KR102503973B1 - Curable composition, method for production of cured product, and hard-coating material - Google Patents

Abstract

A curable composition providing a hard coat layer having excellent flexibility, toughness, surface hardness and transparency, and a method for producing a cured product using the curable composition and a hard coat material.
The curable composition according to the present invention contains (A) a photopolymerization initiator and (B) a polyfunctional acrylate compound containing at least one member selected from the group consisting of a siloxane bond, an aromatic ring, and a bridged saturated ring, wherein (A) ) The photopolymerization initiator contains a compound represented by the following formula (a-1). In the formula, R ¹ is a specific organic group containing an aromatic ring, R ² is a monovalent organic group, and R ³ is a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or a substituent. is an aryl group, and m is 0 or 1.

Description

A curable composition, a method for producing a cured product, and a hard coat material

The present invention relates to a curable composition, a method for producing a cured product using the curable composition, and a hard coat material.

BACKGROUND ART Optical films are used in various image display devices such as liquid crystal displays, plasma displays, CRT displays, EL displays, and field emission displays for purposes such as surface protection, antireflection, and antiglare, for example. It is known that such an optical film uses a hard coat material in which a hard coat layer is formed on the surface of a base material made of triacetyl cellulose (TAC) or the like from the viewpoint of scratch resistance (see, for example, Patent Document 1).

Japanese Unexamined Patent Publication No. 2013-195550

Hard coat layers usually used for hard coat materials are required to have excellent properties such as flexibility, toughness, surface hardness, and transparency. However, conventional hard coat layers do not sufficiently satisfy these requirements.

The present invention has been made in view of the above problems, and provides a curable composition that provides a hard coat layer having excellent flexibility, toughness, surface hardness, and transparency, and a method for producing a cured product using the curable composition and a hard coat material. The purpose.

MEANS TO SOLVE THE PROBLEM The present inventors discovered that the said subject was solvable by the curable composition containing a specific photoinitiator and a specific polyfunctional acrylate compound, and came to complete this invention. Specifically, the present invention provides the following.

The first aspect of the present invention contains (A) a photopolymerization initiator and (B) a polyfunctional acrylate compound containing at least one selected from the group consisting of a siloxane bond, an aromatic ring and a bridged saturated ring,

The (A) photopolymerization initiator has the following formula (a-1):

[Tue 1]

(R ¹ is the following formula (a-2):

[Tue 2]

(R ⁴ is a hydrogen atom, a nitro group, or a monovalent organic group, R ⁵ and R ⁶ are independently a chain alkyl group, a cyclic hydrocarbon group, or a heteroaryl group, and R ⁵ and R ⁶ are bonded to each other to form a spiro ring can be formed.)

Group represented by , the following formula (a-3):

[Tue 3]

(R ⁷ is independently a monovalent organic group, amino group, halogen atom, nitro group, or cyano group, A is S or O, n is an integer from 0 to 4.)

A group represented by or the following formula (a-4):

[Tuesday 4]

(R ⁸ is a monovalent organic group, R ⁹ is a hydrogen atom, a nitro group, or a monovalent organic group), R ² is a monovalent organic group, and R ³ is a hydrogen atom or a substituent It is an alkyl group having 1 to 11 carbon atoms or an aryl group which may have a substituent, and m is 0 or 1.)

It is a curable composition containing the compound represented by.

The second aspect of the present invention is a step of forming a curable composition film using the curable composition;

A method for producing a cured product including a step of exposing the curable composition film.

A third aspect of the present invention is a hard coat material comprising a substrate and a hard coat layer formed on the substrate using the curable composition.

ADVANTAGE OF THE INVENTION According to this invention, the curable composition which provides a hard-coat layer excellent in flexibility, toughness, surface hardness, and transparency, the manufacturing method of hardened|cured material using this curable composition, and a hard-coat material can be provided.

<<curable composition>>

The curable composition according to the present invention contains (A) a photopolymerization initiator and (B) a polyfunctional acrylate compound containing at least one member selected from the group consisting of a siloxane bond, an aromatic ring, and a bridged saturated ring, wherein (A) ) The photopolymerization initiator contains a compound represented by the formula (a-1). The hard coat layer obtained from the curable composition according to the present invention has excellent flexibility, toughness, surface hardness, and transparency, and can be suitably used for a hard coat material.

<(A) photopolymerization initiator>

(A) The photopolymerization initiator is not particularly limited as long as it includes a compound represented by the formula (a-1). Since the curable composition according to the present invention contains (A) a photopolymerization initiator, it has a high sensitivity and sufficiently cures even at a smaller energy dose. (A) A photoinitiator can be used individually or in combination of 2 or more types.

In the formula (a-1), R ¹ is a group represented by the formula (a-2), a group represented by the formula (a-3), or a group represented by the formula (a-4).

Examples of preferable organic groups for R ² include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, a phenyl group which may have a substituent, and a substituent as in R ⁴ described later. A phenoxy group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzoyloxy group which may have a substituent, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a substituent A naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a naphthylalkyl group which may have a substituent, Heterocyclyl group, heterocyclylcarbonyl group which may have a substituent, amino group substituted with 1 or 2 organic groups, morpholin-1-yl group, piperazin-1-yl group, etc. are mentioned.

As for the number of carbon atoms of an alkyl group, when ^R2 is an alkyl group, 1-20 are preferable and 1-6 are more preferable. Moreover, when ^R2 is an alkyl group, it may be straight-chain or branched-chain. Specific examples when R ² is an alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, n-decyl group A real group, an isodecyl group, etc. are mentioned. Moreover, when ^R2 is an alkyl group, the alkyl group may contain the ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include methoxyethyl group, ethoxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, propyloxyethoxyethyl group, and methoxypropyl group.

As for the carbon atom number of an alkoxy group, when ^R2 is an alkoxy group, 1-20 are preferable and 1-6 are more preferable. Moreover, when ^R2 is an alkoxy group, it may be straight-chain or branched-chain. Specific examples in case R ² is an alkoxy group include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, n -Pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octyloxy group, tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, isodecyloxy group, etc. are mentioned. Moreover, when ^R2 is an alkoxy group, the alkoxy group may contain the ether bond (-O-) in a carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include a methoxyethoxy group, an ethoxyethoxy group, a methoxyethoxyethoxy group, an ethoxyethoxyethoxy group, a propyloxyethoxyethoxy group, and a methoxy group. A propyloxy group etc. are mentioned.

As for the carbon atom number of a cycloalkyl group or a cycloalkoxy group, when ^R2 is a cycloalkyl group or a cycloalkoxy group, 3-10 are preferable and 3-6 are more preferable. A cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group etc. are mentioned as a specific example in case R ^<2> is a cycloalkyl group. Specific examples in case R ² is a cycloalkoxy group include cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, cycloheptyloxy group, and cyclooctyloxy group.

As for the carbon atom number of a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, when R ^<2> is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, 2-21 are preferable and 2-7 are more preferable. Specific examples when R ² is a saturated aliphatic acyl group include acetyl group, propanoyl group, n-butanoyl group, 2-methylpropanoyl group, n-pentanoyl group, 2,2-dimethylpropanoyl group, n-hexanoyl group, n -Heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n-tetradecanoyl group, n-pentanoyl group A decanoyl group, and an n-hexadecanoyl group, etc. are mentioned. Specific examples in case R ² is a saturated aliphatic acyloxy group include acetyloxy group, propanoyloxy group, n-butanoyloxy group, 2-methylpropanoyloxy group, n-pentanoyloxy group, and 2,2-dimethylpropanoyloxy group. , n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n-dodecanoyloxy group, n- Tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, n-hexadecanoyloxy group, etc. are mentioned.

As for the carbon atom number of an alkoxycarbonyl group, when ^R2 is an alkoxycarbonyl group, 2-20 are preferable and 2-7 are more preferable. Specific examples of when R ² is an alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyloxycarbonyl group, tert-butyloxy group. carbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, sec- Octyloxycarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, isononyloxycarbonyl group, n-decyloxycarbonyl group, isodecyloxycarbonyl group, etc. are mentioned.

When R ² is a phenylalkyl group, the number of carbon atoms in the phenylalkyl group is preferably 7 to 20, and more preferably 7 to 10. Moreover, as for the number of carbon atoms of a naphthylalkyl group, when R ^<2> is a naphthylalkyl group, 11-20 are preferable and 11-14 are more preferable. Specific examples in the case where R ² is a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group. Specific examples in the case where R ² is a naphthylalkyl group include an α-naphthylmethyl group, a β-naphthylmethyl group, a 2-(α-naphthyl)ethyl group, and a 2-(β-naphthyl)ethyl group. When R ² is a phenylalkyl group or a naphthylalkyl group, R ² may further have a substituent on the phenyl group or naphthyl group.

When R ² is a heterocyclyl group, the heterocyclyl group is a 5-membered or 6-membered monocyclic ring containing at least one of N, S, and O, or a heterocyclyl group formed by condensation of such monocycles or a benzene ring. When the heterocyclyl group is a condensed ring, it is assumed that the ring number is up to 3. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocycle constituting the heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, and pyrimidine. , pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzoimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthala gin, cinoline, and quinoxaline; and the like. When R ² is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When R ² is a heterocyclylcarbonyl group, the heterocyclyl groups included in the heterocyclylcarbonyl group are the same as those in the case where R ² is a heterocyclyl group.

When R ² is an amino group substituted with an organic group of 1 or 2, preferred examples of the organic group include an alkyl group of 1 to 20 carbon atoms, a cycloalkyl group of 3 to 10 carbon atoms, and a saturated aliphatic group of 2 to 21 carbon atoms. A phenyl group which may have a real group, a substituent, a benzoyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a substituent A naphthylalkyl group having 11 to 20 carbon atoms which may have, and a heterocyclyl group. Specific examples of these preferred organic groups are the same as for R ² . Specific examples of the amino group substituted with 1 or 2 organic groups include methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n-butylamino group, di-n-butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, naphthylamino group, acetylamino group, propanoylamino group, n-butanoylamino group , n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n-decanoylamino group, benzoylamino group, α-naphthoylamino group, and β-naphthoylamino group, etc. there is.

Examples of the substituent in case the phenyl group, naphthyl group, and heterocyclyl group included in R ² further have a substituent include an alkyl group of 1 to 6 carbon atoms, an alkoxy group of 1 to 6 carbon atoms, and a carbon atom group of 2 to 7 carbon atoms. A saturated aliphatic acyl group, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms Dialkylamino group, morpholin-1-yl group, piperazin-1-yl group, halogen, nitro group, and cyano group having When the phenyl group, naphthyl group, and heterocyclyl group included in R ² further have substituents, the number of substituents is not limited to the range not impairing the object of the present invention, but is preferably 1 to 4. When the phenyl group, naphthyl group, and heterocyclyl group included in R ² have a plurality of substituents, the plurality of substituents may be the same or different.

Moreover, as R ^<2> , a cycloalkylalkyl group, the phenoxyalkyl group which may have a substituent on the aromatic ring, and the phenylthioalkyl group which may have a substituent on the aromatic ring are preferable. The substituents that the phenoxyalkyl group and the phenylthioalkyl group may have are the same as the substituents that the phenyl group contained in R ² may have.

Among the organic groups, R ² is preferably an alkyl group, a cycloalkyl group, a phenyl group which may have a substituent, a cycloalkylalkyl group, or a phenylthioalkyl group which may have a substituent on the aromatic ring. The alkyl group is preferably an alkyl group of 1 to 20 carbon atoms, more preferably an alkyl group of 1 to 8 carbon atoms, particularly preferably an alkyl group of 1 to 4 carbon atoms, and most preferably a methyl group. Among the phenyl groups which may have a substituent, a methylphenyl group is preferable, and a 2-methylphenyl group is more preferable. 5-10 are preferable, as for the number of carbon atoms of the cycloalkyl group contained in a cycloalkylalkyl group, 5-8 are more preferable, and 5 or 6 are especially preferable. The number of carbon atoms in the alkylene group contained in the cycloalkylalkyl group is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 2. Among the cycloalkylalkyl groups, a cyclopentylethyl group is preferred. As for the carbon atom number of the alkylene group contained in the phenylthioalkyl group which may have a substituent on an aromatic ring, 1-8 are preferable, 1-4 are more preferable, and 2 is especially preferable. Among the phenylthioalkyl groups which may have a substituent on the aromatic ring, a 2-(4-chlorophenylthio)ethyl group is preferable.

As mentioned above, although ^R2 was demonstrated, as ^R2 , the group represented by the following formula (R2-1) or (R2-2) is preferable.

[Tuesday 5]

(In formulas (R2-1) and (R2-2), R ¹⁰ and R ¹¹ are each an organic group, p is an integer of 0 to 4, and R ¹⁰ and R ¹¹ are present at adjacent positions on the benzene ring. In this case, R ¹⁰ and R ¹¹ may combine with each other to form a ring, q is an integer of 1 to 8, r is an integer of 1 to 5, s is an integer of 0 to (r + 3), and R ¹² is an alkyl group am.)

Examples of organic groups for R ¹⁰ and R ¹¹ in formula (R2-1) are the same as for R ² . As R ¹⁰ , an alkyl group or a phenyl group is preferable. As for the number of carbon atoms, when R ^<10> is an alkyl group, 1-10 are preferable, 1-5 are more preferable, 1-3 are especially preferable, and 1 is the most preferable. That is, R ¹⁰ is most preferably a methyl group. When R ¹⁰ and R ¹¹ combine to form a ring, the ring may be an aromatic ring or an aliphatic ring. Preferable examples of the group represented by formula (R2-1), in which R ¹⁰ and R ¹¹ form a ring, include a naphthalen-1-yl group, a 1,2,3,4-tetrahydronaphthalen-5-yl group, and the like. can be heard In the formula (R2-1), p is an integer of 0 to 4, preferably 0 or 1, and more preferably 0.

In the formula (R2-2), R ¹² is an alkyl group. 1-10 are preferable, as for the number of carbon atoms of an alkyl group, 1-5 are more preferable, and 1-3 are especially preferable. As ^R12 , a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, etc. are illustrated preferably, and among these, a methyl group is more preferable.

In the formula (R2-2), r is an integer of 1 to 5, preferably an integer of 1 to 3, and more preferably 1 or 2. In the formula (R2-2), s is 0 to (r+3), preferably an integer of 0 to 3, more preferably an integer of 0 to 2, particularly preferably 0. In the formula (R2-2), q is an integer of 1 to 8, preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and particularly preferably 1 or 2.

In formula (a-1), R ³ is a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent. As a substituent which may have when R ^<3> is an alkyl group, a phenyl group, a naphthyl group, etc. are illustrated preferably. Moreover, as a substituent which may have when R ^<3> is an aryl group, a C1-C5 alkyl group, an alkoxy group, a halogen atom, etc. are illustrated preferably.

In formula (a-1), preferred examples of R ³ include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a phenyl group, a benzyl group, a methylphenyl group, a naphthyl group, and the like. Among them, a methyl group or a phenyl group is more preferable.

In formula (a-2), R ⁴ is a hydrogen atom, a nitro group or a monovalent organic group. R ⁴ bonds to a 6-membered aromatic ring different from the 6-membered aromatic ring bonded to the group represented by -(CO) _m- in formula (a-1) on the fluorene ring in formula (a-2). As long as this condition is satisfied, the bonding position of R ⁴ to the fluorene ring in formula (a-2) is not particularly limited. The bonding position of R ⁴ to the fluorene ring is preferably the 2nd position in the fluorene ring from the viewpoint of easy synthesis of the compound represented by formula (a-1) where R ¹ is a group represented by formula (a-2). .

When R ⁴ is an organic group, R ⁴ is not particularly limited as long as the object of the present invention is not impaired, and is appropriately selected from various organic groups. Preferred examples in case R ⁴ is an organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, a phenyl group which may have a substituent, and a substituent as in R ² . The phenoxy group which may have, the benzoyl group which may have a substituent, the phenoxycarbonyl group which may have a substituent, the benzoyloxy group which may have a substituent, the phenylalkyl group which may have a substituent, the naphthyl group which may have a substituent, the substituent The naphthoxy group which may have a substituent, the naphthoyl group which may have a substituent, the naphthoxycarbonyl group which may have a substituent, the naphthoyloxy group which may have a substituent, the naphthylalkyl group which may have a substituent, the hetero which may have a substituent A cyclyl group, a heterocyclylcarbonyl group which may have a substituent, an amino group substituted with 1 or 2 organic groups, a morpholin-1-yl group, and a piperazin-1-yl group. Specific examples of these groups are the same as those described for R ² .

Among the groups described above, a nitro group or a group represented by R ¹³ -CO- as R ⁴ is preferable because the sensitivity tends to be improved. R ¹³ is not particularly limited as long as the object of the present invention is not impaired, and can be selected from various organic groups. Examples of groups suitable for R ¹³ include an alkyl group having 1 to 20 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a heterocyclyl group which may have a substituent. Among these groups as R ¹³ , a 2-methylphenyl group, a thiophen-2-yl group, and an α-naphthyl group are particularly preferred.

In addition, when R ⁴ is a hydrogen atom, transparency tends to be improved, which is preferable. Further, when R ⁴ is a hydrogen atom and R ² is the above-mentioned (R2-2), the transparency tends to be better.

In formula (a-1), R ⁵ and R ⁶ are each a chain alkyl group, a cyclic hydrocarbon group, or a heteroaryl group. Among these groups, chain alkyl groups are preferred as R ⁵ and R ⁶ .

When R ⁵ and R ⁶ are chain alkyl groups, the chain alkyl group may be either a straight chain alkyl group or a branched chain alkyl group. When R ⁵ and R ⁶ are chain alkyl groups, the number of carbon atoms in the chain alkyl group is preferably 1 to 20, and more preferably 1 to 6. Specific examples when R ⁵ and R ⁶ are chain alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, Isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group , n-decyl group, and isodecyl group. Moreover, when ^R5 and ^R6 are chain|stranded alkyl groups, the chain|stranded alkyl group may contain the ether bond (-O-) in a carbon chain. Examples of the chain alkyl group having an ether bond in the carbon chain include methoxyethyl group, ethoxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, propyloxyethoxyethyl group, and methoxypropyl group.

When R ⁵ and R ⁶ are cyclic hydrocarbon groups, the cyclic hydrocarbon group may be either an aliphatic cyclic hydrocarbon group or an aromatic cyclic hydrocarbon group.

When R ⁵ and R ⁶ are aromatic cyclic hydrocarbon groups, the aromatic cyclic hydrocarbon group is preferably a phenyl group, a group formed by bonding of a plurality of benzene rings via a carbon-carbon bond, or a group formed by condensation of a plurality of benzene rings. When the aromatic cyclic hydrocarbon group is a phenyl group or a group formed by bonding or condensation of a plurality of benzene rings, the number of rings of the benzene rings contained in the aromatic cyclic hydrocarbon group is not particularly limited, and is preferably 3 or less, more preferably 2 or less, and 1 is particularly preferred. Preferred specific examples of the aromatic cyclic hydrocarbon group include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, and a phenanthryl group.

When R ⁵ and R ⁶ are aliphatic cyclic hydrocarbon groups, the aliphatic cyclic hydrocarbon group may be monocyclic or polycyclic. The number of carbon atoms in the aliphatic cyclic hydrocarbon group is not particularly limited, but is preferably 3 to 20 and more preferably 3 to 10. Examples of the monocyclic cyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, A tetracyclododecyl group, an adamantyl group, etc. are mentioned.

When R ⁵ and R ⁶ are heteroaryl groups, the heteroaryl group is a 5-membered or 6-membered monocyclic ring containing at least one of N, S, and O, or a heteroaryl group formed by condensing such monocycles or a benzene ring. When the heteroaryl group is a condensed ring, the number of rings is up to 3. Examples of the heterocycle constituting the heteroaryl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, Pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzoimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine , cinoline, and quinoxaline; and the like.

R ⁵ and R ⁶ may combine with each other to form a spiro ring. It is preferable that the group which consists of a spiro ring formed by ^R5 and ^R6 is a cycloalkylidene group. When R ⁵ and R ⁶ combine to form a cycloalkylidene group, the spiro ring constituting the cycloalkylidene group is preferably a 5-membered to 6-membered ring, more preferably a 5-membered ring.

When the group formed by combining R ⁵ and R ⁶ is a cycloalkylidene group, the cycloalkylidene group may be condensed with one or more other rings. Examples of rings that may be condensed with a cycloalkylidene group include a benzene ring, a naphthalene ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a furan ring, a thiophene ring, a pyrrole ring, a pyridine ring, and a pyraline ring. A true ring, and a pyrimidine ring, etc. are mentioned.

When R ⁷ is an organic group, it can be selected from various organic groups within a range not impairing the object of the present invention. Preferred examples in the case where R ⁷ is an organic group include an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; A saturated aliphatic acyl group having 2 to 7 carbon atoms; alkoxycarbonyl group having 2 to 7 carbon atoms; A saturated aliphatic acyloxy group having 2 to 7 carbon atoms; phenyl group; naphthyl group; benzoyl group; naphthoyl group; a benzoyl group substituted with a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group; a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms; dialkylamino group having an alkyl group having 1 to 6 carbon atoms; morpholine-1-yl group; piperazine-1-yl group; halogen; nitro group; A cyano group is mentioned.

Among R ⁷ , a benzoyl group; naphthoyl group; a benzoyl group substituted with a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group; A nitro group is preferable, and a benzoyl group; naphthoyl group; 2-methylphenylcarbonyl group; 4-(piperazin-1-yl)phenylcarbonyl group; A 4-(phenyl)phenylcarbonyl group is more preferred.

Moreover, n is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1. When n is 1, the bonding position of R ⁷ is preferably para-position with respect to the bond where the phenyl group to which R ⁷ is bonded is bonded to the atom A.

It is preferable that A is S.

R ⁸ can be selected from various organic groups within a range not impairing the object of the present invention. Preferred examples of R ⁸ include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a phenyl group which may have a substituent, and a phenyl group which may have a substituent. Benzoyl group, phenoxycarbonyl group which may have a substituent, phenylalkyl group which may have a substituent having 7 to 20 carbon atoms, naphthyl group which may have a substituent, naphthoyl group which may have a substituent, naphthoxycarbonyl group which may have a substituent , a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, a heterocyclyl group which may have a substituent, and a heterocyclylcarbonyl group which may have a substituent.

Among R ⁸ , an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an ethyl group is particularly preferable.

Examples of substituents in the case where the phenyl group, naphthyl group, and heterocyclyl group in R ⁷ or R ⁸ further have a substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a saturated aliphatic group having 2 to 7 carbon atoms. Sil group, alkoxycarbonyl group of 2 to 7 carbon atoms, saturated aliphatic acyloxy group of 2 to 7 carbon atoms, monoalkylamino group having an alkyl group of 1 to 6 carbon atoms, dialkylamino group having an alkyl group of 1 to 6 carbon atoms, morpholine-1- diyl group, piperazin-1-yl group, halogen, nitro group, and cyano group; and the like. When the phenyl group, naphthyl group, and heterocyclyl group included in R ⁷ or R ⁸ further have substituents, the number of substituents is not limited to the range not impairing the object of the present invention, but is preferably 1 to 4. . When the phenyl group, naphthyl group, and heterocyclyl group contained in R ⁷ or R ⁸ have a plurality of substituents, the plurality of substituents may be the same or different.

R ⁹ is the same as R ⁴ .

The compound represented by formula (a-1) can be synthesized, for example, according to the following scheme 1 when m is 0. In Scheme 1, a compound represented by the following formula (1-1) is used as a raw material. For example, when R ¹ is a group represented by formula (a-2), in Scheme 1, a fluorene derivative represented by formula (1-1-1) is used as a raw material. When R ⁴ is a nitro group or a monovalent organic group, the fluorene derivative represented by formula (1-1-1) is a fluorene derivative in which the 9th position is substituted with R ⁵ and R ⁶ , by a known method, substituent R ⁴ can be obtained by introducing A fluorene derivative in which the 9-position is substituted with R ⁴ and R ⁵ , for example, when R ⁴ and R ⁵ are alkyl groups, as described in Japanese Patent Laid-Open No. 06-234668, in the presence of an alkali metal hydroxide, It can be obtained by reacting fluorene with an alkylating agent in a protic polar organic solvent. In addition, an alkylating agent such as an alkyl halide, an aqueous solution of an alkali metal hydroxide, and a phase transfer catalyst such as tetrabutylammonium iodide or potassium tert-butoxide are added to an organic solvent solution of fluorene to carry out an alkylation reaction, 9-alkyl substituted fluorene can be obtained.

The compound represented by formula (1-1) is acylated using the halocarbonyl compound represented by formula (1-2) by a Friedel Craft reaction to obtain a ketone compound represented by formula (1-3). In Formula (1-2), Hal is a halogen atom. The position to be acylated by the compound represented by the formula (1-2) on the aromatic ring contained in R ¹ can be acylated by appropriately changing the conditions of the Friedel Craft reaction or by the compound represented by the formula (1-2) on the aromatic ring. It is possible to select from a method of carrying out protection and deprotection at a position other than the position to be misfired.

Next, the ketone compound represented by the obtained formula (1-3) is oxime-treated with hydroxylamine to obtain an oxime compound represented by the following formula (1-4). An oxime compound of formula (1-4), an acid anhydride ((R ³ CO) ₂ O) represented by formula (1-5) below, or an acid halide (R ³ COHal, Hal) represented by formula (1-6) below silver halogen atom) can be reacted to obtain a compound represented by the following formula (1-7).

Also, equations (1-1), (1-2), (1-3), (1-4), (1-5), (1-6), (1-7), and (1-1- In 1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ are the same as in Formula (a-1).

<Scheme 1>

[Tue 6]

When m is 1, the compound represented by formula (a-1) can be synthesized, for example, according to the following scheme 2. In Scheme 2, a compound represented by the following formula (2-1) is used as a raw material. The compound represented by Formula (2-1) is obtained by acylating the compound represented by Formula (1-1) by a Friedel Craft reaction in the same manner as in Scheme 1. A compound represented by formula (2-1) is reacted with a nitrite ester (RONO, R is an alkyl group having 1 to 6 carbon atoms) represented by formula (2-2) in the presence of hydrochloric acid, represented by formula (2-3) A ketoxime compound is obtained. Next, a ketoxime compound represented by the following formula (2-3), an acid anhydride ((R ³ CO) ₂ O) represented by the following formula (2-4), or an acid represented by the following formula (2-5) A compound represented by the following formula (2-6) can be obtained by reacting a halide (R ³ COHal, where Hal is a halogen atom). Further, in the following formulas (2-1), (2-3), (2-4), (2-5), and (2-6), R ¹ , R ² , and R ³ are the formula (a-1 ) is the same as

When m is 1, there exists a tendency that the generation|occurrence|production of a foreign material in the hardened|cured material formed using the curable composition containing the compound represented by Formula (a-1) can be reduced more.

<Scheme 2>

[Tue 7]

The following compounds are mentioned as a preferable specific example of the compound represented by Formula (a-1).

[Tue 8]

[Tue 9]

[Tue 10]

[Tue 11]

[Tue 12]

[Tue 13]

[Tue 14]

(A) The content of the photopolymerization initiator is preferably 0.1 to 90 parts by weight, more preferably 1 to 80 parts by weight, based on 100 parts by weight of the total solid content of the curable composition. (A) When the content of the photopolymerization initiator is within the above range, the curable composition according to the present invention tends to be more sensitive.

<(B) multifunctional acrylate compound>

(B) It is not specifically limited as long as it contains at least 1 sort(s) selected from the group which consists of a siloxane bond, an aromatic ring, and a crosslinked saturated ring as a polyfunctional acrylate compound. (B) The polyfunctional acrylate compound contributes to improvement in flexibility, toughness, and surface hardness of the hard coat layer obtained from the curable composition according to the present invention. (B) A polyfunctional acrylate compound can be used individually or in combination of 2 or more types. (B) The polyfunctional acrylate compound may be a low molecular weight compound, an oligomer and/or polymer having a specific repeating unit, or a combination thereof.

(B) What contains a siloxane bond containing polyfunctional acrylate compound as a polyfunctional acrylate compound, for example; polyfunctional acrylate compounds containing at least one selected from the group consisting of an aromatic ring and a crosslinked saturated ring; siloxane bond-containing polyfunctional acrylics from the viewpoint that the properties of the obtained hard coat layer are easily improved; It is preferable to include a polyfunctional acrylate compound containing a rate compound and at least one selected from the group consisting of an aromatic ring and a bridged saturated ring.

[Multifunctional Acrylate Compound Containing Siloxane Bond]

Although the polyfunctional acrylate compound containing siloxane bonds does not significantly contribute to the effect of improving the flexibility or inhibiting curing shrinkage (reduction of curling properties) of the obtained hard coat layer, it greatly contributes to the increase in surface hardness of the hard coat layer. Examples of the siloxane bond-containing polyfunctional acrylate compound include polysilsesquioxane compounds containing two or more (meth)acryloyl groups. In particular, as the polysilsesquioxane compound, a cage-like polysilsesquioxane compound containing two or more (meth)acryloyl groups is preferable since the surface hardness of the hard coat layer obtained is more likely to be improved.

As said polysilsesquioxane compound, the following formula, for example:

[RSiO _{3 / 2} ] _n

(Wherein, R is independently a (meth)acryloyl group or a carboxyl group-containing group, n is 8, 10, 12, or 14, provided that two or more R are (meth)acryloyl groups.) Type polysilsesquioxane is mentioned.

Examples of the carboxyl group-containing group include a monovalent group represented by -X-B-Y-COOH.

X is a single bond, an alkylene group having 1 to 6 carbon atoms, an allylene group, or -R5-NH-R6- (wherein R5 and R6 represent an alkylene group having 1 to 3 carbon atoms. R5 and R6 may be the same; may be different), and Y is a divalent group generated by removing one hydrogen atom from each of two ring carbon atoms from an aromatic ring group or an alicyclic group, or a carbon number 1 to 1 which may have a branched chain and/or a double bond 4 represents a divalent alkylene group, and B represents -NHCO- or -CONH-. However, X and/or Y may have at least one group selected from the group consisting of a (meth)acrylic group, a vinyl group, and an epoxy group as a substituent.

Specifically as a C1-C6 alkylene group in said X, a methylene group, an ethylene group, a propylene group, a butylene group etc. are mentioned, for example. As the allylene group in the above X, those having 6 to 10 carbon atoms are preferable. As such a thing, a phenylene group (ortho, meta, para etc.), a naphthylene group (1,4-, 1,5-, 2,6- etc.) etc. are mentioned, for example. Specific examples of -R5-NH-R6- in X include -CH ₂ -NH-CH ₂ -, -(CH2) ₂ -NH-(CH ₂ ) ₂ -, -(CH ₂ ) ₃ -NH-(CH ₂ ) ₃ -, -CH ₂ -NH-(CH ₂ ) ₂ -, -(CH ₂ ) ₂ -NH-CH ₂ -, -(CH ₂ ) ₂ -NH-(CH ₂ ) ₃ -, -(CH ₂ ) ₃ -NH-(CH ₂ ) ₂ -, -CH ₂ -NH-(CH ₂ ) ₃ -, -(CH ₂ ) ₃ -NH-CH ₂ - and the like.

Examples of the aromatic ring in Y include aromatic rings having 6 to 10 carbon atoms which may have substituents having 1 to 2 carbon atoms (eg, benzene ring, naphthalene ring, tolyl group, xylyl group, etc.). Examples of the alicyclic ring in Y include an alicyclic ring having 5 to 10 carbon atoms (eg, a monocyclic cycloalkyl group, a monocyclic cycloalkenyl group, a bicyclic alkyl group, a cage alkyl group, etc., specifically, for example, a cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, dicyclopentadiene ring, norbornane ring, norbornene ring, cubane ring, basketane ring, etc.). Specific examples of the alkylene group having 1 to 4 carbon atoms that may have a branched chain and/or double bond in Y include a methylene group, an ethylene group, a propylene group, a vinylene group, and a (2-octenyl)ethylene group. , (2,4,6-trimethyl-2-nonenyl) an alkylene group such as an ethylene group, an alkylene group having a double bond, or an alkylene group having a branched chain of 1 to 9 carbon atoms.

[Polyfunctional acrylate compound containing at least one member selected from the group consisting of aromatic rings and bridged saturated rings]

A polyfunctional acrylate compound containing at least one selected from the group consisting of an aromatic ring and a bridged saturated ring has a moderate contribution to the effect of increasing the surface hardness of the obtained hard coat layer, but an aromatic ring and/or a bridged saturated ring By the synergistic action of the rigid partial skeleton and the flexible partial skeleton such as an alkylene group (eg, methylene group, ethylene group, etc.), an ether bond, and / or a urethane bond, the flexibility improvement or curing of the hard coat layer It greatly contributes to suppression of shrinkage (reduction of curling properties).

Examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a fluorene ring, a furan ring, a pyrrole ring, an imidazole ring, a thiophene ring, a phosphole ring, a pyrazole ring, an oxazole ring, and an isoxazole ring. , Thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, triazine ring, tetrazine ring, benzofuran ring, isobenzofuran ring, indole ring, isoindole ring, benzothiophene ring, benzophosphole ring, benzo Imidazole ring, purine ring, indazole ring, benzoxazole ring, benzoisoxazole ring, benzothiazole ring, quinoline ring, isoquinoline ring, quinoxaline ring, quinazoline ring, cinoline ring, isocyanurate ring, etc. From the viewpoints of flexibility, curl resistance and the like of the resulting hard coat layer, an isocyanurate ring, a fluorene ring, and a triazine ring are preferable.

Examples of the bridged saturated ring include a norbornane ring, an isobornane ring, an adamantane ring, a tricyclodecane ring, and a tetracyclododecane ring. A tricyclodecane ring is preferable.

(B) The content of the polyfunctional acrylate compound is preferably 10 to 99.9 parts by weight, more preferably 20 to 99 parts by weight, based on 100 parts by weight of the total solid content of the curable composition. (B) When the content of the polyfunctional acrylate compound is within the above range, the hard coat layer obtained from the curable composition according to the present invention tends to have further excellent flexibility, toughness and surface hardness.

＜Other ingredients＞

The curable composition according to the present invention may contain various additives as needed. Specifically, solvents, sensitizers, curing accelerators, photocrosslinking agents, photosensitizers, dispersing aids, fillers, adhesion promoters, antioxidants, ultraviolet absorbers, aggregation inhibitors, thermal polymerization inhibitors, antifoaming agents, surfactants and the like are exemplified.

Examples of the solvent used in the curable composition according to the present invention include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol mono-n-butyl ether, and diethylene glycol monomethyl ether. , Diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol Monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono -(poly)alkylene glycol monoalkyl ethers such as n-butyl ether, tripropylene glycol monomethyl ether, and tripropylene glycol monoethyl ether; (Poly)alkylenes such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate glycol monoalkyl ether acetates; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; Ketones, such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; lactate alkyl esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; 2-Hydroxy-2-methylethylpropionate, 3-methoxymethylpropionate, 3-methoxyethylpropionate, 3-ethoxymethylpropionate, 3-ethoxyethylpropionate, ethoxyacetate ethyl, hydroxyacetate ethyl, 2 -Hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutylacetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-acetic acid Butyl, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, acetoacetic acid other esters such as methyl, ethyl acetoacetate, and ethyl 2-oxobutanoate; Aromatic hydrocarbons, such as toluene and xylene; and amides such as N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide. These solvents may be used alone or in combination of two or more.

Among the above solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 3- Methoxybutyl acetate is preferable because it exhibits excellent solubility to the above-mentioned components (A) and (B), and it is particularly preferable to use propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate. The amount of the solvent used may be appropriately determined depending on the use of the curable composition, but as an example, it is about 50 to 900 parts by weight relative to 100 parts by weight of the total solid content of the curable composition. In the present invention, the use of a solvent tends to facilitate control of the film thickness. This tendency is particularly remarkable when thinning is required. Moreover, when component (B) is solid at room temperature, it is preferable to use a solvent in this invention.

As a thermal polymerization inhibitor used for the curable composition concerning this invention, hydroquinone, hydroquinone monoethyl ether, etc. are mentioned, for example. Moreover, compounds, such as silicone type and a fluorine type, can be illustrated as an antifoamer, and compounds, such as anionic type, cationic type, a nonionic type, etc., can be illustrated as surfactant, respectively.

[Preparation Method of Curable Composition]

The curable composition according to the present invention is prepared by mixing all of the above components with a stirrer. Moreover, when the prepared curable composition does not contain insoluble components, such as a filler, you may filter using a filter so that a curable composition may become uniform.

≪Method for producing cured material≫

A method for producing a cured product according to the present invention comprises the steps of forming a curable composition film using the curable composition according to the present invention;

and exposing the curable composition film to light. The hardened|cured material manufactured by this manufacturing method may be patterned as needed.

As a method for forming a curable composition film using the curable composition according to the present invention, for example, a contact transfer type coating device such as a roll coater, a reverse coater, and a bar coater, or a non-contact type coating device such as a spinner (rotary coating device) and a curtain flow coater A method of applying a curable composition on a substrate using a. Although it does not specifically limit as a board|substrate, For example, the thing mentioned later is mentioned.

You may dry the said curable composition film formed as needed. The drying method is not particularly limited, and examples thereof include (1) a method of drying on a hot plate at a temperature of, for example, 80 to 120°C, preferably 90 to 100°C for 60 to 120 seconds, (2) water at room temperature A method of leaving it for several hours to several days, (3) a method of drying by placing it in a warm air heater or an infrared heater for several tens of minutes to several hours, and the like.

Then, the curable composition film is irradiated with active energy rays such as ultraviolet rays and excimer laser light to expose the curable composition film. Exposure may be performed position-selectively by, for example, a method of exposing through a negative mask or the like, or may be performed by full-surface exposure. In the case of performing full-surface exposure, for example, the curable composition film may be continuously irradiated with active energy rays during the line step while winding the film substrate on which the curable composition film is formed in a line. The energy dose to be irradiated varies depending on the composition of the curable composition, but is preferably, for example, about 40 to 200 mJ/cm ² . A light source is not specifically limited, For example, a high-pressure mercury-vapor lamp and LED etc. are mentioned, From a viewpoint of energy saving or environmental load reduction, LED is preferable. In exposure by LED, the wavelength used is, for example, 365 to 405 nm, more specifically, those in the UV region such as 385 nm, 395 nm, and 405 nm. Generally, the energy dose irradiated by the LED tends to be small. However, since the curable composition according to the present invention contains (A) a photopolymerization initiator and has excellent sensitivity, it is sufficiently cured even when exposed to light using an LED as a light source, and a cured product having good properties can be effectively obtained. As already explained, since the curable composition according to the present invention is excellent in sensitivity, by using the curable composition of the present invention, a hard coat material can be efficiently produced, and as a result, the productivity of a display device such as a liquid crystal display panel is improved. can improve

When the curable composition film is positionally selectively exposed, the film after exposure is developed with a developer to be patterned into a desired shape. The developing method is not particularly limited, and for example, an immersion method, a spray method, or the like can be used. A developer is appropriately selected depending on the composition of the curable composition. When the curable composition contains an alkali-soluble component such as an alkali-soluble resin, the developer is an organic developer such as monoethanolamine, diethanolamine, or triethanolamine, sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, quaternary ammonium salt, etc. Aqueous solutions can be used.

Next, it is preferable to post-bake the pattern after development at about 200 to 250°C.

The cured product produced by the method for producing a cured product according to the present invention can be suitably used as a hard coat layer in a hard coat material, for example.

≪Hard coat materials≫

The hard coat material according to the present invention includes a base material and a hard coat layer formed on the base material using the curable composition according to the present invention.

The substrate is not particularly limited, and a known substrate can be used as a substrate for a hard coat material. Specifically, triacetyl cellulose (TAC), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyamide (PA), polymethyl methacrylate (PMMA), nylon (Ny), polyether sulfone (PES) , film substrates such as polyvinyl chloride (PVC), polypropylene (PP), and polycarbonate (PC); A glass base material etc. are mentioned. Among these, a film substrate is preferable, and a TAC film, a PC film, and a PET film are more preferable.

The hard coat material according to the present invention can be produced by first forming a curable composition film using the curable composition according to the present invention and exposing the curable composition film. Formation and exposure of the curable composition film are the same as those in the method for producing a cured product according to the present invention. As for the film thickness of a hard-coat layer, 1-10 micrometers is preferable.

≪Image display device≫

An image display device according to the present invention is provided with the hard coat material according to the present invention. Examples of the image display device include a liquid crystal display, a plasma display, a CRT display, an EL display, an organic EL display, a field emission display, and the like, and the hard coat material according to the present invention is bonded to the surface of the display or its wiring protective layer.

[ Example ]

Hereinafter, the present invention will be described in more detail by showing examples, but the scope of the present invention is not limited to these examples.

[Examples 1 to 12 and Comparative Examples 1 to 8]

As shown in Table 1, (A) a photopolymerization initiator, (B1) a polyfunctional acrylate compound containing a siloxane bond, and (B2) a polyfunctional acrylate containing at least one selected from the group consisting of an aromatic ring and a bridged saturated ring. The compound and (B3) other acrylate compounds were uniformly mixed to obtain a solvent-free curable composition. Numerical values in parentheses in Table 1 indicate the blending amount of each component (unit: parts by mass).

Compound 1: Photopolymerization initiator represented by the formula on the left in the first column below

Compound 2: photopolymerization initiator represented by the formula on the right in the first column below

Compound 3: photopolymerization initiator represented by the formula in the second column below

[Tuesday 15]

Irg819: Photopolymerization initiator represented by the formula on the left below

Irg184: photopolymerization initiator represented by the formula in the middle below

OXE01: photopolymerization initiator represented by the formula on the right below

[Tue 16]

Silsesquioxane 1: Silsesquioxane represented by the formula on the left below, wherein all of R ¹⁹ to R ²⁶ are acryloyloxy groups.

Silsesquioxane 2: It is represented by the formula on the left below, 30 mol% of R ¹⁹ to R ²⁶ is a group represented by the formula on the right below, and 70 mol% of R ¹⁹ to R ²⁶ is a silsesqui group represented by an acryloyloxy group. jade acid

[Tue 17]

Tricyclodecane type: a compound represented by the formula on the left of the first column below

Isocyanuric acid type 1: a compound represented by the formula on the right side of the first column below

Fluorene type: a compound represented by the formula in the second column below

Isocyanuric acid type 2: a compound represented by the formula in the third column below, wherein X represents an acryloyloxy group

[Tue 18]

[Method of forming]

The obtained curable composition was dropped onto a PET film having a thickness of 100 μm and applied with an applicator to obtain a curable composition film. Thereafter, the curable composition film was exposed with a high-pressure mercury lamp exposure machine (ORC) or an LED light (wavelength: 395 nm) to obtain a cured film having a thickness of 50 µm. This cured film was peeled from the said PET film and the following evaluation was performed. These evaluation results are shown in Table 1.

[Surface Hardness]

The pencil hardness of the cured film was measured according to JIS K 5600-5-4. Surface hardness was evaluated according to the following criteria.

◎ (very good): The pencil hardness was 7H or higher.

(circle) (good): The said pencil hardness was 4H - 6H.

x (poor): The said pencil hardness was 3H or less.

[transparency]

The transmittance at 400 nm of the cured film was measured using a transmittance meter MCPD (manufactured by Otsuka Electronics). Transparency was evaluated according to the following criteria.

◎ (very good): The transmittance was 95% or more.

○ (good): The transmittance was 90% or more and less than 95%.

x (poor): The transmittance was less than 90%.

[Flexibility and Toughness]

A stainless rod having a radius n (unit mm, n is an integer greater than or equal to 1) was prepared. The cured film was wound around each prepared stainless rod. Among the stainless steel rods that could be wound without breaking the cured film, those having the smallest radius were specified. Flexibility and toughness were evaluated according to the following criteria.

◎ (very good): The minimum radius was 2 mm or less.

○ (Good): The minimum radius was 3 mm to 5 mm.

x (defective): The minimum radius was 6 mm or more.

As can be seen from Table 1, the hard coat layer obtained from the curable composition according to the present invention has excellent flexibility, toughness, surface hardness, and transparency, and can be suitably used as a hard coat material.

Claims (6)

(A) a photopolymerization initiator and (B) a siloxane bond-containing polyfunctional acrylate compound,
The (A) photopolymerization initiator has the following formula (a-1):

(R ¹ is the following formula (a-2):

(R ⁴ is a hydrogen atom, a nitro group, or a monovalent organic group, R ⁵ and R ⁶ are independently a chain alkyl group, a cyclic hydrocarbon group, or a heteroaryl group, and R ⁵ and R ⁶ are bonded to each other to form a spiro ring can be formed.)
A group represented by or the following formula (a-3):

(R ⁷ is independently a monovalent organic group, amino group, halogen atom, nitro group, or cyano group, A is S or O, n is an integer from 0 to 4.)
is a group represented by , R ² is a monovalent organic group, R ³ is a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent, m is 0 or 1 . However, when R ¹ is a group represented by the above formula (a-3), R ² is the following formula (R2-1):

(In formula (R2-1), R ¹⁰ and R ¹¹ are each an organic group, p is an integer of 0 to 4, and when R ¹⁰ and R ¹¹ are present at adjacent positions on the benzene ring, R ¹⁰ and R ¹¹ may combine with each other to form a ring.)
It is a group represented by .)
A curable composition comprising a compound represented by The method of claim 1,
R ² is the following formula (R2-1):

(In formula (R2-1), R ¹⁰ and R ¹¹ are each an organic group, p is an integer of 0 to 4, and when R ¹⁰ and R ¹¹ are present at adjacent positions on the benzene ring, R ¹⁰ and R ¹¹ may combine with each other to form a ring.)
A group represented by , a curable composition. (A) a photopolymerization initiator and (B) a siloxane bond-containing polyfunctional acrylate compound,
The (A) photopolymerization initiator has the following formula (a-1):

(R ¹ is the following formula (a-2):

(R ⁴ is a hydrogen atom, a nitro group, or a monovalent organic group, R ⁵ and R ⁶ are independently a chain alkyl group, a cyclic hydrocarbon group, or a heteroaryl group, and R ⁵ and R ⁶ are bonded to each other to form a spiro ring can be formed.)
A group represented by or the following formula (a-3):

(R ⁷ is independently a monovalent organic group, amino group, halogen atom, nitro group, or cyano group, A is S or O, n is an integer from 0 to 4.)
is a group represented by , R ² is a monovalent organic group, R ³ is a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent, m is 0 or 1 . However, when R ¹ is a group represented by the formula (a-3), R ² is an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, or a phenyl group which may have a substituent. , a phenoxy group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzoyloxy group which may have a substituent, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent , a naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, a naphthyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a substituent A heterocyclyl group which may have a substituent, a heterocyclylcarbonyl group which may have a substituent, an amino group substituted with 1 or 2 organic groups, a morpholin-1-yl group, a piperazin-1-yl group, a cycloalkylalkyl group, a substituent on an aromatic ring It is the phenoxyalkyl group which may have, or the phenylthioalkyl group which may have a substituent on the aromatic ring.)
Including the compound represented by
The siloxane bond-containing multifunctional acrylate compound is a polysilsesquioxane compound containing two or more (meth)acryloyl groups,
The polysilsesquioxane compound has the following formula:
[RSiO _3/2 ] _n
(Wherein, R is independently a (meth) acryloyl group or a carboxyl group-containing group, n is 8, 10, 12, or 14, provided that two or more R are (meth) acryloyl groups. The carboxyl group-containing group A monovalent group represented by -XBY-COOH, where X is a single bond, an alkylene group having 1 to 6 carbon atoms, an allylene group, or -R5-NH-R6- (wherein R5 and R6 are alkylene groups having 1 to 3 carbon atoms) R5 and R6 may be the same or different), and Y is a divalent group or branched chain formed by removing one hydrogen atom from each of two ring carbon atoms from an aromatic or alicyclic group; / or represents a divalent alkylene group having 1 to 4 carbon atoms, which may have a double bond, and B represents -NHCO- or -CONH-, where X and / or Y represent a (meth)acrylic group, a vinyl group, or an epoxy group It may have at least 1 sort(s) of group selected from the group which consists of as a substituent.) The curable composition which is a cage polysilsesquioxane represented by). The method according to any one of claims 1 to 3,
The (B) curable composition comprising a polyfunctional acrylate compound containing at least one selected from the group consisting of an aromatic ring and a crosslinked saturated ring. A step of forming a curable composition film using the curable composition according to any one of claims 1 to 3;
A method for producing a cured product including a step of exposing the curable composition film. A hard coat material comprising a substrate and a hard coat layer formed on the substrate using the curable composition according to any one of claims 1 to 3.