KR20160149147A - Curable composition, method for production of cured product, and hard-coating material - Google Patents

Abstract

The present invention relates to a curable composition which provides a hard coating layer having excellent bending properties, toughness, surface hardness and transparency, and a method for preparing a cured product and a hard coating material using the curable composition. The curable composition according to the present invention comprises (A) a photopolymerization initiator, and (B) a multi-functional acrylate compound including at least one selected from the group consisting of a siloxane bond, an aromatic ring and a crosslinked saturated ring, wherein (A) the photopolymerization initiator comprises a compound represented by chemical formula (a-1). In chemical formula (a-1), R^1 is a specific organic group containing an aromatic ring; R^2 is a monovalent organic group; R^3 is H, an optionally substituted C1-C11 alkyl group, or an optionally substituted aryl group; and m is 0 or 1.

Description

CURABLE COMPOSITION, METHOD FOR PRODUCTION OF CURED PRODUCT, AND HARD-COATING MATERIAL BACKGROUND OF THE INVENTION 1. Field of the Invention [0001]

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

BACKGROUND ART Various image display devices such as a liquid crystal display, a plasma display, a CRT display, an EL display, and a field emission display use optical films for the purpose of, for example, protecting the surface, preventing reflection, and preventing glare. From the viewpoint of scratch resistance, it is known to use a hard coat material in which a hard coat layer is formed on the surface of a substrate made of triacetylcellulose (TAC) or the like (see, for example, Patent Document 1).

Japanese Patent Application Laid-Open No. 2013-195550

Generally, the hard coat layer used in the hard coat material is required to have excellent properties such as flexibility, toughness, surface hardness, and transparency. However, the conventional hard coat layer does not sufficiently satisfy such a demand.

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and an object of the present invention is to provide a curable composition which gives a hard coat layer excellent in 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.

The present inventors have found out that the above problems can be solved by a curable composition containing a specific photopolymerization initiator and a specific polyfunctional acrylate compound, and have completed the present invention. Specifically, the present invention provides the following.

A first aspect of the present invention relates to a photopolymerizable composition comprising (A) a photopolymerization initiator, (B) a polyfunctional acrylate compound containing at least one member selected from the group consisting of siloxane bonds, aromatic rings and crosslinking rings,

Wherein the photopolymerization initiator (A) is represented by the following formula (a-1):

However,

(R ¹ is a group represented by the following formula (a-2):

[Figure 2]

(R ⁴ is a hydrogen atom, a nitro group, or a monovalent organic group, R ⁵ and R ⁶ are independently a straight 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 .

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

[Figure 3]

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

, Or a group represented by the following formula (a-4):

[Figure 4]

(R ⁸ is a monovalent organic group and 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, a substituent Or an aryl group which may have a substituent, and m is 0 or 1.)

, ≪ / RTI >

A second aspect of the present invention is a process for producing a curable composition comprising the steps of forming a curable composition film using the curable composition,

And a step of exposing the curable composition film to light.

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.

According to the present invention, it is possible to provide a curable composition that gives a hard coat layer excellent in flexibility, toughness, surface hardness, and transparency, and a method of producing a cured product using the curable composition and a hard coat material.

&Quot; Curing Composition "

The curable composition according to the present invention comprises (A) a photopolymerization initiator, and (B) a polyfunctional acrylate compound comprising at least one member selected from the group consisting of siloxane bonds, aromatic rings and crosslinking rings, ) The photopolymerization initiator includes the compound represented by the above formula (a-1). The hard coat layer obtained from the curable composition according to the present invention is excellent in flexibility, toughness, surface hardness and transparency and can be suitably used for hard coat materials.

<(A) Photopolymerization initiator>

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

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).

As examples of R ² A preferred organic group in the same manner as described below R ^4, an alkyl group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, a phenyl group, the substituent 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 naphthoyl 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 heterocyclyl group, a heterocyclyl group which may have a substituent, an amino group substituted by an organic group of 1 or 2, And the like can be mentioned 1-yl group, and a piperazin-1-yl group.

When R ² is an alkyl group, the number of carbon atoms of the alkyl group is preferably from 1 to 20, more preferably from 1 to 6. When R ² is an alkyl group, it may be straight chain or branched chain. Specific examples of the case where R ² is an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec- n-hexyl group, n-heptyl group, n-octyl group, iso-octyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, n- And an isodecyl group. When R ² is an alkyl group, the alkyl group may contain an ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.

When R ² is an alkoxy group, the number of carbon atoms of the alkoxy group is preferably from 1 to 20, more preferably from 1 to 6. When R ² is an alkoxy group, it may be a straight chain or a branched chain. Specific examples of the case where R ² is an alkoxy group include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, tert- N-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octyloxy group, isohexyloxy group, isopentyloxy group, sec- tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, and isodecyloxy group. When R ² is an alkoxy group, the alkoxy group may contain an ether bond (-O-) in the 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 propoxyoxyethoxyethoxy group, and a methoxy Propyloxy group and the like.

When R ² is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms of the cycloalkyl group or the cycloalkoxy group is preferably from 3 to 10, more preferably from 3 to 6. Specific examples of the case where R ² is a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Specific examples of when R ² is a cycloalkoxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group.

When R ² is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms of the saturated aliphatic acyl group or the saturated aliphatic acyloxy group is preferably 2 to 21, more preferably 2 to 7. Specific examples of when R ² is a saturated aliphatic acyl group include an acetyl group, a propanoyl group, an n-butanoyl group, a 2-methylpropanoyl group, an n-pentanonyl group, a 2,2-dimethylpropanoyl group, Heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, Decanoyl group, n-hexadecanoyl group, and the like. Specific examples of the case where R ² is a saturated aliphatic acyloxy group include an acetyloxy group, propanoyloxy group, n-butanoyloxy group, 2-methylpropanoyloxy group, n-pentanoyloxy group, 2,2- , n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, Tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, and n-hexadecanoyloxy group.

When R ² is an alkoxycarbonyl group, the number of carbon atoms of the alkoxycarbonyl group is preferably from 2 to 20, more preferably from 2 to 7. 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, Sec-butyloxycarbonyl, n-pentyloxycarbonyl, n-heptyloxycarbonyl, n-octyloxycarbonyl, iso-octyloxycarbonyl, sec-pentyloxycarbonyl, Octyloxycarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, isononyloxycarbonyl group, n-decyloxycarbonyl group, and isodecyloxycarbonyl group.

When R ² is a phenylalkyl group, the number of carbon atoms of the phenylalkyl group is preferably 7 to 20, more preferably 7 to 10. When R ² is a naphthylalkyl group, the number of carbon atoms of the naphthylalkyl group is preferably from 11 to 20, more preferably from 11 to 14. Specific examples of 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 of when R ² is a naphthylalkyl group include an a-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 the naphthyl group.

When R ² is a heterocyclyl group, the heterocyclyl group may be a 5-membered or 6-membered monocyclic ring containing one or more N, S or O, or a heterocyclyl group in which these monocyclic rings and condensed benzene rings are condensed. And in the case where the heterocyclyl group is a condensed ring, the number of rings is 3. The heterocyclyl group can 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, pyrimidine , Pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzoimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, Ginsenosin, and quinoxaline. When R ² is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When R ² is a heterocyclylcarbonyl group, the heterocyclyl group contained in the heterocyclylcarbonyl group is the same as the case where R ² is a heterocyclyl group.

When R ² is an amino group substituted with 1 or 2 organic groups, preferred examples of the organic group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic group having 2 to 21 carbon atoms A phenyl group which may have 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 naphthylalkyl group having from 11 to 20 carbon atoms which may have a substituent, and heterocyclyl group. Specific examples of these preferred organic groups are the same as R &lt; ² &gt;. Specific examples of the amino group substituted with 1 or 2 organic groups include a methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n-butylamino group, an n-butylamino group, an n-hexylamino group, an n-heptylamino group, an n-octylamino group, an n-nonylamino group, a n-decylamino group, a phenylamino group, a naphthylamino group, an acetylamino group, a propanoylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n-decanoylamino group, benzoylamino group,? -naphthoylamino group and? have.

The substituent when the phenyl group, naphthyl group and heterocyclyl group contained in R ² have a substituent further includes an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxy group having 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 A morpholin-1-yl group, a piperazin-1-yl group, a halogen atom, a nitro group, and a cyano group. When the phenyl group, the naphthyl group, and the heterocyclyl group contained in R ² further have a substituent, the number of the substituent is not limited within 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 ² have a plurality of substituents, the plurality of substituents may be the same or different.

As R ² , a cycloalkylalkyl group, a phenoxyalkyl group which may have a substituent on an aromatic ring, and a phenylthioalkyl group which may have a substituent on an aromatic ring are also preferable. The phenoxyalkyl group and the substituent which the phenylthioalkyl group may have are the same as the substituent which 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 an aromatic ring. The alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, particularly preferably an alkyl group having 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. The number of carbon atoms of the cycloalkyl group contained in the cycloalkylalkyl group is preferably 5 to 10, more preferably 5 to 8, and particularly preferably 5 or 6. The number of carbon atoms of the alkylene group contained in the cycloalkylalkyl group is preferably from 1 to 8, more preferably from 1 to 4, and particularly preferably 2. [ Among the cycloalkylalkyl groups, a cyclopentylethyl group is preferable. The number of carbon atoms of the alkylene group contained in the phenylthioalkyl group which may have a substituent on the aromatic ring is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 2. Among the phenylthioalkyl groups which may have a substituent on the aromatic ring, 2- (4-chlorophenylthio) ethyl group is preferable.

Above has been described for the R ^2, R ² is preferably a group represented by the following formula (R2-1) or (R2-2) As.

[Figure 5]

(Wherein (R2-1) and (R2-2), R ¹⁰ and R ¹¹ are each an organic group, p is an integer of 0 ~ 4, R ¹⁰ and R ¹¹ are present in the adjacent position of the benzene ring case, R ¹⁰ and R ^11, and form a ring by combining to each other, q is an integer of 1 ~ 8, r is an integer of 1 ~ 5, s is an integer of 0 ~ (r + 3), R 12 is an alkyl group to be.)

An example of an organic group for R ¹⁰ and R ¹¹ in the formula (R 2-1) is the same as R ² . R ¹⁰ is preferably an alkyl group or a phenyl group. When R ¹⁰ is an alkyl group, the number of carbon atoms is preferably 1 to 10, more preferably 1 to 5, particularly preferably 1 to 3, most preferably 1. That is, R ¹⁰ is most preferably a methyl group. When R ¹⁰ and R ¹¹ are bonded to form a ring, the ring may be an aromatic ring or an aliphatic ring. Preferable examples of the group represented by the 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- . 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. The number of carbon atoms in the alkyl group is preferably from 1 to 10, more preferably from 1 to 5, and particularly preferably from 1 to 3. R ¹² is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group, 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, 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, and 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 the 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 the substituent which R ³ may be an alkyl group, a phenyl group, a naphthyl group and the like are preferably exemplified. The substituent which may be taken when R ³ is an aryl group is preferably an alkyl group, an alkoxy group or a halogen atom having 1 to 5 carbon atoms.

In the formula (a-1), R ^{3 is preferably} hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, phenyl, benzyl, Among them, a methyl group or a phenyl group is more preferable.

In the 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 a 6-membered aromatic ring bonded to a group represented by - (CO) _m - in formula (a-1) on a fluorene ring in formula (a-2). As long as this condition is satisfied, the bonding position of R ^{4 to} the fluorene ring in the formula (a-2) is not particularly limited. Binding to the fluorene ring of the R ⁴ position is R ¹ is preferably formula (a-2) a group formula (a-1) as shown in, etc. that the synthesis is easy of compounds, two of the fluorene ring position shown .

When R &lt; ⁴ &gt; is an organic group, R &lt; ⁴ &gt; is not particularly limited within the range not impairing the object of the present invention, and is appropriately selected from various organic groups. R ⁴ a preferable example equal to, alkyl, alkoxy, cycloalkyl, cycloalkoxy, and R ² in the case organic group group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, a phenyl group which may have a substituent, a substituent A phenoxy 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 naphthoyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthoylcarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, A heterocyclylcarbonyl group which may have a substituent, an amino group substituted by an organic group of 1 or 2, a morpholine-1 -Yl group, and a piperazin-1-yl group. Specific examples of these groups are the same as those described for R &lt; ^{2 &} gt ;.

Among the groups described above, R ⁴ is preferably a nitro group or a group represented by R ¹³ -CO- because sensitivity tends to be improved. R &lt; ¹³ &gt; is not particularly limited as long as the object of the present invention is not impaired, and R &lt; ¹³ &gt; Examples of a preferable group as 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. As R ¹³ , among these groups, a 2-methylphenyl group, a thiophen-2-yl group and an a-naphthyl group are particularly preferable.

When R ⁴ is a hydrogen atom, transparency tends to be good, which is preferable. Further, when R ⁴ is a hydrogen atom and R ² is the above-mentioned (R ^{2 - 2} ), the transparency tends to be better.

In the formula (a-1), R ⁵ and R ⁶ are each a straight chain alkyl group, a cyclic hydrocarbon group or a heteroaryl group. Of these groups, R ⁵ and R ⁶ are preferably chain alkyl groups.

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

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

When R ⁵ and R ⁶ are an aromatic cyclic hydrocarbon group, the aromatic cyclic hydrocarbon group may be a phenyl group, or a group formed by bonding a plurality of benzene rings through a carbon-carbon bond, or a group in which a plurality of benzene rings are condensed to form. In the case where the aromatic cyclic hydrocarbon group is a phenyl group or a group in which a plurality of benzene rings are formed by bonding or condensation, the number of the ring of the benzene ring contained in the aromatic cyclic hydrocarbon group is not particularly limited and is preferably 3 or less, more preferably 2 or less, Particularly preferred. Preferable 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, aliphatic cyclic hydrocarbon groups may be monocyclic or polycyclic. The number of carbon atoms of the aliphatic cyclic hydrocarbon group is not particularly limited, but is preferably 3 to 20, 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 isobonyl group, a tricyclodecyl group, Tetradecyldodecyl group, adamantyl group, and the like.

When R ⁵ and R ⁶ are a heteroaryl group, the heteroaryl group is a 5-membered or 6-membered monocyclic ring containing one or more N, S or O, or a heteroaryl group in which these monocyclic rings and condensed benzene rings are condensed. When the heteroaryl group is a condensed ring, it is assumed to be 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, Benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, benzothiazole, benzothiazole, , Syninorine, and quinoxaline.

R ⁵ and R ⁶ may combine with each other to form a spiro ring. The group consisting of spiro rings formed by R ⁵ and R ⁶ is preferably 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 the ring which 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, And pyrimidine rings, and the like.

When R &lt; ⁷ &gt; is an organic group, various organic groups can be selected within the range not hindering the object of the present invention. Preferable examples of the organic group when R ⁷ is an alkyl 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; An alkoxycarbonyl group having 2 to 7 carbon atoms; A saturated aliphatic acyloxy group having 2 to 7 carbon atoms; A phenyl group; Naphthyl group; Benzoyl group; A naphthoyl group; A benzoyl group substituted by 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; A dialkylamino group having an alkyl group having 1 to 6 carbon atoms; Morpholin-1-yl group; Piperazin-1-yl group; halogen; A nitro group; And cyano group.

R ⁷ is a benzoyl group; A naphthoyl group; A benzoyl group substituted by 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, a benzoyl group; A naphthoyl group; A 2-methylphenylcarbonyl group; 4- (piperazin-1-yl) phenylcarbonyl group; And a 4- (phenyl) phenylcarbonyl group is more preferable.

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 binding position of R ⁷ is a phenyl group for bonding hands binding with the atom to which A is bonded R ^7, preferably in the para position.

A is preferably S.

R ⁸ may be selected from a variety of organic groups as long as the object of the present invention is not impaired. Preferable 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, A phenoxycarbonyl 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 naphthoxycarbonyl group which may have a substituent , A naphthylalkyl group having a carbon number of 11 to 20 which may have a substituent, a heterocyclyl group which may have a substituent, and a heterocyclylcarbonyl group which may have a substituent.

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

When the phenyl group, naphthyl group and heterocyclyl group contained in R ⁷ or R ⁸ have a substituent further, examples of the substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a saturated aliphatic group having 2 to 7 carbon atoms 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, a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, A piperazine-1-yl group, a halogen atom, a nitro group, and a cyano group. When the phenyl group, the naphthyl group, and the heterocyclyl group contained in R ⁷ or R ⁸ further have a substituent, the number of the substituent is not limited to the extent that the object of the present invention is not impaired, but is preferably 1 to 4 . When the phenyl group, naphthyl group, and heterocyclyl group contained in R ⁷ or R ⁸ have plural substituents, plural substituents may be the same or different.

R ⁹ is the same as R ⁴ .

The compound represented by the formula (a-1) can be synthesized according to the following Scheme 1 when m is 0, for example. 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), a fluorene derivative represented by the following formula (1-1-1) is used as a raw material in scheme 1. When R ⁴ is a nitro group or a monovalent organic group, the fluorene derivative represented by the formula (1-1-1) is reacted with a fluorene derivative substituted at the 9-position with R ⁵ and R ⁶ by a known method to obtain a substituent R ⁴ can be obtained. 9 where the fluorene derivative is substituted by R ⁴ and R ⁵ is, for example, R ^4, and if R ⁵ is an alkyl group, under the presence of an alkali metal hydroxide, as described in Japanese Patent Laid-Open No. Hei-06-234668, non- Can be obtained by reacting fluorene with an alkylating agent in a protonic polar organic solvent. An alkylation reaction such as an alkyl halide such as an alkyl halide, an aqueous solution of an alkali metal hydroxide and an interphase transfer catalyst such as tetrabutylammonium iodide or potassium tert-butoxide iodide is added to an organic solvent solution of fluorene, 9-alkyl substituted fluorene can be obtained.

The ketone compound represented by the formula (1-3) is obtained by acylating the compound represented by the formula (1-1) with a halocarbonyl compound represented by the formula (1-2) by the Friedel-Craft reaction. In the formula (1-2), Hal is a halogen atom. The position to be acylated by the compound represented by the formula (1-2) in the aromatic ring contained in R ¹ can be appropriately changed by the conditions of the Friedel-Craft reaction or by the compound represented by the formula (1-2) Or a method of performing protection and deprotection at another position of the position where the misfire occurs.

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

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

<Scheme 1>

[6]

The compound represented by the formula (a-1) can be synthesized according to the following scheme 2 when m is 1, for example. In Scheme 2, a compound represented by the following formula (2-1) is used as a raw material. The compound represented by the formula (2-1) can be obtained by acylation of the compound represented by the formula (1-1) by the Friedel-Craft reaction in the same manner as scheme 1. A nitrite ester (RONO, R is an alkyl group having 1 to 6 carbon atoms) represented by the following formula (2-2) is reacted with a compound represented by the formula (2-1) in the presence of hydrochloric acid to prepare a compound represented by the following formula To obtain a keto oxime compound. Next, a ketooxime compound represented by the following formula (2-3), an acid anhydride ((R ³ CO) ₂ O) represented by the following formula (2-4) (R ³ COHal, Hal is a halogen atom) to obtain a compound represented by the following formula (2-6). In addition, the following formula (2-1), (2-3), (2-4), (2-5) and (2-6) in a, R ^1, R ^2, and R ³ is the formula (a-1 ).

When m is 1, the generation of foreign matters in the cured product formed by using the curable composition containing the compound represented by the formula (a-1) tends to be further reduced.

<Scheme 2>

[Figure 7]

Specific preferred examples of the compound represented by the formula (a-1) include the following compounds.

[Figure 8]

[Figure 9]

[10]

[Figure 11]

[Figure 12]

[Figure 13]

[14]

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

<(B) Polyfunctional acrylate compound>

The polyfunctional acrylate compound (B) is not particularly limited as long as it contains at least one member selected from the group consisting of a siloxane bond, an aromatic ring and a crosslinking ring. The polyfunctional acrylate compound (B) contributes to the improvement of the bendability, toughness and surface hardness of the hard coat layer obtained from the curable composition of the present invention. (B) polyfunctional acrylate compounds may be used alone or in combination of two or more. The polyfunctional acrylate compound (B) may be a low molecular compound, an oligomer and / or polymer having a specific repeating unit, or a combination thereof.

Examples of the polyfunctional acrylate compound (B) include those containing a siloxane bond-containing polyfunctional acrylate compound; Aromatic rings and cross-linking rings, and from the viewpoint of improving the properties of the obtained hard coat layer, it is preferable that the siloxane bond-containing polyfunctional acrylate A polyfunctional acrylate compound containing at least one member selected from the group consisting of an aromatic compound, an aromatic compound, and an aromatic ring and a crosslinking ring.

[Siloxane bond-containing polyfunctional acrylate compound]

The siloxane bond-containing polyfunctional acrylate compound largely contributes to the increase in the surface hardness of the hard coat layer, though it does not contribute to the improvement of the bending property of the obtained hard coat layer or the effect of the suppression of shrinkage shrinkage (curl reduction). Examples of the siloxane bond-containing polyfunctional acrylate compound include a polysilsesquioxane compound containing two or more (meth) acryloyl groups. Particularly, as the polysilsesquioxane compound, a cage-shaped polysilsesquioxane compound containing two or more (meth) acryloyl groups is preferable in that the surface hardness of the obtained hard coat layer is more easily improved.

Examples of the polysilsesquioxane compound include compounds represented by the following formulas:

[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, and at least two R are (meth) acryloyl groups. Type polysilsesquioxane.

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

Wherein 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, Y represents a divalent group formed by removing one hydrogen atom from each of two ring carbon atoms from an aromatic ring group or a divalent group, or a divalent group which may have a branched chain and / or double bond, 4, 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.

Examples of the alkylene group having 1 to 6 carbon atoms for X include a methylene group, an ethylene group, a propylene group and a butylene group. The allylene group in X preferably has 6 to 10 carbon atoms. Examples of such groups include a phenylene group (ortho, meta or para), a naphthylene group (1,4-, 1,5-, 2,6- or the like), and the like. Specifically, as the -R5-NH-R6- in said X is, for example, _{-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 (for example, benzene ring, naphthalene ring, tolyl group, xylyl group, etc.) which may have a substituent having 1 to 2 carbon atoms. Examples of the aliphatic ring in Y include an alicyclic group having 5 to 10 carbon atoms (e.g., a monocyclic cycloalkyl group, a monocyclic cycloalkenyl group, a bicyclic alkyl group, a cage-type alkyl group and the like, and specific examples thereof include a cyclopentane ring, Cyclobutane ring, cycloheptane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, dicyclopentadiene ring, norbornane ring, norbornene ring, quercetin ring, and busket ring). Examples of the alkylene group having 1 to 4 carbon atoms which may have a branched chain and / or a double bond in Y include a methylene group, an ethylene group, a propylene group, a vinylene group, a (2-octenyl) ethylene group , And (2,4,6-trimethyl-2-nonenyl) ethylene group, an alkylene group having a double bond or an alkylene group having a branched chain having 1 to 9 carbon atoms.

[A polyfunctional acrylate compound containing at least one member selected from the group consisting of aromatic rings and crosslinked phthalocyanines]

A multifunctional acrylate compound containing at least one member selected from the group consisting of an aromatic ring and a crosslinked phthalocyanine ring has a medium contribution to the effect of increasing the surface hardness of the obtained hard coat layer, And a flexible partial skeleton such as an alkylene group (e.g., a methylene group, an ethylene group or the like), an ether bond, and / or a urethane bond in order to improve the flexibility of the hard coat layer, This contributes greatly to suppression of shrinkage (curl reduction).

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 thiophen ring, a phosphone ring, a pyrazole ring, , Thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazin ring, triazine ring, tetrazine ring, benzofuran ring, isobenzofuran ring, indole ring, isoindole ring, benzothiophen ring, Benzoxazole ring, benzothioxazole ring, benzothiazole ring, quinoline ring, isoquinoline ring, quinoxaline ring, quinazoline ring, cininoline ring, isocyanurate ring and the like are exemplified as the imidazole ring, purine ring, indazole ring, benzoxazole ring, And isocyanurate ring, fluorene ring, and triazine ring are preferable from the viewpoints of flexural strength, anti-curl property and the like of the obtained hard coat layer.

Examples of the bridged tetrahydric rings include a norbornane ring, an isoboronic ring, an adamantane ring, a tricyclodecane ring, a tetracyclododecane ring, and the like. From the viewpoints of flexibility, Tricyclodecane ring is preferable.

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

&Lt; Other components &gt;

The curable composition according to the present invention may contain various additives as required. Specifically, examples thereof include a solvent, a sensitizer, a curing accelerator, a photo-crosslinking agent, a photosensitizer, a dispersing aid, a filler, an adhesion promoter, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, a thermal polymerization inhibitor, a defoaming agent and a surfactant.

Examples of the solvent used in the curable composition of the present invention include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol mono-n-butyl ether, 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 n-butyl ether, tripropylene glycol monomethyl ether, tripropyl Glycol monoethyl ether and (poly) alkylene glycol monoalkyl ether; (Poly) alkylene ethers 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; Lactic acid alkyl esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; Methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, Methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n- Butyl acetate, isobutyl acetate, isopentyl acetate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, 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 two or more solvents may be used in combination.

Among these 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 preferred because it exhibits excellent solubility in the components (A) and (B), and propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate are particularly preferred. The amount of the solvent to be used may be appropriately determined depending on the use of the curable composition, but is, for example, about 50 to 900 parts by weight based on 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 remarkable particularly when thinning is necessary. When the component (B) is a solid at room temperature, it is preferable to use a solvent in the present invention.

Examples of the thermal polymerization inhibitor used in the curable composition according to the present invention include hydroquinone, hydroquinone monoethyl ether and the like. Examples of the antifoaming agent include silicon compounds and fluorine compounds, and surfactants include anionic compounds, cationic compounds, and nonionic compounds.

[Method of preparing the curable composition]

The curable composition of the present invention is prepared by mixing all of the above components with a stirrer. When the prepared curable composition does not contain an insoluble component such as a filler, it may be filtered using a filter so that the curable composition is uniform.

&Lt; Process for producing cured product &

The 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. The cured product produced by this production method may be patterned as required.

Examples of the method for forming the curable composition film using the curable composition according to the present invention include a non-contact type coating apparatus such as a contact transfer type coating apparatus such as a roll coater, a reverse coater and a bar coater, a spinner (rotary coating apparatus), a curtain flow coater A method of applying a curable composition on a substrate can be mentioned. The substrate is not particularly limited, and examples thereof may be mentioned below.

The curable composition film formed as needed may be dried. The drying method is not particularly limited and includes, for example, (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) (3) a method of putting in a hot air heater or an infrared heater for several minutes to several hours for drying.

Then, the curable composition film is exposed to actinic energy rays such as ultraviolet rays and excimer laser rays. The exposure may be performed in a position-selective manner, for example, by a method of performing exposure through a negative-type mask, or may be performed by front exposure. In the case of performing the entire surface exposure, for example, the film of the curable composition may be continuously irradiated with the active energy ray in the line process while winding the film base provided with the curable composition film thereon in a line. The energy dose to be irradiated varies depending on the composition of the curable composition, but is preferably about 40 to 200 mJ / cm ² , for example. The light source is not particularly limited, and examples thereof include a high-pressure mercury lamp, an LED, and the like. From the viewpoints of energy saving and environmental load reduction, LED is preferable. The wavelength used in the exposure by the LED is, for example, 365 to 405 nm, and more specifically, UV region such as 385 nm, 395 nm, and 405 nm. In general, the energy dose irradiated by the LED is liable to be reduced. However, since the curable composition according to the present invention contains (A) a photopolymerization initiator and is excellent in sensitivity, even when the LED is used as a light source and exposure is performed, the curable composition can be sufficiently cured and a cured product having good characteristics can be effectively obtained. As described above, since the curable composition of the present invention is excellent in sensitivity, the hard coat material can be efficiently produced by using the curable composition of the present invention, and as a result, the productivity of a display device such as a liquid crystal display Can be improved.

When the curable composition film film is selectively exposed, the film after exposure is patterned into a desired shape by developing with a developing solution. The developing method is not particularly limited, and for example, a dipping method, a spraying method, or the like can be used. The 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, examples of the developer include organic ones such as monoethanolamine, diethanolamine and triethanolamine, and organic solvents such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, quaternary ammonium salt Can be used.

Then, post-baking is preferably performed at about 200 to 250 DEG C with respect to the pattern after development.

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

«Hard coat material»

The hard coat material according to the present invention comprises a substrate and a hard coat layer formed on the substrate using the curable composition of the present invention.

The substrate is not particularly limited and those known as substrates of a hard coat material can be used. Specific examples thereof include triacetylcellulose (TAC), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyamide (PA), polymethyl methacrylate (PMMA), nylon (Ny), polyether sulfone , Polyvinyl chloride (PVC), polypropylene (PP), and polycarbonate (PC); Glass substrates and the like. Of 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 in the case of the method for producing a cured product according to the present invention. The thickness of the hard coat layer is preferably 1 to 10 mu m.

&Quot; Image display device &quot;

The image display apparatus according to the present invention comprises 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 hard coat material according to the present invention is applied to the display surface or its wiring protection layer.

[ Example ]

Hereinafter, the present invention will be described in more detail with reference to 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 polyfunctional acrylate (B) containing at least one kind selected from the group consisting of (A) a photopolymerization initiator, (B1) a siloxane bond-containing polyfunctional acrylate compound, , And (B3) other acrylate compounds were uniformly mixed to obtain a solventless curable composition. The numerical values in parentheses in Table 1 represent the compounding amount (unit: parts by mass) of each component.

Compound 1: A photopolymerization initiator represented by the formula on the left side in the following first column

Compound 2: A photopolymerization initiator represented by the formula on the right side of the first step

Compound 3: A photopolymerization initiator represented by the following formula

[Figure 15]

Irg819: A photopolymerization initiator represented by the following formula

Irg184: a photopolymerization initiator represented by the formula shown below

OXE01: The photopolymerization initiator represented by the formula on the right side

[16]

Silsesquioxane 1: represented by the formula on the left side and silsesquioxane in which all of R ¹⁹ to R ²⁶ are acryloyloxy groups

Silsesquioxane 2: 30% by mole of R ¹⁹ to R ²⁶ is a group represented by the right-hand side formula, and 70% by mole of R ¹⁹ to R ²⁶ is an acryloyloxy group. Oxane

[Figure 17]

Tricyclodecane-based compound: a compound represented by the formula on the left side of the first step

Isocyanuric acid system 1: Compound represented by the formula on the right side of the first step

Fluorene type: A compound represented by the following formula

Isocyanuric acid-based compound 2: a compound represented by the following formula (3) and X represents an acryloyloxy group

[Figure 18]

[Film forming method]

The obtained curable composition was dropped onto a PET film having a thickness of 100 탆 and coated with an applicator to obtain a curable composition film. Thereafter, the curable composition film was exposed with a high-pressure mercury lamp exposing machine (ORC company) or an LED light (wavelength: 395 nm) to obtain a cured film having a thickness of 50 탆. This cured film was peeled from the PET film, and the following evaluation was carried out. The results of these evaluations are shown in Table 1.

[Surface hardness]

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

⊚ (very good): The pencil hardness was 7H or more.

(Good): The pencil hardness was 4H to 6H.

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

[Transparency]

Transmittance The transmittance of the cured film at 400 nm was measured using MCPD (manufactured by Otsuka Electronics Co., Ltd.). The 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%.

× (poor): the transmittance was less than 90%.

[Flexibility and toughness]

A stainless steel rod having a radius n (unit mm, n is an integer of 1 or more) was prepared. The cured film was wound around each prepared stainless steel rod. Among the stainless steel rods which could be wound without breaking the cured film, those having the minimum 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 of the present invention is excellent in flexibility, toughness, surface hardness and transparency, and can be suitably used for a hard coat material.

Claims (6)

(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 crosslinking ring,
Wherein the photopolymerization initiator (A) is represented by the following formula (a-1):

(R ¹ is a group represented by 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 straight 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 .
, A group represented by the following formula (a-3):

(Wherein R ⁷ is independently a monovalent organic group, an amino group, a halogen atom, a nitro group, or a cyano group, A is S or O, and n is an integer of 0 to 4.)
, Or a group represented by the following formula (a-4):

(R ⁸ is a monovalent organic group and R ⁹ is a hydrogen atom, a nitro group, or a monovalent organic group.)
A group represented by, R ² is a monovalent organic group, R ³ is an aryl group which may have a number of carbon atoms which may have a hydrogen atom, an optionally substituted alkyl group of 1 to 11, or a substituent, m is 0 or 1, .)
Lt; RTI ID = 0.0 &gt; 1, &lt; / RTI &gt; The method according to claim 1,
Wherein the polyfunctional acrylate compound (B) comprises a siloxane bond-containing polyfunctional acrylate compound. The method of claim 2,
Wherein the siloxane bond-containing polyfunctional acrylate compound is a polysilsesquioxane compound containing two or more (meth) acryloyl groups. The method of claim 2,
Wherein the polyfunctional acrylate compound (B) further comprises at least one member selected from the group consisting of an aromatic ring and a crosslinking silane ring. Forming a curable composition film using the curable composition of claim 1;
And exposing the curable composition film to light. A hard coat material comprising a substrate and a hard coat layer formed on the substrate using the curable composition of claim 1.