resin composition of the present invention includes an ink material, a light emitting material (for example, a light emitting material for organic EL), an organic semiconductor, a graphitization precursor, a gas separation membrane (for example, a CO ₂ gas separation membrane), a coating, and the like. Agents (for example, optical overcoat agents such as LED (light-emitting diode) element coating agents, hard coat agents, etc.), lenses [pickup lenses (eg, pickup lenses for DVD (digital versatile disc)), micro, etc. Lens (for example, microlens for liquid crystal projector), eyeglass lens, etc.], polarizing film (for example, polarizing film for liquid crystal display), antireflection film (or antireflection film, for example, antireflection film for display device), Film for touch panel, film for flexible substrate, film for display [For example, PDP (plasma display), LCD (liquid crystal display), VFD (vacuum fluorescent display), SED (surface conduction electron-emitting device display), FED (field emission display), NED (nano-emissive display), OLED (Organic EL display), cathode ray tube, electronic paper and other displays (especially thin displays) films (filters, protective films, etc.), color filters [eg, lens filters, display color filters, etc.], liquid crystal display resists [For example, TFT array etching photoresist, pigment dispersion type photoresist, protective film, etc.], interlayer insulating film, solder resist, fuel cell film, optical fiber, optical waveguide, hologram, etc. In particular, since the hard coat resin composition of the present invention has a high refractive index, it can be suitably used for optical material applications. Examples of the shape of the optical material include a film or sheet shape, a plate shape, a lens shape, and a tubular shape.

Claims (10)

And the following formula (1) represented Ru fluorene-containing (meth) acrylate having 50 to 200 of (meth) acryloyl groups in the molecule, Ri Weight average molecular weight of 10,000 to 30,000 der, and 4-8 polyhydric alcohol poly (meth) acrylate having a methylol group and a Okan capacity (meth) acrylate fused multivalent thiols of formula ^{R 1 R 2 R 3 R 4} N + X - [ in the formula, ^{R 1} , R ² , R ³ , and R ⁴ are groups selected from CH ₃ , C ₂ H ₅ , C ₂ H ₄ OCH ₃ , C ₆ H ₁₃ , and C ₈ H ₁₇ , and each group may be the same. May be different. X is a group selected from N (SO ₂ CF ₃ ) ₂ , BF ₄ , and PF ₆ ].

(In the formula, the rings Ar are the same or different and are aromatic hydrocarbon rings; A is the same or different and an alkylene group; R ¹ is the same or different and represents a hydrogen atom or a methyl group; and R ² is the same or different and is a halogen atom. , An alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, a cycloalkyloxy group, an aryloxy group, an aralkyloxy group, an acyl group, a nitro group, a cyano group, or a substituted amino group, and R ³ is the same or Differently represents a halogen atom, a cyano group or an alkyl group, n is 0 or an integer of 1 to 10, m is an integer of 1 to 3, q is an integer of 0 or 1 to 3, and r is an integer of 0 or 1 to 3. Indicates) Polyfunctional polyester (meth) weight average molecular weight of acrylate hard coat resin composition of claim 1 Symbol placement is 15,000 to 30,000. The hard coat resin composition according to claim 1 or 2 , wherein in the formula (1), m is 1. Ratio of Okan capacity (meth) acrylate, relative to the fluorene-containing (meth) acrylate 100 parts by weight, the hard coat resin composition according to any one of claims 1 to 3 which is 30 to 100 parts by weight. Furthermore, the hard-coat resin composition in any one of Claims 1-4 containing the monofunctional (meth) acrylate which has one (meth) acryloyl group in a molecule | numerator. The hard coat resin composition according to claim 5 , wherein the proportion of the monofunctional (meth) acrylate is 10 to 100 parts by weight with respect to 100 parts by weight of the fluorene-containing (meth) acrylate. The manufacturing method of the hardened | cured material which gives active energy to the hard-coat resin composition in any one of Claims 1-6 , and is hardened. The manufacturing method of the hardened | cured material of Claim 7 which makes it harden | cure by irradiating actinic light after apply | coating a hard-coatable resin composition on a light transmissive base material. Hardened | cured material which hardened | cured the hard-coat property resin composition in any one of Claims 1-6 . The cured product according to claim 9 , wherein the refractive index is 1.57 or more, and the pencil hardness with a thickness of 10 µm is 2H or more.