WO2014065517A1 - Hardening resin composition and optical film manufactured by using same - Google Patents

Abstract

The present invention relates to a hardening resin composition and an optical film manufactured by using same, and more specifically, to a hardening resin composition and an optical film manufactured by using same, the hardening resin composition comprising: a photopolymerization initiator comprising a compound having at least two photoactive oxime ester structures in one molecule; a first monomer comprising an isocyanate group and a (meta) acrylate group at the terminal thereof and thus allowing hardening by photocuring and thermal curing; a multifunctional second monomer having a hydroxy group or a carboxyl group; and an organic acid, thereby having superior adhesive force between layers and hardening by photocuring and thermal curing.

Description

Curable resin composition and optical film manufactured using the same

The present invention relates to a curable resin composition and an optical film produced using the same. More specifically, the present invention relates to a curable resin composition capable of photocuring and thermosetting, which can produce a resin layer having low energy consumption and excellent interlayer adhesion, and an optical film manufactured using the same.

Various optical films, such as a polarizing film and a retarder, are used for the various image display apparatuses currently used. Such an optical film is formed by stacking a plurality of thin films.

Taking the case of a retarder as an example, a retarder is normally formed by laminating | stacking a base film, an orientation film, and a cured liquid crystal layer sequentially. As a base film, the transparent film formed from TAC, COP, etc. is used, but the use of the base film which uses PMMA is increasing in recent years.

However, since PMMA has a brittle characteristic compared to TAC or COP, there is a problem that cracks are easily generated when used as it is. Therefore, this problem is usually solved by dispersing a filler such as a rubber bead in the interior thereof.

However, when the filler is applied during the manufacturing process of the base film and the retarder, such a filler may be driven to the surface of the base film. In this case, the surface roughness of the base film may increase. When the surface roughness of the base film is increased, the adhesive force between the base film and the alignment film is lowered, or the flatness of the cured liquid crystal layer is lowered on the alignment film, thereby degrading the function as a retarder. Penetration problems will occur.

In order to solve such a problem, a method of forming an alignment layer thicker has been performed, but when the alignment layer becomes thick, a problem arises in that the alignment capability of the alignment layer decreases, which is not a preferable solution.

Therefore, there is a need for a new solution that can improve the adhesive force without degrading the optical performance required for an optical film such as a retarder.

An object of the present invention is to provide a curable resin composition capable of forming a resin layer having excellent interlayer adhesion.

In addition, an object of the present invention is to provide a curable resin composition capable of both photocuring and thermal curing to reduce energy during the manufacturing process.

Moreover, an object of this invention is to provide the optical film provided with the resin layer formed from the said curable resin composition.

1. a photopolymerization initiator having at least two photoactive oxime ester backbones in one molecule; A first monomer capable of photocuring and thermosetting by including an isocyanate group and a (meth) acrylate group at its terminals; Polyfunctional second monomer having a hydroxy group or a carboxy group; And an organic solvent.

2. The curable resin composition according to the above 1, wherein the photopolymerization initiator having at least two photoactive oxime ester skeletons in one molecule is dimerized through R ₁ or R ₂ .

[Formula 1]

Wherein R ₁ , R ₂ and R ₃ independently of one another represent R ₁₁ , OR ₁₁ , COR ₁₁ , SR ₁₁ , CONR ₁₂ R ₁₃ or CN,

R ₄ and R ₅ are each independently R ₁₁ , OR ₁₁ , SR ₁₁ , COR ₁₁ , CONR ₁₂ R ₁₃ , NR ₁₂ COR ₁₁ , OCOR ₁₁ , COOR ₁₁ , SCOR ₁₁ , OCSR ₁₁ , COSR ₁₁ , CSOR ₁₁ , CN Represents a halogen atom or a hydroxy group,

a and b are each independently an integer of 0 to 3,

R ₁₁ , R ₁₂ and R ₁₃ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms Wherein the hydrogen atom of the alkyl group, aryl group, arylalkyl group and heterocyclic group is also R ₂₁ , OR ₂₁ , COR ₂₁ , SR ₂₁ , NR ₂₂ R ₂₃ , CON R ₂₂ R ₂₃ , -NR ₂₂ -OR ₂₃ , -NCOR ₂₂ -OCOR ₂₃ , -C (= N-OR ₂₁ ) -R ₂₂ , -C (= N-OCOR ₂₁ ) -R ₂₂ , CN, halogen atom, -CR ₂₁ = CR ₂₂ R ₂₃ , -CO- CR ₂₁ = CR ₂₂ R ₂₃ , OCO-CR ₂₁ = CR ₂₂ R ₂₃ , OC _1-6 alkylene-OCOR ₂₁ , COOR ₂₁ , or may be substituted with an epoxy group,

R ₂₁ , R ₂₂ and R ₂₃ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms Indicates,

The methylene group of the alkylene moiety of the substituent represented by R ₁₁ , R ₁₂ , R ₁₃ , R ₂₁ , R ₂₂ and R ₂₃ is an unsaturated bond, ether bond, thioether bond, ester bond, thioester bond, amide bond or urethane It may be interrupted 1 to 5 times by a bond, the alkyl moiety of the substituent may have a branched chain, a cyclic alkyl, the alkyl terminal of the substituent may be an unsaturated bond, and R ₁₂ , R ₁₃ and R ₂₂ and R ₂₃ may each form a ring together, and R ₃ may form a ring together with an adjacent benzene ring.)

3. The curable resin composition according to the above 2, wherein the photopolymerization initiator having at least two photoactive oxime ester skeletons in one molecule is a compound represented by the following Chemical Formula 2 or Chemical Formula 3:

[Formula 2]

[Formula 3]

Wherein R ₁ to R ₅ are as defined in 2 above.

4. The curable resin composition according to the above 1, wherein the photopolymerization initiator having at least two photoactive oxime ester skeletons in one molecule is a compound represented by the following formula (11):

[Formula 11]

5. In the above 1, wherein the first monomer capable of photocuring and thermosetting including the isocyanate group and the (meth) acrylate group at its terminals is one or more selected from the group consisting of compounds of the formula Curable Resin Composition:

[Formula 16]

(Wherein R ₁ and R ₂ are each independently hydrogen or a methyl group,

R ₃ and R ₇ are each independently an alkylene group having 1 to 10 carbon atoms unsubstituted or substituted with a group selected from the group consisting of a ketone group, an ester group and a thiol group,

R ₄ and R ₆ are each independently an alkylene group having 1 to 10 carbon atoms unsubstituted or substituted with a group selected from the group consisting of an amide group, a ketone group, an ester group and a thiol group,

R ₅ is an alkylene group having 1 to 10 carbon atoms unsubstituted or substituted with an alkoxy group having 1 to 8 carbon atoms,

[Formula 17]

(Wherein R ₇ and R ₈ are each independently hydrogen or a methyl group,

R ₉ and R ₁₁ are each independently an alkylene group having 1 to 10 carbon atoms unsubstituted or substituted with a group selected from the group consisting of a ketone group, an ester group and a thiol group,

R ₁₀ is (a)

Or (b)

E ₁ and E ₃ are each independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, and E ₂ is an alkoxy group having 1 to 8 carbon atoms. Substituted or unsubstituted alkylene group having 1 to 10 carbon atoms,

[Formula 18]

(Wherein R ₁₂ is hydrogen or a methyl group,

R ₁₃ is an alkylene group having 1 to 10 carbon atoms unsubstituted or substituted with a group selected from the group consisting of a ketone group, an ester group and a thiol group; and

[Formula 19]

(Wherein, R ₁₄ is hydrogen or a methyl group,

R ₁₅ is an alkylene group having 1 to 10 carbon atoms unsubstituted or substituted with a group selected from the group consisting of a ketone group, an ester group and a thiol group.

6. In the above 1, wherein the polyfunctional second monomer having a hydroxy group is a curable resin composition represented by the following formula 31:

[Formula 31]

Wherein at least one of R ₁ , R ₂ , R ₃ and R ₄ is hydrogen or a carboxy group and the rest are independently selected from methyl or acryloyl groups, and A is

,

,

,

,

or

Is a integer of 1 to 3, b is an integer of 0 to 12).

7. In the above 1, the second monomer is a polystyrene reduced weight average molecular weight of 200 to 3,000 curable resin composition.

8. In the above 1, wherein the mixed weight ratio of the first monomer and the second monomer is the first monomer: the second monomer = 1: 1-2 curable resin composition.

9. The curable resin composition according to the above 1, wherein the organic solvent is a mixed solvent of a solvent having an SP _DS value of 1 or less and a solvent of 15 or more represented by Equation 1 below:

[Equation 1]

(In formula, SP _SUB is SP value of a base film, SP _SOL is SP value of a solvent.).

10. An optical film having a resin layer cured with the curable resin composition of any one of the above 1 to 9.

11. The optical film according to the above 10, wherein the optical film is a retarder.

12. The optical film according to the above 11, wherein the retarder has a structure in which the resin layer is interposed between the base film and the alignment layer.

13. In the above 12, wherein the base film is an optical film formed including the PMMA resin.

14. In the above 13, wherein the carbon-carbon saturated bond is present between the base film and the resin layer.

15. Image display device having the optical film of the above 10.

The curable resin composition of the present invention is excellent in interlayer adhesion, and in particular, when a reactive group having a carbon double bond is left in the adjacent film, it may also form a chemical bond therewith.

In addition, since the curable resin composition of the present invention is capable of both photocuring and thermosetting, it is possible to advance the thermal curing during the drying process after applying the curable resin composition, and thus only the uncured portion after the drying process photocured Since it is possible to cure with only a low exposure amount can be saved energy.

In particular, when the curable resin composition of the present invention is applied to a retarder using PMMA as the base film, when used as a resin layer between the alignment film and the base film, the surface of the base film becomes flat, so that the alignment film can be thickly formed. There is no need.

The present invention provides a photopolymerization initiator comprising a compound having at least two photoactive oxime ester skeletons in one molecule; A first monomer capable of photocuring and thermosetting by including an isocyanate group and a (meth) acrylate group at its terminals; Polyfunctional second monomer having a hydroxy group or a carboxy group; And it comprises an organic solvent, excellent in interlayer adhesion, and a curable resin composition capable of photocuring and thermosetting, and relates to an optical film produced using the same.

Hereinafter, the present invention will be described in detail.

Curable resin composition of this invention is a photoinitiator; A first monomer capable of photocuring and thermosetting; And polyfunctional second monomers.

Preferably, the curable resin composition of the present invention comprises a photopolymerization initiator comprising a compound having at least two photoactive oxime ester skeletons in one molecule; A first monomer capable of photocuring and thermosetting by including an isocyanate group and a (meth) acrylate group at its terminals; And a polyfunctional second monomer having a hydroxy group or a carboxy group.

The photopolymerization initiator of the present invention includes a compound having two or more photoactive oxime esters skeleton in one molecule. Having two or more photoactive oxime ester skeletons in one molecule results in excellent polymerization initiation efficiency since two radicals are generated from one compound at the start of the polymerization reaction.

Preferably, the compound having two or more photoactive oxime ester skeletons in one molecule is dimerized through R ₁ or R ₂ .

[Formula 1]

Wherein R ₁ , R ₂ and R ₃ independently of one another represent R ₁₁ , OR ₁₁ , COR ₁₁ , SR ₁₁ , CONR ₁₂ R ₁₃ or CN,

R ₄ and R ₅ are each independently R ₁₁ , OR ₁₁ , SR ₁₁ , COR ₁₁ , CONR ₁₂ R ₁₃ , NR ₁₂ COR ₁₁ , OCOR ₁₁ , COOR ₁₁ , SCOR ₁₁ , OCSR ₁₁ , COSR ₁₁ , CSOR ₁₁ , CN Represents a halogen atom or a hydroxy group,

a and b are each independently an integer of 0 to 3.

R ₁₁ , R ₁₂ and R ₁₃ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms Wherein the hydrogen atom of the alkyl group, aryl group, arylalkyl group and heterocyclic group is also R ₂₁ , OR ₂₁ , COR ₂₁ , SR ₂₁ , NR ₂₂ R ₂₃ , CON R ₂₂ R ₂₃ , -NR ₂₂ -OR ₂₃ , -NCOR ₂₂ -OCOR ₂₃ , -C (= N-OR ₂₁ ) -R ₂₂ , -C (= N-OCOR ₂₁ ) -R ₂₂ , CN, halogen atom, -CR ₂₁ = CR ₂₂ R ₂₃ , -CO- CR ₂₁ = CR ₂₂ R ₂₃ , OCO-CR ₂₁ = CR ₂₂ R ₂₃ , OC _1-6 alkylene-OCOR ₂₁ , COOR ₂₁ , or may be substituted with an epoxy group,

R ₂₁ , R ₂₂ and R ₂₃ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms Indicates,

The methylene group of the alkylene moiety of the substituent represented by R ₁₁ , R ₁₂ , R ₁₃ , R ₂₁ , R ₂₂ and R ₂₃ is an unsaturated bond, ether bond, thioether bond, ester bond, thioester bond, amide bond or urethane It may be interrupted 1 to 5 times by a bond, the alkyl moiety of the substituent may have a branched chain, a cyclic alkyl, the alkyl terminal of the substituent may be an unsaturated bond, and R ₁₂ , R ₁₃ and R ₂₂ and R ₂₃ may each form a ring together, and R ₃ may form a ring together with an adjacent benzene ring.)

Preferably, as the alkyl group represented by R ₁₁ , R ₁₂ , R ₁₃ , R ₂₁ , R ₂₂ and R ₂₃ in Chemical Formula 1, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl , t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl , Hexadecyl, octadecyl, isocil, cyclopentyl, cyclohexyl, cyclohexylmethyl, vinyl, allyl, butenyl, ethynyl, propynyl, methoxyethyl, ethoxyethyl, propoxyethyl, pentyloxyethyl, octyl Oxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propoxy oxyethyl, methoxypropyl, 2-methoxy-1-methylethyl and the like. As the aryl group represented by R ₁₁ , R ₁₂ , R ₁₃ , R ₂₁ , R ₂₂ and R ₂₃ , for example, phenyl, tolyl, xylyl, ethylphenyl, chlorophenyl, naphthyl, anthryl, phenanthrenyl, And phenyl, biphenylyl, naphthyl, anthryl and the like substituted with one or more of the above alkyl groups. Examples of the arylalkyl group represented by R ₁₁ , R ₁₂ , R ₁₃ , R ₂₁ , R ₂₂ and R ₂₃ include benzyl, chlorobenzyl, α-methylbenzyl, α, α-dimethylbenzyl, phenylethyl and phenylethenyl Etc. can be mentioned. As the heterocyclic group represented by R ₁₁ , R ₁₂ , R ₁₃ , R ₂₁ , R ₂₂ and R ₂₃ , for example, pyridyl, pyrimidyl, furyl, thienyl, tetrahydrofuryl, dioxolanyl, benzoxazole- 2-yl, tetrahydropyranyl, pyrrolidyl, imidazolidil, pyrazolidyl, thiazolidyl, isothiazolidil, oxazolidyl, isoxazolidyl, piperidyl, piperazil, morpholinyl 5-7 membered heterocycles, such as these, are illustrated preferably. As also ring which may be formed with a ring of benzene which R ₁₂ and R ₁₃ rings, which can be formed with R ₂₂ and R ₂₃ the ring, and R ₃ which can form with the adjacent, for example, a cyclopentyl bullet, 5-7 membered rings, such as a cyclohexane ring, a cyclopentene ring, a benzene ring, a piperidine ring, a morpholine ring, a lactone ring, and a lactam ring, are mentioned. Examples of the halogen atom that may be substituted for R ₁₁ , R ₁₂ , R ₁₃ , R ₂₁ , R ₂₂ and R ₂₃ and the halogen atom represented by R ₄ , R ₅ include fluorine, chlorine, bromine and iodine.

The methylene group of the alkylene moiety of the substituent may be interrupted 1 to 5 times by an unsaturated bond, an ether bond, a thioether bond, an ester bond, a thioester bond, an amide bond or a urethane bond, and at this time, one or more bond groups are interrupted Two or more types of contribution may also be sufficient, and when it is the group which can be interrupted continuously, you may interrupt 2 or more consecutively. In addition, the alkyl part of the said substituent may have a branched side chain, cyclic alkyl may be sufficient, and the alkyl terminal of the said substituent may be an unsaturated bond.

Among the oxime ester compounds of the present invention, in Formula 1, R ₁ is an alkyl group having 11 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, and a complex having 2 to 20 carbon atoms. Ventilation, OR ₁₁ , COR ₁₁ , SR ₁₁ , CONR ₁₂ R ₁₃ or CN, but R ₃ is an alkyl group having 1 to 12 carbon atoms interrupted 1 to 5 times by ether or ester bond, 13 to 20 carbon atoms An alkyl group, OR ₁₁ , COR ₁₁ , SR ₁₁ , CONR ₁₂ R ₁₃ or CN, in particular R ₁ is an alkyl group having 11 to 20 carbon atoms or an aryl group having 6 to 30 carbon atoms, or R ₃ is an alkylene of an alkyl group The methylene group of the moiety is a branched alkyl group having 8 or more carbon atoms which may be interrupted 1 to 5 times by an ether bond or ester bond; The methylene group of the alkylene portion of the alkyl group is an alkyl group of 13 or more small atoms which may be interrupted 1 to 5 times by an ether bond or ester bond; R ₃ is an alkyl group interrupted 1 to 5 times by an ether bond; It is easy to synthesize | combine that R <_3> is the alkyl group interrupted 1-5 times by the ester bond, and when used as a photoinitiator, it is 1 mass in the solvent propylene glycol-1-nomethylether-2-acetate or cyclohexanone. It is preferable because it dissolves in at least% and satisfies the requirements as a photopolymerization initiator.

In the oxime ester compound of the present invention, as shown in the following Chemical Formula 2 and Chemical Formula 3, the compound represented by Chemical Formula 1 is preferably dimerized through R ₁ or R ₂ .

[Formula 2]

[Formula 3]

Wherein R ₁ to R ₅ are as defined in Formula 1 above.

Preferred specific examples of the oxime ester compound of the present invention represented by Formula 1 include, but are not limited to, the compounds of Formulas 4 to 10 shown below.

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

As a preferable specific example of the oxime ester compound of this invention represented by said Formula (3), the compound of following formula (11) is mentioned. However, this invention is not restrict | limited at all by the following compounds.

[Formula 11]

The photopolymerization initiator having two or more photoactive oxime ester skeletons in one molecule may be included in an amount of 0.1 to 40% by weight based on the total weight of the curable resin composition of the present invention. Preferably, it may be included in an amount of 1 to 30% by weight. When included in the above content range, it exhibits high sensitivity to light, and thus the polymerization reaction proceeds sufficiently even at a low exposure amount, so that the interlayer adhesion is excellent.

The photopolymerization initiator contained in the curable resin composition of the present invention includes, but is not limited to, a triazine-based compound, an acetophenone-based compound, a biimidazole-based compound, and an oxime compound, in addition to the compound having two or more photoactive oxime ester skeletons in one molecule. One or more compounds selected from the group can be used together. Curable resin composition containing the said photoinitiator is highly sensitive, and the film | membrane formed using this composition becomes favorable in strength and surface smoothness.

As said triazine type compound, it is 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1, 3, 5- triazine, 2, 4-bis (trichloromethyl)-, for example. 6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4- Bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2 -Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-tri Azine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloro Methyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like.

Moreover, as said acetophenone type compound, for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 2-hydroxy-1- [4- ( 2-hydroxyethoxy) phenyl] -2-methylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1 -One, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] And oligomers of propane-1-one.

Moreover, as an acetophenone type compound which can be used other than the acetophenone type compound enumerated above, the compound represented by following formula (12) is mentioned, for example.

[Formula 12]

In Formula 12, R ₁ to R ₄ are independently a hydrogen atom, a halogen atom, a hydroxyl group, a phenyl group which may be substituted by an alkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms The naphthyl group which may be substituted by the benzyl group or C1-C12 alkyl group which may be substituted by this is shown.

Specific examples of the compound represented by Formula 12 include 2-methyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-ethyl-2-amino (4-morpholinophenyl) ethane- 1-one, 2-propyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-butyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-methyl- 2-amino (4-morpholinophenyl) propane-1-one, 2-methyl-2-amino (4-morpholinophenyl) butan-1-one, 2-ethyl-2-amino (4-morpholin Nophenyl) propane-1-one, 2-ethyl-2-amino (4-morpholinophenyl) butan-1-one, 2-methyl-2-methylamino (4-morpholinophenyl) propane-1- On, 2-methyl-2-dimethylamino (4-morpholinophenyl) propan-1-one, 2-methyl-2-diethylamino (4-morpholinophenyl) propan-1-one, etc. may be mentioned. have.

As said biimidazole compound, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- tetraphenyl biimidazole, 2,2'-bis (2,3-, for example) Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimi Dazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole or a phenyl group at the 4,4', 5,5 'position The imidazole compound substituted with the alkoxy group etc. are mentioned. Among them, 2,2'bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole or 2,2'-bis (2,3-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole is preferably used.

Examples of the oxime compound include 0-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one and the compounds represented by the following formulas (13) to (15).

[Formula 13]

[Formula 14]

[Formula 15]

Moreover, the other photoinitiator etc. which are normally used in this field can also be used together, without departing from the scope of the present invention. As another photoinitiator, a benzoin compound, a benzophenone type compound, a thioxanthone type compound, an anthracene type compound etc. are mentioned, for example. These can be used individually or in combination of 2 or more types, respectively.

As said benzoin type compound, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. are mentioned, for example.

As said benzophenone type compound, for example, benzophenone, methyl 0- benzoyl benzoate, 4-phenyl benzophenone, 4-benzoyl-4'- methyl diphenyl sulfide, 3, 3 ', 4, 4'- tetra ( tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, etc. are mentioned.

As said thioxanthone type compound, 2-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro-4- propoxy thioxanthone, etc. are mentioned, for example. Can be mentioned.

Examples of the anthracene-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and the like. Can be mentioned.

Others include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone, methyl phenyloxyoxylate, A titanocene compound etc. are mentioned as another photoinitiator.

In addition, you may use combining a photoinitiator with a photoinitiator. When a photoinitiator adjuvant is used together with a photoinitiator, since curable resin composition containing these is more sensitive and productivity at the time of forming a resin layer using this composition is preferable, it is preferable.

As the photopolymerization initiation aid, an amine compound and a carboxylic acid compound are preferably used.

Specific examples of the amine compound in the photopolymerization initiation aid include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanol amine, 4-dimethylaminobenzoate methyl, 4-dimethylaminobenzoate ethyl, 4-dimethylaminobenzoic acid, and pediatric wheat. -Dimethylaminobenzoic acid 2-ethylhexyl, benzoic acid 2-dimethylaminoethyl, N, N-dimethyl paratoluidine, 4,4'-bis (dimethylamino) benzophenone (common name: Michler's ketone), 4,4'- Aromatic amine compounds, such as bis (diethylamino) benzophenone, are mentioned. As an amine compound, an aromatic amine compound is used preferably.

Specific examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethyl phenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichloro And aromatic heteroacetic acids such as phenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid. The content of the photopolymerization initiation aid may be usually 0.1 to 40% by weight based on the total weight of the curable resin composition. Preferably it may be included in 0.5 to 30% by weight.

When the content of the photopolymerization initiation aid is in the above range, the sensitivity of the curable resin composition is higher, and thus the formation of the resin layer formed by using the composition is preferable.

The first monomer according to the present invention is characterized by including an isocyanate group and a (meth) acrylate group at its terminals to enable photocuring and thermosetting. In the first monomer, the (meth) acrylate group participates in the photocuring reaction, and the isocyanate group participates in the thermosetting reaction. (Meth) acrylate groups react with carbon-carbon double bonds of other molecules to form carbon-carbon saturated bonds, and isocyanate groups react with hydroxyl or carboxyl groups of the second monomer to form urethane bonds.

The isocyanate group of the first monomer is reacted with a hydroxyl group or a carboxyl group at a temperature of about 80 to 130 ° C., which is the temperature of a typical drying step carried out in the process of producing an optical film (thermosetting).

As such, since the first monomer is crosslinked with the second monomer, the hardness and the adhesion of the resin layer can be enhanced.

In addition, the (meth) acrylate group of the first monomer reacts with the unreacted carbon-carbon unsaturated bond reactive group remaining on the surface of the PMMA when the base film to which the resin layer is in contact is made of PMMA to form a carbon-carbon saturated bond. It may be formed. In this case, the resin layer and the base film may be connected by chemical bonding to have a stronger interlayer adhesion.

Examples of the first monomer according to the present invention include at least one selected from the group consisting of compounds represented by the following Chemical Formulas 16 to 19.

[Formula 16]

(Wherein R ₁ and R ₂ are each independently hydrogen or a methyl group,

R ₃ and R ₇ are each independently an alkylene group having 1 to 10 carbon atoms unsubstituted or substituted with a group selected from the group consisting of a ketone group, an ester group and a thiol group,

R ₄ and R ₆ are each independently an alkylene group having 1 to 10 carbon atoms unsubstituted or substituted with a group selected from the group consisting of an amide group, a ketone group, an ester group and a thiol group,

R ₅ is an alkylene group having 1 to 10 carbon atoms unsubstituted or substituted with an alkoxy group having 1 to 8 carbon atoms,

[Formula 17]

(Wherein R ₇ and R ₈ are each independently hydrogen or a methyl group,

R ₉ and R ₁₁ are each independently an alkylene group having 1 to 10 carbon atoms unsubstituted or substituted with a group selected from the group consisting of a ketone group, an ester group and a thiol group,

R ₁₀ is (a)

Or (b)

E ₁ and E ₃ are each independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, and E ₂ is an alkoxy group having 1 to 8 carbon atoms. Substituted or unsubstituted alkylene group having 1 to 10 carbon atoms,

[Formula 18]

(Wherein R ₁₂ is hydrogen or a methyl group,

R ₁₃ is an alkylene group having 1 to 10 carbon atoms unsubstituted or substituted with a group selected from the group consisting of a ketone group, an ester group and a thiol group; and

[Formula 19]

(Wherein, R ₁₄ is hydrogen or a methyl group,

R ₁₅ is an alkylene group having 1 to 10 carbon atoms unsubstituted or substituted with a group selected from the group consisting of a ketone group, an ester group and a thiol group.

In the curable resin composition of the present invention, the first monomer represented by the above formulas (16) to (19) is at least one of the compounds represented by the formulas (17) to (19) and the compound represented by the formula (16) in order to ensure better interlayer adhesion It can be used as a mixture of.

More specific examples of the first monomer of Formula 16 to Formula 19 may include at least one selected from the group consisting of compounds represented by Formula 20 to Formula 30:

[Formula 20]

[Formula 21]

[Formula 22]

[Formula 23]

[Formula 24]

[Formula 25]

[Formula 26]

[Formula 27]

[Formula 28]

[Formula 29]

[Formula 30]

Compounds represented by the above formula (19) and compounds represented by the above formula 27, 28, 29 and 30, which is an example of the compound is the terminal dimethyl pyrazole group is separated through a heat treatment process, such as drying process, and thus It will have an isocyanate group.

The first monomer according to the present invention is preferably included in 5 to 90% by weight, preferably 10 to 70% by weight relative to the total weight of the composition. It is possible to secure sufficient adhesive strength in the above range, when excessively added, the adhesive strength is improved, but when applied to the optical film, other physical properties may be lowered.

The composition for forming a curable resin layer of the present invention may further include a thermal polymerization initiator to promote thermal curing. The thermal polymerization initiator usable in the present invention can be used without particular limitation as long as it is used in the art.

The second monomer according to the invention is characterized in that the polyfunctional monomer having a hydroxy group or a carboxyl group. As described above, the second monomer performs a crosslinking reaction through a hydroxy group or a carboxyl group, and, if necessary, also has a carbon-carbon unsaturated bond as a functional group, and may also perform a polymerization reaction.

As a specific example of a 2nd monomer, the compound represented by following General formula (31) is mentioned.

[Formula 31]

Wherein at least one of R ₁ , R ₂ , R ₃ and R ₄ is hydrogen or a carboxy group and the rest are independently selected from methyl or acryloyl groups, and A is

,

,

,

,

or

Is a integer of 1 to 3, b is an integer of 0 to 12).

More specific examples of the compound represented by Chemical Formula 31 may include a compound represented by Chemical Formula 32 to Chemical Formula 39, but are not limited thereto.

[Formula 32]

[Formula 33]

[Formula 34]

[Formula 35]

[Formula 36]

[Formula 37]

[Formula 38]

[Formula 39]

It is preferable that the weight average molecular weight of polystyrene conversion of the 2nd monomer which concerns on this invention is 200-3,000, More preferably, it may be 500-1,000. If the weight average molecular weight of the second monomer exceeds 3,000, the dispersibility may be reduced, or the brightness of the optical film may be lowered because a stable dispersion is not obtained. If the molecular weight is less than 200, the brightness of the optical film may be lowered.

The second monomer according to the invention is preferably included in 5 to 60% by weight relative to the total weight of the composition. If the content is less than 5% by weight, the degree of curing may be lowered, and if it is more than 60% by weight, it may be detrimental to heat curing.

Preferably, the mixing weight ratio of the first monomer and the second monomer according to the present invention may be the first monomer: the second monomer = 1: 1-2, in this range it can be more maximized the effect of the present invention.

Curable resin composition of this invention contains the organic solvent which can melt | dissolve the said components. The organic solvent maintains the dissolution and proper viscosity of the components so that the composition exhibits the desired coating properties, processability, and the like.

Examples of such an organic solvent may be appropriately used a component capable of dissolving the above components, but preferably a solvent containing an oxygen atom, a solvent having an SP _DS value of 1 or less and a solvent of 15 or more, represented by Equation 1 below. It is preferable to use a mixed solvent of

[Equation 1]

The degree of miscibility and corrosion between the solvent used in the curable composition and the base film to which the curable composition is applied can be known by correlation of the solubility parameter (SP) of the solvent and the base film. A solvent having an SP _DS value of 1 or less represented by Equation 1 may corrode the surface of the base film to a predetermined amount or more. When the surface of the base film is melted in a predetermined amount, the rainbow phenomenon may be prevented due to the occurrence of irregularities between the interfaces, and adhesion, coating property, and the like may be improved. However, if the degree of corrosion is large and the unevenness between the interfaces is too large, the haze value may increase, or whitening may occur, and mechanical properties, in particular, film strength and flex resistance may be reduced. Therefore, it is preferable to mix and use 2 or more types of solvents with the said SP _DS value of 1 or less which are highly corrosive on the surface of a base film, and the solvent whose SP _DS value is 15 or more of small degree of corrosion simultaneously. When only a solvent having an SP _DS value of 1 or less is used, whitening and haze increase may occur. When only a solvent having an SP _DS value of 15 or more is used, a rainbow phenomenon may occur and adhesion may be reduced.

The SP of the base film and the solvent may use values known in the art, for example, the values set forth in VII / 671-VII / 714 of the Polymer Handbook (4th Ed. J. Brandrup et al.). Can be used. In general, SP can be defined as (ΔH / V) 1/2, ΔH is the molar evaporation enthalpy, and V is the molar volume.

More specific examples of the solvent that can be used include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol Ethyl methyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether Acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, methoxypentyl acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, Propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol ethyl methyl ether, propylene glycol dipropyl ether propylene glycol propyl methyl ether, propylene glycol ethyl propyl ether, propylene glycol methyl ether propionate, propylene glycol Ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate, methoxy butyl alcohol, ethoxy butyl alcohol, propoxy butyl alcohol, butoxy butyl alcohol, methoxy butyl acetate, ethoxy butyl Acetate, propoxybutyl acetate, butoxybutyl acetate, methoxybutyl propionate, ethoxybutyl propionate, propoxybutyl propionate, butoxybutyl propionate, dipropylene glycol dimethyl ether, dipropylene glycol Recalled diethyl ether, dipropylene glycol methyl ethyl ether, benzene, toluene, xylene, mesitylene, methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone, ethanol, propanol, butanol, hexanol, Cyclohexanol, ethylene glycol, glycerin, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, Methyl hydroxy acetate, ethyl hydroxy acetate, butyl acetate acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 3-hydroxypropionate methyl, 3-hydroxypropionate ethyl, 3-hydroxypropionate propyl, 3- Butyl hydroxypropionate, methyl 2-hydroxy-3-methylbutyrate, methyl methoxyacetate, ethyl methoxyacetate, methoxyacetic acid propyl, methoxyacetic acid moiety Methyl ethoxyacetate, ethoxyacetic acid ethyl, ethoxyacetic acid propyl, ethoxyacetic acetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetic acid, ethyl butoxyacetate Propyl butoxy acetate, butyl butoxy acetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxy Ethyl propionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, 3-methoxypropionic acid Methyl, 3-Methoxypropionate, 3-Methoxypropionate, 3-Methoxypropionate, 3-Ethoxypropionate, 3-Ethoxypropionate, 3- Propyl oxypropionate, butyl 3-ethoxy propionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, 3-butoxy methyl propionate, 3-butoxy What satisfy | _{fills the} said SP _DS value can be employ | adopted and used among solvents, such as ethyl propionate, propyl 3-butoxy propionate, butyl 3-butoxypropionate, tetrahydrofuran, pyran, and (gamma) -butyrolactone.

The organic solvent in the present invention may be included as the balance of the content of the components based on 100% by weight of the total weight of the composition in order to maintain an appropriate viscosity.

Curable resin composition of this invention may further contain additives, such as a filler, a hardening | curing agent, a leveling agent, an adhesion promoter, antioxidant, a ultraviolet absorber, an aggregation inhibitor, a chain transfer agent, as needed.

Curable resin composition of the present invention containing the above components are used in the optical film to improve the interlayer adhesion, in particular can be useful for the surface planarization of the film is not flat surface. For example, in the case of a retarder using a PMMA substrate film containing polymer beads, a resin layer is formed between the PMMA substrate and the alignment film to cover the irregularities on the surface of the PMMA substrate by the polymer beads, thereby securing flatness and ensuring the PMMA substrate and the alignment film. Adhesion between can be strengthened.

As an embodiment of the optical film of the present invention, the retarder has a structure in which a base film, a resin layer formed of the composition of the present invention, an alignment film, and a cured liquid crystal layer are sequentially stacked, which will be described in detail below.

The base film according to the present invention can be used without particular limitation the base film commonly used in the art.

A transparent film is generally used as the base film in the art, and is, for example, a film including a triacetyl cellulose (TAC), a cyclo-olefin polymer (COP), a poly (methyl methacrylate) polymer, or the like. . The base film may be surface treated such as safonification treatment, remote plasma treatment, direct plasma treatment, monomer plasma treatment, or the like. When using a PMMA type base film, it is preferable to disperse | distribute a polymeric bead like a urethane bead in a base film, and to use it.

The alignment film according to the present invention may be formed of a composition for forming an alignment film including an alignment agent, a polymerization initiator, and an organic solvent commonly used in the art. As the alignment agent, an alignment agent conventionally used in the art may be used without particular limitation. For example, a polymer having a cinnamate group and having a weight average molecular weight of about 10,000-500,000 may be used, but is not limited thereto. As the polymerization initiator, a photopolymerization initiator or a thermal polymerization initiator commonly used in the art may be used. As the photopolymerization initiator, the photopolymerization initiators exemplified above may be used. An organic solvent may also be appropriately selected from among the organic solvents exemplified above.

The cured liquid crystal layer according to the present invention may be prepared by curing a composition comprising a liquid crystal compound, a polymerization initiator, and an organic solvent having a polymerizable functional group at the terminal, and as a polymerization initiator, a photopolymerization initiator commonly used in the art or A thermal polymerization initiator may be used, and the photopolymerization initiator exemplified above may be used as the photopolymerization initiator. An organic solvent may also be appropriately selected from among the organic solvents exemplified above.

Hereinafter, preferred examples are provided to aid the understanding of the present invention, but these examples are merely illustrative of the present invention and are not intended to limit the scope of the appended claims, which are within the scope and spirit of the present invention. It is apparent to those skilled in the art that various changes and modifications can be made to the present invention, and such modifications and changes belong to the appended claims.

Example 1-6 and Comparative Example 1-5

A curable resin composition was prepared by mixing a photopolymerization initiator, a first monomer, a second monomer, a leveling agent, and an organic solvent in the composition shown in Table 1 below (unit: g).

Table 1

Experimental Example

The prepared compositions of Example 1-6 and Comparative Examples 1-5 were applied to the PMMA film, dried at 100 ° C. for 30 seconds, and then exposed to 30 mJ, respectively, to form a resin layer. After apply | coating an orientation composition and drying at 100 degreeC for 50 second, exposure was performed each 20mJ, and the alignment film was formed. Applying a curable liquid crystal composition (RMS) comprising a liquid crystal compound having a carbon-carbon unsaturated bond on the terminal on the alignment film and dried for 1 minute at a temperature of 60 ℃, 1J exposure to induce a curing reaction to prepare a retardation film It was.

<Orientation angle>

The orientation angles of A in the A and B patterns of the retardation film manufactured by the Wake-100L equipment of Lukeo Corp. were measured.

◎; 45 ° ± 3 (A pattern), 135 ° ± 3 (B pattern)

○: Less than 45 ° ± 6 (A pattern), Less than 135 ° ± 6 (B pattern)

X: 45 ° ± 6 or more (A pattern), 135 ° ± 6 or more (B pattern)

<Hardness degree>

After coating curable resin composition on PMMA, drying and exposing, curing degree by FT-IR

◎; More than 95%

○: less than 85%

△: less than 75%

×: less than 65%

<Surface roughness>

After apply | coating curable resin composition on PMMA, it dries and exposes and measures surface roughness of curable resin composition.

◎; Ra value less than 2.0

(Circle): Ra value 2-5.

△: Ra value 5-10

×: Ra value 12 or more

<Layer adhesion>

When the generated pattern was evaluated through an optical microscope, the degree of tearing was evaluated on the following pattern.

◎; No tearing on the pattern

○: 1 to 3 tearing patterns

△: 4 to 8 tears on the pattern

×: more than 8 tears in pattern

TABLE 2

As described in Table 2 above, the retarder of the embodiments provided with a cured layer according to the present invention can be confirmed that the overall excellent in terms of curing degree, surface roughness and interlayer adhesion of the resin layer compared to the retarder of the comparative examples. Particularly, in Example 1, since the photopolymerization initiator has a dimerized structure, the photoactive site is twice as large as that in the conventional case, and it can be confirmed that other components are more excellent in curing degree than Example 2, which was used in the same manner.

Claims (15)

1. Photopolymerization initiators having at least two photoactive oxime ester backbones in one molecule; A first monomer capable of photocuring and thermosetting by including an isocyanate group and a (meth) acrylate group at its terminals; Polyfunctional second monomer having a hydroxy group or a carboxy group; And an organic solvent.
2. The curable resin composition of claim 1, wherein the photopolymerization initiator having at least two photoactive oxime ester skeletons in one molecule is dimerized through R ₁ or R ₂ .

   [Formula 1]

   

   Wherein R ₁ , R ₂ and R ₃ independently of one another represent R ₁₁ , OR ₁₁ , COR ₁₁ , SR ₁₁ , CONR ₁₂ R ₁₃ or CN,

   R ₄ and R ₅ are each independently R ₁₁ , OR ₁₁ , SR ₁₁ , COR ₁₁ , CONR ₁₂ R ₁₃ , NR ₁₂ COR ₁₁ , OCOR ₁₁ , COOR ₁₁ , SCOR ₁₁ , OCSR ₁₁ , COSR ₁₁ , CSOR ₁₁ , CN Represents a halogen atom or a hydroxy group,

   a and b are each independently an integer of 0 to 3,

   R ₁₁ , R ₁₂ and R ₁₃ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms Wherein the hydrogen atom of the alkyl group, aryl group, arylalkyl group and heterocyclic group is also R ₂₁ , OR ₂₁ , COR ₂₁ , SR ₂₁ , NR ₂₂ R ₂₃ , CON R ₂₂ R ₂₃ , -NR ₂₂ -OR ₂₃ , -NCOR ₂₂ -OCOR ₂₃ , -C (= N-OR ₂₁ ) -R ₂₂ , -C (= N-OCOR ₂₁ ) -R ₂₂ , CN, halogen atom, -CR ₂₁ = CR ₂₂ R ₂₃ , -CO- CR ₂₁ = CR ₂₂ R ₂₃ , OCO-CR ₂₁ = CR ₂₂ R ₂₃ , OC _1-6 alkylene-OCOR ₂₁ , COOR ₂₁ , or may be substituted with an epoxy group,

   R ₂₁ , R ₂₂ and R ₂₃ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms Indicates,

   The methylene group of the alkylene moiety of the substituent represented by R ₁₁ , R ₁₂ , R ₁₃ , R ₂₁ , R ₂₂ and R ₂₃ is an unsaturated bond, ether bond, thioether bond, ester bond, thioester bond, amide bond or urethane It may be interrupted 1 to 5 times by a bond, the alkyl moiety of the substituent may have a branched chain, a cyclic alkyl, the alkyl terminal of the substituent may be an unsaturated bond, and R ₁₂ , R ₁₃ and R ₂₂ and R ₂₃ may each form a ring together, and R ₃ may form a ring together with an adjacent benzene ring.)
3. The curable resin composition of claim 2, wherein the photopolymerization initiator having at least two photoactive oxime ester skeletons in one molecule is a compound represented by the following Chemical Formula 2 or Formula 3:

   [Formula 2]

   

   [Formula 3]

   

   Wherein R ₁ to R ₅ are as defined in claim 2.
4. The curable resin composition according to claim 1, wherein the photopolymerization initiator having at least two photoactive oxime ester skeletons in one molecule is a compound represented by the following general formula (11):

   [Formula 11]

   
5. The curable resin according to claim 1, wherein the first monomer capable of photocuring and thermosetting including an isocyanate group and a (meth) acrylate group at its terminal is one or more selected from the group consisting of compounds represented by Formulas 16 to 19: Composition:

   [Formula 16]

   

   (Wherein R ₁ and R ₂ are each independently hydrogen or a methyl group,

   R ₃ and R ₇ are each independently an alkylene group having 1 to 10 carbon atoms unsubstituted or substituted with a group selected from the group consisting of a ketone group, an ester group and a thiol group,

   R ₄ and R ₆ are each independently an alkylene group having 1 to 10 carbon atoms unsubstituted or substituted with a group selected from the group consisting of an amide group, a ketone group, an ester group and a thiol group,

   R ₅ is an alkylene group having 1 to 10 carbon atoms unsubstituted or substituted with an alkoxy group having 1 to 8 carbon atoms,

   [Formula 17]

   

   (Wherein R ₇ and R ₈ are each independently hydrogen or a methyl group,

   R ₉ and R ₁₁ are each independently an alkylene group having 1 to 10 carbon atoms unsubstituted or substituted with a group selected from the group consisting of a ketone group, an ester group and a thiol group,

   R ₁₀ is (a)

   

   Or (b)

   

   E ₁ and E ₃ are each independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, and E ₂ is an alkoxy group having 1 to 8 carbon atoms. Substituted or unsubstituted alkylene group having 1 to 10 carbon atoms,

   [Formula 18]

   

   (Wherein R ₁₂ is hydrogen or a methyl group,

   R ₁₃ is an alkylene group having 1 to 10 carbon atoms unsubstituted or substituted with a group selected from the group consisting of a ketone group, an ester group and a thiol group; and

   [Formula 19]

   

   (Wherein, R ₁₄ is hydrogen or a methyl group,

   R ₁₅ is an alkylene group having 1 to 10 carbon atoms unsubstituted or substituted with a group selected from the group consisting of a ketone group, an ester group and a thiol group.
6. The curable resin composition of claim 1, wherein the multifunctional second monomer having a hydroxyl group is represented by the following Chemical Formula 31:

   [Formula 31]

   Wherein at least one of R ₁ , R ₂ , R ₃ and R ₄ is hydrogen or a carboxy group and the rest are independently selected from methyl or acryloyl groups, and A is

   

   ,

   

   ,

   

   ,

   

   ,

   

   or

   

   Is a integer of 1 to 3, b is an integer of 0 to 12).
7. The curable resin composition according to claim 1, wherein the second monomer has a weight average molecular weight in terms of polystyrene of 200 to 3,000.
8. The curable resin composition of Claim 1 whose mixing weight ratio of a 1st monomer and a 2nd monomer is 1st monomer: 2nd monomer = 1: 1-2.
9. The curable resin composition of claim 1, wherein the organic solvent is a mixed solvent of a solvent having an SP _DS value of 1 or less and a solvent of 15 or more represented by the following Equation 1:

   [Equation 1]

   

   (In formula, SP _SUB is SP value of a base film, SP _SOL is SP value of a solvent.).
10. The optical film provided with the resin layer hardened | cured with curable resin composition of any one of Claims 1-9.
11. The optical film of claim 10, wherein the optical film is a retarder.
12. The optical film according to claim 11, wherein the retarder has a structure in which the resin layer is interposed between the base film and the alignment film.
13. The optical film of claim 12, wherein the base film is formed including a PMMA resin.
14. The optical film of claim 13, wherein a carbon-carbon saturated bond exists between the base film and the resin layer.
15. An image display device comprising the optical film of claim 10.