WO2013051831A2 - Composition for forming an alignment layer, and alignment layer and phase difference film manufactured using same - Google Patents

Abstract

The present invention relates to a composition for forming an alignment layer and to an alignment layer manufactured using same. More particularly, the present invention relates to a composition for forming an alignment layer for aligning liquid crystal compounds. The composition includes an adhesion-reinforcing agent including an isocyanate group and a (meth)acrylate group at an end portion for forming a bond with a reactive group in the liquid crystal compound. While curing the composition for forming the alignment layer, a chemical bond may be formed with another layer formed at the side portion so as to manufacture a phase difference film having very strong interlayer adhesion.

Description

Composition for forming an alignment film, alignment film and retardation film prepared therefrom

The present invention relates to a composition for forming an alignment film, and an alignment film prepared therefrom and a retardation film having excellent interlayer adhesion.

The factors that make a person feel three-dimensional are physiological and empirical factors. In general, three-dimensional image display technology uses a binocular parallax, which is the biggest factor for recognizing three-dimensional effect at a close range.

The principle of binocular parallax is a method of photographing a left eye image viewed through a left eye and a right eye image viewed through a right eye from at least two stereoscopic image capturing cameras, and then separating and transmitting them to the viewer's eyes. This is possible because two human eyes receive objects through the retina from different angles and these two images are synthesized in the cerebrum.

There are two methods of observing a stereoscopic image, a method of wearing glasses and a glasses-free method of not wearing glasses. The way of wearing glasses is (1) anaglyph method that uses sunglasses of colors that are distinct from each other, (2) polarization method that uses polarized glasses with different polarization directions, and (3) time-divided screen There is a time-sharing method of wearing glasses with an electronic shutter that is periodically repeated and synchronized with the period.

Among them, the polarized glasses are able to express a three-dimensional feeling regardless of the viewer's position, and have the most attention because they have less dizziness or fatigue of eyes and are easy to manufacture.

A display device for displaying a stereoscopic image using polarized glasses includes a patterned retardation film (having a patterned retardation layer formed on the substrate), and the patterned retardation film is formed by applying an adhesive or an adhesive to one side of the polarizing plate. Is bonded.

This patterned retardation film has a structure in which a transparent substrate, an alignment film and a cured liquid crystal layer are sequentially stacked. However, the retardation film has a problem that the adhesion strength between the layers is small, the interlayer peeling of the retardation film occurs in the process of removing the protective film after attaching the retardation film on the substrate with an adhesive.

An object of the present invention is to provide a composition for forming an alignment film which can improve the adhesive force with another film in contact with the alignment film.

Moreover, an object of this invention is to provide the retardation film excellent in the adhesive force between layers in the retardation film provided with an oriented film.

1. An alignment film-forming composition for forming an alignment film for orienting a liquid crystal compound, comprising: an alignment film including an adhesion enhancing agent including an isocyanate group and a (meth) acrylate group at its terminals that may be bonded to a reactive group of the liquid crystal compound. Formation composition.

2. The composition of claim 1, wherein the reactive group of the liquid crystal compound is a carbon-carbon unsaturated bond, a hydroxyl group, an epoxy group, or a cyano group.

3. The composition of claim 1, wherein the adhesion enhancer is at least one selected from the group consisting of compounds of Formulas 1 to 4 below:

[Formula 1]

(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 2]

(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 3]

(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 4]

(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.

4. The composition of claim 3, wherein the adhesion enhancer is a mixture of any one of the compounds represented by Formulas 2 to 4 and the compound represented by Formula 1.

5. according to the above 1, the composition for forming an alignment film comprising a polymer containing a cinnamate group as a photo-alignment agent.

6. In the above 5, the composition for forming an alignment film, including 0.1 to 20 parts by weight of the adhesion enhancer with respect to 100 parts by weight of the optical alignment agent.

7. In the above 1, selected from the group consisting of triazine compound, acetophenone compound, biimidazole compound, oxime compound, benzoin compound, benzophenone compound, thioxanthone compound and anthracene compound Composition for forming an alignment film comprising at least one photoinitiator.

8. In the above 1, 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, methoxy butyl acetate, methoxypentyl acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether Le, 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 propio Nitrate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate, methoxybutyl alcohol, ethoxybutyl alcohol, propoxybutyl alcohol, butoxybutyl alcohol, methoxybutyl acetate, ethoxybutyl acetate, propoxy Butyl acetate, butoxybutyl acetate, methoxybutyl propionate, ethoxybutyl propionate, propoxybutyl propionate, butoxybutyl propionate, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, di profile Ethylene 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 hydroxyacetate, hydroxide Ethyl hydroxy acetate, butyl hydroxy acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, 3-hydroxypropionate, butyl 3-hydroxypropionate, 2 -Hydroxy-3-methylbutyrate, methyl methoxyacetate, ethyl methoxyacetate, methoxyacetic propyl, methoxy butyl acetate, methyl ethoxyacetate, Ethyl acetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, butoxypropyl propyl, Butoxy Butyl Acetate, 2-Methoxy Propionate, 2-Methyl Propionate, 2-Methyl Propionate, 2-Methoxy Propionate, 2-Methoxypropionate, 2-Ethoxy Propionate, 2-E Propyl oxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, 3-methoxy Ethyl propionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, 3- Butyl oxypropionate, 3-propoxy methyl propionate, 3-propoxy propionate, 3-propoxy propionate, 3-butyl propoxypropionate, 3-butoxy methyl propionate, 3-butoxy ethyl propionate, 3-butoxy A composition for forming an alignment film comprising at least one organic solvent selected from the group consisting of propyl propionate, butyl 3-butoxypropionate, tetrahydrofuran, pyran and γ-butyrolactone.

9. The alignment film formed of the composition for forming an alignment film of any one of the above 1 to 8.

10. A retardation film comprising a substrate, an alignment film of 9 above formed on the substrate, and a liquid crystal layer formed on the alignment film.

11. In the above 10, wherein the substrate is a retardation film comprising a reactive group that can be bonded to the isocyanate group and (meth) acrylate groups contained in the adhesion enhancer of the composition for forming the alignment film on its surface.

12. The retardation film of 11 above, wherein the reactive group on the surface of the substrate is a hydroxyl group, a thiol group, a carboxyl group, a (meth) acrylate group, an amine group, or an epoxy group.

13. In the above 11, wherein the alignment layer is a phase difference film bonded by the substrate and the urethane bond, thiene bond or carbon-carbon saturated bond.

14. In the above 11, wherein the substrate is a retardation film containing triacetyl cellulose-based, cycloolefin-based or PMMA-based polymer.

15. The retardation film of claim 14, wherein the surface treatment is at least one treatment selected from the group consisting of saponification treatment, primer treatment, corona treatment, plasma treatment, and coating treatment.

16. The retardation film of claim 15, wherein the plasma treatment is at least one selected from the group consisting of a remote plasma treatment, a direct plasma treatment, and a monomer plasma treatment.

17. In the above 13, wherein the urethane bond is formed by the reaction of an isocyanate group of the compound represented by any one of formulas 1 to 4 of the alignment layer with the hydroxyl group, thiol group, carboxyl group, amine group or epoxy group of the substrate Retardation film:

[Formula 1]

(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 2]

(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 3]

(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 4]

(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.

18. In the above 13, wherein the carbon-carbon saturated bond is formed by the reaction of the (meth) acrylate of the compound represented by any one of the following formulas 1 to 4 of the alignment layer and the (meth) acrylate group of the substrate Retardation film being:

[Formula 1]

(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 2]

(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 3]

(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 4]

(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.

19. The retardation film of claim 13, wherein the thiylene bond is formed by a reaction of a (meth) acrylate group of a compound represented by any one of the following Chemical Formulas 1 to 4 of the alignment layer with a thiol group of the substrate:

[Formula 1]

(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 2]

(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 3]

(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 4]

(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.

20. The retardation film of 10 above, wherein the alignment layer is bonded to the liquid crystal layer and a urethane bond or a carbon-carbon saturated bond.

21. The retardation film of claim 10, wherein the liquid crystal layer is formed of a liquid crystal compound having a carbon-carbon unsaturated bond, a hydroxyl group, an epoxy group, or a cyano group.

22. In the above 20, wherein the urethane bond is formed by the reaction of an isocyanate group of the compound represented by any one of the following formula 1 to 4 of the alignment layer and the hydroxyl group, epoxy group or cyano group of the liquid crystal compound of the liquid crystal layer Retardation film:

[Formula 1]

(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 2]

(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 3]

(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 4]

(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.

23. The reaction of 20 above, wherein the carbon-carbon saturated bond is a reaction of a (meth) acrylate group of a compound represented by one of the following Chemical Formulas 1 to 4 of the alignment layer with a carbon-carbon unsaturated bond of the liquid crystal compound of the liquid crystal layer: Retardation film formed by:

[Formula 1]

(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 2]

(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 3]

(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 4]

(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.

24. The retardation film of any one of 10 to 23 above, wherein the liquid crystal layer is further formed by further comprising an adhesion enhancer including an isocyanate group and a (meth) acrylate group at its ends.

25. The retardation film of claim 24, wherein the liquid crystal layer and the alignment layer are bonded to each other by a chemical bond including a carbon-carbon saturated bond between the adhesion enhancer containing all of each other.

26. The retardation film of claim 24, wherein the adhesion promoter is one or more selected from the group consisting of compounds of Formulas 1 to 4 below:

[Formula 1]

(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 2]

(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 an alkyl group having 1 to 10 carbon atoms substituted or unsubstituted or substituted with an alkoxy group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms, E ₂ is an alkylene group having 1 to 10 carbon atoms unsubstituted or substituted with an alkoxy group having 1 to 8 carbon atoms,

[Formula 3]

(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 4]

(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.

27. In the above 24, wherein the liquid crystal layer retardation film containing 0.1 to 15 parts by weight of the adhesion strength enhancer based on 100 parts by weight of the liquid crystal compound.

The composition for forming an alignment film of the present invention may be used to prepare a retardation film having a very high adhesion between the layers by chemically forming bonds with different layers formed on both sides in the process of curing the alignment film.

In addition, since the retardation film of the present invention has a very high interlayer adhesion, the peeling phenomenon is remarkably reduced in manufacturing an optical film such as a polarizing film using the retardation film, thereby lowering a defective rate and thus improving productivity.

1 is a schematic cross-sectional view of a retardation film.

The present invention provides a composition for forming an alignment film for forming an alignment film for orienting a liquid crystal compound, the composition comprising an adhesion enhancing agent comprising an isocyanate group and a (meth) acrylate group at its terminals that can be bonded to a reactive group of the liquid crystal compound. The present invention relates to a composition for forming an alignment film used in the production of a retardation film having a very high interlayer adhesion by chemically forming a bond with another layer formed on the side surface in the process of curing the alignment film.

Hereinafter, the present invention will be described in detail.

The composition for forming an alignment film of the present invention is characterized by including an adhesion enhancing agent capable of chemically bonding with another layer formed on the side of the alignment film. The adhesion enhancer according to the present invention comprises at least one (meth) acrylate group terminal and one isocyanate group terminal. In the present invention, (meth) acrylate means acrylate or methacrylate.

In the present invention, the (meth) acrylate group and the isocyanate group of the adhesion enhancer are liquid crystalline compounds even if the (meth) acrylate group and / or the isocyanate group are not contained at the terminal at the time when the adhesion enhancer is mixed with the composition for forming an alignment film. And functional groups where (meth) acrylate groups or isocyanate groups are produced through further treatment, such as heat treatment, prior to chemical bonding with the substrate. For example, as a functional group in which an isocyanate group is produced through heat treatment, a pyrazole group connected by an amide bond to the terminal of the adhesion promoter may be mentioned. Gastric pyrazole groups are separated through a heat treatment process, an isocyanate group is formed at the end.

Usually, an alignment film is a layer which induces alignment of liquid crystals, and an alignment film used for a retardation film or the like is in contact with the liquid crystal layer on one surface thereof and in contact with the base film on the other side thereof. As described above, conventionally, there was a problem in that the interlayer adhesion between the alignment layer and other layers in contact with the alignment layer was not good, but the present invention introduced an adhesion enhancing agent containing an isocyanate group and a (meth) acrylate group at its ends into the alignment layer. Thus, the interlayer adhesion may be enhanced by chemically bonding the reactive groups exposed on the surface of the liquid crystal layer to which the above isocyanate group and the (meth) acrylate group contact each other, and more preferably the reactive groups on the surface of the base film.

Examples of the reactive group of the liquid crystal compound forming the liquid crystal layer in contact with one surface of the alignment film include carbon-carbon unsaturated bonds, hydroxyl groups, epoxy groups, cyano groups, and the like, and preferably carbon-carbon unsaturated bonds. More specifically, the carbon-carbon unsaturated bond may be a carbon-carbon unsaturated bond included in an acryloyloxy group, cyanoacrylate group, allyl group, cinnamate group, or allyloxy group.

Therefore, any base material having a reactive group among the liquid crystal compounds used in the art may be used in the present invention without limitation, and the liquid crystal compounds commonly used in the art may be known in the art even if they do not have such a reactive group. Any reactive group can be introduced at the end through the pretreatment process and can be used in the present invention without limitation.

More preferably, the substrate in contact with the other surface of the alignment film may also have a reactive group capable of reacting with an isocyanate group or a (meth) acrylate group on its surface. As such a reactive group, a hydroxyl group, a thiol group, a carboxy group, a (meth) acrylate group, an amine group, an epoxy group, etc. are mentioned.

Therefore, any substrate having such a reactive group among the substrates used in the art can be used in the present invention without limitation, and a substrate treatment process known in the art even if the substrate commonly used in the art does not have such a reactive group per se. If the reactive group can be introduced to the surface through may be used in the present invention without limitation.

More specific examples of the adhesion enhancer according to the present invention may be one or more selected from the group consisting of compounds represented by the following formula (1), (2), (3) and (4):

 [Formula 1]

(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 2]

(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 3]

(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 4]

(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 composition for forming an alignment layer of the present invention, the adhesion enhancer represented by Chemical Formula 1 to Chemical Formula 4 is at least one of the compounds represented by Chemical Formula 2 to Chemical Formula 4 and the compound represented by Chemical Formula 1 to secure better interlayer adhesion. It can be used as a mixture of.

More specific examples of the adhesion enhancer of Formula 1 to Formula 4 may include at least one selected from the group consisting of compounds represented by the following Formulas 5 to 15:

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

Compounds represented by the above formula (4) and compounds represented by the above formulas (12), (13), (14) and (15), which are examples of the compounds, are separated from the terminal by dimethyl pyrazole group through a heat treatment process such as a drying process, and thus It will have an isocyanate group.

The composition for forming an alignment layer of the present invention may include a photo-alignment agent, a photoinitiator and an organic solvent commonly used in the art in addition to the above adhesion enhancer.

As the photoalignment agent, a photoalignment 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.

Adhesion enhancers according to the present invention is preferably included in 0.1 to 20 parts by weight relative to 100 parts by weight of the photo-alignment agent. 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.

As the photoinitiator, photoinitiators conventionally used in the art may be used without particular limitation. For example, a triazine compound, an acetophenone compound, a biimidazole compound, an oxime compound, a benzoin compound, a benzophenone compound, a thioxanthone compound, an anthracene compound, etc. may be used, but is not limited thereto. no.

As the above triazine-based compound, for example, 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl)- 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.

As the acetophenone-based 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- On, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane Oligomer of -1-one, 2-methyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-ethyl-2-amino (4-morpholinophenyl) ethan-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-morpholinophenyl) propane- 1-one, 2-ethyl-2-amino (4-morpholinophenyl) butan-1-one, 2-methyl-2-meth Amino (4-morpholinophenyl) propane-1-one, 2-methyl-2-dimethylamino (4-morpholinophenyl) propane-1-one, 2-methyl-2-diethylamino (4-mor Polynophenyl) propan-1-one etc. are mentioned.

As the biimidazole-based compound, for example, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3 -Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) ratio Imidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, phenyl group at 4,4', 5,5 'position And imidazole compounds substituted with a boalkoxy group. Among these, 2,2'bis (2-chlorophenyl) -4,4 ', 5,5'-tetra phenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole is preferably used.

Examples of the above oxime compounds include 0-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one and the like.

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

As the above benzophenone-based compound, for example, benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3 ', 4,4'-tetra ( tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, etc. are mentioned.

Examples of the thioxanthone-based compound include 2-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichloro thioxanthone, 1-chloro-4-propoxy thioxanthone, and the like. 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.

In addition, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, phenylclioxylic acid Methyl, a titanocene compound, the photoinitiator which has group which can cause the chain transfer described in Unexamined-Japanese-Patent No. 2002-544205, etc. are mentioned.

In another aspect of the composition for forming an alignment film of the present invention, it may not include a photoinitiator. Photoinitiators have the advantage of facilitating the photopolymerization reaction of the photo-alignment agent. However, when the photoinitiator is used in an excessive amount, it acts as an impurity, lowers the orientation force, breaks down the liquid crystal orientation, and may cause light leakage phenomenon during cross polarization, or the photoinitiator may be sublimated after photocuring to contaminate the mask. When the intensity of the initiator reaction wavelength is very high compared to the wavelength at which the reaction occurs, side effects may be reduced such as lowering the line speed for the optical alignment. In this aspect, the composition for forming an alignment film of the present invention may or may not contain a very small amount of photoinitiator.

As the organic solvent, an organic solvent conventionally used in the art may be used without particular limitation. Ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, and ethylene glycol monoethyl ether acetate; Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxy butyl acetate, and methoxy pentyl acetate; Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether; Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol ethyl methyl ether, propylene glycol dipropyl ether propylene glycol propyl methyl ether and propylene glycol ethyl propyl ether; Propylene glycol alkyl ether propionates such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate and propylene glycol butyl ether propionate; Butyl diol monoalkyl ethers such as methoxy butyl alcohol, ethoxy butyl alcohol, propoxy butyl alcohol and butoxy butyl alcohol; Butanediol monoalkyl ether acetates such as methoxy butyl acetate, ethoxy butyl acetate, propoxy butyl acetate and butoxy butyl acetate; Butanediol monoalkyl ether propionates such as methoxybutyl propionate, ethoxybutyl propionate, propoxybutyl propionate and butoxybutyl propionate; Dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, and dipropylene glycol methyl ethyl ether; Aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone; Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin; Methyl acetate, ethyl acetate, propyl acetate, butyl acetate, 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate , Butyl hydroxy acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 3-hydroxypropionate methyl, 3-hydroxypropionate ethyl, 3-hydroxypropionate propyl, 3-hydroxypropionate butyl, 2-hydroxy 3-Methyl methyl butyrate, methyl methoxy acetate, ethyl methoxy acetate, methoxy acetate propyl, butyl acetate, ethoxy acetate methyl, ethoxy acetate, ethoxy acetate propyl, butyl ethoxy acetate, propoxy Methyl acetate, ethyl propoxy acetate, propyl propoxy acetate, butyl propoxy acetate, methyl butoxy acetate, ethyl butoxy acetate, Propyl acetate, butyl butoxy acetate, methyl 2-methoxypropionate, 2-methoxy ethylpropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate Propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, 3-methoxy ethylpropionate, 3-methoxy propylpropionate, 3-methoxy propylpropionate, 3-ethoxy propylpropionate, 3-ethoxy propylpropionate, 3-ethoxy propylpropionate, 3-ethoxy propylpropionate, 3 Methyl propoxypropionate, 3-propoxy propionate, 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, 3-butoxypropionic acid Esters such as ropil, 3-butoxy-propionic acid butyl; Cyclic ethers such as tetrahydrofuran and pyran; Cyclic esters, such as (gamma) -butyrolactone, etc. can be used individually or in mixture of 2 or more types, respectively.

The composition for forming an alignment film of the present invention may further include additives such as fillers, curing agents, leveling agents, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents, chain transfer agents and the like, as necessary.

The composition for forming an alignment film of the present invention forms an alignment film through a curing process, and may be applied without limitation as long as a conventionally used alignment film is used. Preferably, it can be usefully used for the patterned retardation film (patterned retarder) provided in the display apparatus used for three-dimensional image display.

The structure of a conventional retardation film is shown in FIG. The retardation film 100 has a structure in which an alignment layer 130 is interposed between the transparent substrate 110 and the photocurable liquid crystal layer 120.

The transparent substrate 110 according to the present invention is preferably reactive to react with isocyanate groups or (meth) acrylate groups, such as hydroxyl groups, thiol groups, carboxyl groups, (meth) acrylate groups, amine groups or epoxy groups on the surface. It may have a group.

The transparent substrate 110 according to the present invention may be used without limitation as long as it is a substrate having such a reactive group among substrates commonly used in the art, and even without such a reactive group, the reactive group is introduced to the surface through a pretreatment process known in the art. If possible, it can be used in the present invention without limitation.

As a substrate in the art, a transparent film is generally used. For example, a film including a triacetyl cellulose (TAC), a cyclo-olefin polymer (COP), a poly (methyl methacrylate) polymer, or the like is used. Substrates made of TAC, COP, PMMA do not have reactive groups on their surface that can react with isocyanates or (meth) acrylates. Therefore, the reactive group can be introduced to the surface through surface treatment. When the hydroxyl group is described as an example, the hydroxyl group is introduced to the surface when the saponification treatment is performed on the TAC surface, and the hydroxyl group is applied to the surface when the plasma treatment is performed on the surface of the COP. Can be introduced. Other surface treatments include dry treatments such as corona treatment and primer treatment; Chemical treatment such as alkali treatment including saponification treatment; The coating process etc. which form an easy adhesive bond layer is mentioned. Preferably, the cellulose-based film is alkali treatment including saponification treatment; Acrylic, polyolefin and polyester films are advantageous for dry treatment such as corona treatment or plasma treatment. As a more specific example of the plasma treatment, at least one process may be performed among a remote plasma, a direct plasma, and a monomer plasma.

The photocurable liquid crystal layer 120 is prepared by curing a composition comprising a liquid crystal compound having a carbon-carbon unsaturated carbon bond, a hydroxyl group, an epoxy group or a cyano group, a polymerization initiator, and an organic solvent at the end thereof, In general, a photopolymerization initiator or a thermal polymerization initiator may be used, and the photoinitiator exemplified above may be used as the photopolymerization initiator. An organic solvent may also be appropriately selected from among the organic solvents exemplified above.

In another aspect of the present invention, if necessary, the composition for forming the photocurable liquid crystal layer 20 may further include an adhesion enhancer according to the present invention described above. In this case, a carbon-carbon saturated bond is formed between the isocyanate group and the (meth) acrylate group containing both of the liquid crystal layer and the alignment layer at the end thereof, so that the adhesion between the layers can be further improved. desirable. In this case, the content of the adhesion enhancing agent, while containing 0.1 to 15 parts by weight of the adhesion enhancing agent with respect to 100 parts by weight of the liquid crystal compound effectively exerts the effect of strengthening the adhesion between the substrate and the alignment film and between the alignment film and the liquid crystal layer, the liquid crystal orientation It is preferable in terms of maintaining and not lowering the phase difference.

In the present invention, the reactive groups exposed on the surfaces of the transparent substrate 110 and the photocurable liquid crystal layer 120 may be the same or different.

The alignment layer 130 according to the present invention is an isocyanate group capable of forming a chemical bond by reacting with a reactive group on the surface of the transparent substrate 110 and a reactive group of the liquid crystal compound exposed on the surface of the photocurable liquid crystal layer 120 and a (meth) ) Adhesion enhancer comprising an acrylate group at the end.

As a specific example of the chemical bond, the isocyanate end of the adhesion promoter may react with the hydroxyl group, thiol group, carboxyl group, amine group, epoxy group or cyano group of the transparent substrate 110 or the photocurable liquid crystal layer 120 to form a urethane bond. have.

The hydroxyl, thiol, carboxyl, amine, epoxy or cyano group reacts with the isocyanate group to form a urethane bond as follows. For reference, the cyano group may be pretreated with H ₂ O while being heated, transformed into an amine group or carboxylic acid, and reacted with an isocyanate group.

Scheme 1

Scheme 2

Scheme 3

Scheme 4

Scheme 5

Scheme 6

As another specific example of the chemical bond, the (meth) acrylate end of the adhesion enhancing agent of the alignment layer reacts with the (meth) acrylate group and the carbon-carbon unsaturated bond of the transparent substrate 110 or the photocurable liquid crystal layer 120 It may form a carbon-carbon saturated bond. In addition, as described above, when the liquid crystal layer 120 includes an adhesion enhancer, each (meth) acrylate terminal of the adhesion enhancer of the alignment layer and the adhesion enhancer of the liquid crystal layer may react to form a carbon-carbon saturated bond. .

As another specific example of the chemical bond, the (meth) acrylate end of the adhesion enhancer may react with the thiol group of the transparent substrate 110 to form a thiylene bond.

Through the chemical bonding such as a urethane bond, a carbon-carbon saturated bond, a thiylene bond, and the like, the alignment layer 130 of the present invention is attached to the transparent substrate 110 and the photocurable liquid crystal layer 120 with high adhesion.

The retardation film according to the present invention is applied to the alignment layer composition according to the invention on a transparent substrate and then dried and exposed to form a pattern on the alignment layer, and then the photocurable liquid crystal layer forming composition on the alignment layer and dried photocurable It can be prepared by carrying out the process. As described above, the chemical bonding of the alignment film and the liquid crystal layer according to the present invention is made in the curing process of the liquid crystal layer, and the chemical bonding of the alignment film and the transparent substrate is made in a drying process (heat treatment).

Hereinafter, the present invention will be described in detail with reference to Examples. However, embodiments according to the present invention can be modified in many different forms, the scope of the present invention should not be construed as limited to the embodiments described below. The embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art.

Example 1-7 and Comparative Example 1-2

A composition for forming an alignment layer was prepared by mixing a photo-alignment agent, an adhesion enhancing agent, a photoinitiator (Irgacure 907, manufactured by BASF) and an organic solvent (toluene) in the composition shown in Table 1 below (unit: g).

Table 1

Sample manufacturing

The compositions of Examples 1-7 and Comparative Examples 1-2 prepared were saponified and applied to Fuji TAC Film having a hydroxyl group introduced thereon, dried at 100 ° C. for 1 minute, and then subjected to exposure to produce alignment films. It was. Applying a photocurable liquid crystal composition (RMS) comprising a liquid crystal compound having a carbon-carbon unsaturated bond on the terminal on the upper alignment layer and dried at a temperature of 60 ℃ for 1 minute, and then exposed to induce a curing reaction to give a retardation film Prepared.

Example 8-14 and Comparative Example 3-4

A liquid crystal compound (RMS), an adhesion enhancing agent, a photoinitiator (Irgacure 907, manufactured by BASF), and an organic solvent (toluene) were mixed in the composition shown in Table 2 to prepare a composition for forming a liquid crystal layer (unit: g).

In addition, a photo-alignment agent, an adhesion enhancing agent, a photoinitiator (Irgacure 907, manufactured by BASF) and an organic solvent (toluene) were mixed with the composition shown in Table 2 to prepare an alignment film-forming composition (unit: g).

TABLE 2

Sample manufacturing

Apply the alignment film forming composition of Example 8-14 and Comparative Example 3-4 to Fuji TAC film having a hydroxyl group introduced to the surface by saponification, and dried at 100 ° C. for 1 minute, followed by exposure to each alignment film. Produced. The composition for forming a liquid crystal layer of Example 8-14 and Comparative Example 3-4 was coated on the alignment layer and dried at a temperature of 60 ° C. for 1 minute, and then exposed to induce a curing reaction to prepare a retardation film.

Test Example

<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)

<Phase difference>

Rr; Retardation of the retardation film prepared in Comparative Example 1 (Table 3) or Comparative Example 3 (Table 4)

Rs; Retardation of the retardation film

◎; 0.97 <Rs / Rr <1.03

○: 0.95 <Rs / Rr <0.97 or 1.03 <Rs / Rr <1.05

△: 0.90 <Rs / Rr <0.95 or 1.05 <Rs / Rr <1.1

×: Rs / Rr 1.1 or more or Rs / Rr 0.90 or less

<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 3

Evaluation item	Example							Comparative example
	One	2	3	4	5	6	7	One	2
Orientation Angle (A Pattern)	◎	○	○	○	○	○	○	◎	◎
Orientation Angle (B Pattern)	◎	○	○	○	○	○	○	◎	◎
Phase difference (A pattern)	◎	○	○	○	○	○	○	◎	◎
Phase difference (B pattern)	◎	○	○	○	○	○	○	◎	◎
Interlayer adhesion	△	○	◎	○	△	△	◎	×	×

Table 4

Evaluation item	Example							Comparative example
	8	9	10	11	12	13	14	3	4
Orientation Angle (A Pattern)	◎	○	○	○	○	○	○	◎	◎
Orientation Angle (B Pattern)	◎	○	○	○	○	○	○	◎	◎
Phase difference (A pattern)	◎	○	○	○	○	○	○	◎	◎
Phase difference (B pattern)	◎	○	○	○	○	○	○	◎	◎
Interlayer adhesion	△	◎	○	◎	○	△	△	×	×

As described in Tables 3 and 4 above, the retardation film of the embodiments according to the present invention exhibits the same or similar optical performance as the retardation film of the comparative examples, it can be seen that the interlayer adhesion is superior to the comparative examples.

Claims (27)

1. An alignment film forming composition for forming an alignment film for orienting a liquid crystalline compound, the composition for forming an alignment film comprising an adhesion enhancing agent including an isocyanate group and a (meth) acrylate group at its terminals that may be bonded to a reactive group of the liquid crystal compound. Composition.
2. The composition for forming an alignment film according to claim 1, wherein the reactive group of the liquid crystal compound is a carbon-carbon unsaturated bond, a hydroxyl group, an epoxy group, or a cyano group.
3. The composition of claim 1, wherein the adhesion enhancer is at least one selected from the group consisting of compounds of Formulas 1 to 4:

   [Formula 1]

   

   (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 2]

   

   (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 3]

   

   (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 4]

   

   (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.
4. The composition of claim 3, wherein the adhesion enhancer is a mixture of any one of the compounds represented by Formulas 2 to 4 and the compound represented by Formula 1. 4.
5. The composition for forming an alignment film according to claim 1, comprising a polymer containing a cinnamate group as a photoalignment agent.
6. The composition for forming an alignment layer of claim 5, further comprising 0.1 part by weight to 20 parts by weight of an adhesion enhancing agent with respect to 100 parts by weight of the photoalignment agent.
7. The compound according to claim 1, which is selected from the group consisting of a triazine compound, an acetophenone compound, a biimidazole compound, an oxime compound, a benzoin compound, a benzophenone compound, a thioxanthone compound and an anthracene compound The composition for forming an alignment film containing the above photoinitiator.
8. The method of claim 1, wherein 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, di Ethylene 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 propio Nitrate, 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, propoxy Butyl acetate, butoxybutyl acetate, methoxybutyl propionate, ethoxybutyl propionate, propoxybutyl propionate, butoxybutyl propionate, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, diph in Pylene 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 hydroxyacetate, hydroxy Ethyl hydroxy acetate, butyl hydroxy acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, 3-hydroxypropionate, butyl 3-hydroxypropionate, 2 Hydroxy-3-methylbutyrate, methyl methoxyacetate, ethyl methoxyacetate, methoxyacetate, methoxy butyl acetate, methyl ethoxyacetate, Ethyl oxyacetate, ethoxy acetate propyl, butyl ethoxy acetate, methyl propoxy acetate, ethyl propoxy acetate, propyl propoxy acetate, butyl propoxy acetate, methyl butoxy acetate, butoxy acetate, butoxy acetate propyl Butyl oxyacetate, 2-methoxy methyl propionate, 2-methoxy ethylpropionate, 2-methoxy propyl propionate, 2-methoxy butyl propionate, 2-ethoxy propionate, 2-ethyl ethoxypropionate, 2-ethoxy Propyl propionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, 3-methoxypropionic acid Ethyl, 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, 3 Butyl ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, 3- A composition for forming an alignment film comprising at least one organic solvent selected from the group consisting of propyl butoxypropionate, butyl 3-butoxypropionate, tetrahydrofuran, pyran and γ-butyrolactone.
9. An alignment film formed of the composition for forming an alignment film of any one of claims 1 to 8.
10. A retardation film comprising a substrate, an alignment film of claim 9 formed on the substrate, and a liquid crystal layer formed on the alignment film.
11. The retardation film of claim 10, wherein the substrate includes an isocyanate group and a reactive group which may be bonded to a (meth) acrylate group included in an adhesion enhancing agent of the composition for forming an alignment layer on a surface thereof.
12. The retardation film according to claim 11, wherein the reactive group on the surface of the substrate is a hydroxyl group, a thiol group, a carboxyl group, a (meth) acrylate group, an amine group or an epoxy group.
13. The retardation film of claim 11, wherein the alignment layer is bonded to the substrate by a urethane bond, a thiylene bond, or a carbon-carbon saturated bond.
14. The retardation film of claim 11, wherein the substrate comprises a triacetylcellulose-based, cycloolefin-based, or PMMA-based polymer.
15. The retardation film of claim 14, wherein the surface treatment is at least one treatment selected from the group consisting of saponification treatment, primer treatment, corona treatment, plasma treatment, and coating treatment.
16. The retardation film of claim 15, wherein the plasma treatment is at least one selected from the group consisting of a remote plasma treatment, a direct plasma treatment, and a monomer plasma treatment.
17. The retardation film according to claim 13, wherein the urethane bond is formed by a reaction of an isocyanate group of a compound represented by any one of the following Chemical Formulas 1 to 4 of the alignment layer with a hydroxyl group, a thiol group, a carboxyl group, an amine group, or an epoxy group of the substrate. :

    [Formula 1]

    

    (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 2]

    

    (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 3]

    

    (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 4]

    

    (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.
18. The method according to claim 13, wherein the carbon-carbon saturated bond is formed by the reaction of the (meth) acrylate of the compound represented by any one of the following formulas 1 to 4 of the alignment layer with the (meth) acrylate group of the substrate Retardation film:

    [Formula 1]

    

    (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 2]

    

    (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 3]

    

    (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 4]

    

    (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.
19. The phase difference film of claim 13, wherein the thiylene bond is formed by a reaction of a (meth) acrylate group of a compound represented by any one of the following Chemical Formulas 1 to 4 of the alignment layer with a thiol group of the substrate:

    [Formula 1]

    

    (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 2]

    

    (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 3]

    

    (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 4]

    

    (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.
20. The retardation film of claim 10, wherein the alignment layer is bonded to the liquid crystal layer by a urethane bond or a carbon-carbon saturated bond.
21. The retardation film of claim 10, wherein the liquid crystal layer is formed of a liquid crystal compound having a carbon-carbon unsaturated bond, a hydroxyl group, an epoxy group, or a cyano group.
22. The retardation film of claim 20, wherein the urethane bond is formed by a reaction of an isocyanate group of a compound represented by any one of the following Formulas 1 to 4 of the alignment layer with a hydroxyl group, an epoxy group, or a cyano group of the liquid crystal compound of the liquid crystal layer. :

    [Formula 1]

    

    (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 2]

    

    (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 3]

    

    (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 4]

    

    (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.
23. The method of claim 20, wherein the carbon-carbon saturation bond is a reaction of a (meth) acrylate group of the compound represented by any one of the following formulas 1 to 4 of the alignment layer and the carbon-carbon unsaturated bond of the liquid crystal compound of the liquid crystal layer Retardation film to be formed:

    [Formula 1]

    

    (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 2]

    

    (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 3]

    

    (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 4]

    

    (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.
24. The retardation film according to any one of claims 10 to 23, wherein the liquid crystal layer further includes an adhesion enhancing agent including an isocyanate group and a (meth) acrylate group at its terminals.
25. The retardation film of claim 24, wherein the liquid crystal layer and the alignment layer are bonded by a chemical bond including a carbon-carbon saturation bond between the adhesion promoters, which are both included in each other.
26. The retardation film of claim 24, wherein the adhesion promoter is one or more selected from the group consisting of compounds of Formulas 1 to 4:

    [Formula 1]

    

    (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 2]

    

    (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 3]

    

    (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 4]

    

    (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.
27. The retardation film according to claim 24, wherein the liquid crystal layer comprises 0.1 to 15 parts by weight of the adhesion enhancing agent with respect to 100 parts by weight of the liquid crystal compound.

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