KR20150083846A - Photo-polymerizable liquid crystal composition, optical compensation film, optical compensation laminate film, electrode substrate, liquid crystal device substrate, and liquid crystal device - Google Patents

Abstract

Provided is a photopolymerizable liquid crystal composition capable of forming a positive A plate having excellent sputtering resistance, heat resistance and adhesion to a negative C plate, an optical compensation film using the same, an optical compensation laminated film, a substrate for a liquid crystal device, and a liquid crystal device .
A photopolymerizable liquid crystal composition (B) comprising a monofunctional photopolymerizable liquid crystal (A) for forming an optical compensatory film exhibiting positive uniaxial anisotropy and one photopolymerizable reactive group and a bifunctional photopolymerizable liquid crystal (B) having two photopolymerizable reactive groups . The optical compensation laminated film 12 has an optical compensation film 12A showing negative uniaxial anisotropy and an optical compensation film 12B showing positive uniaxial anisotropy produced by using the above composition.

Description

TECHNICAL FIELD [0001] The present invention relates to a photopolymerizable liquid crystal composition, an optical compensation film, an optical compensation laminated film, an electrode substrate, a substrate for a liquid crystal device, and a liquid crystal device. LIQUID CRYSTAL DEVICE}

The present invention relates to a photopolymerizable liquid crystal composition, and to an optical compensation film, an optical compensation laminated film, an electrode substrate, a substrate for a liquid crystal device, and a liquid crystal device using the photopolymerizable liquid crystal composition.

In the liquid crystal device, an optical compensation film (also referred to as a retardation film) for controlling the phase of light with birefringence is used in order to enlarge a viewing angle or the like.

Conventionally, the optical compensation film and the polarizing film generally adhere to the outside of the liquid crystal cell, and the thickness of the optical compensation film is about 50 to 150 mu m.

In recent years, thinning of a liquid crystal device and an electronic apparatus on which the liquid crystal device is mounted has been studied by forming an optical compensation laminated film in a liquid crystal cell.

In the form of an optically compensated laminated film,

An optically compensated laminated film (i) in which a biaxial plate is laminated on an alignment film such as polyimide,

An optical compensation film (hereinafter also referred to as a positive A plate) showing positive uniaxial anisotropy and an optical compensation film showing negative uniaxial anisotropy (hereinafter, referred to as a negative C plate (Ii), (iii), < RTI ID = 0.0 >

An optical compensation laminated film (iii) in which a positive A plate is laminated on the negative C plate via an orientation film,

And an optical compensation laminated film (iv) in which a positive A plate is directly laminated on a negative C plate functioning as an alignment film.

Patent Documents 1 and 2 disclose a substrate for a liquid crystal device having the optical compensation laminated film (iii) or (iv).

In Examples 1 and 2 of Patent Document 1, polyester was coated on a substrate, the obtained coating film was subjected to heat drying and firing, and then subjected to rubbing treatment to form a negative C plate having a function as an alignment film have. Thereafter, a biphenyl-based photopolymerizable liquid crystal is coated on the negative C plate, heated and dried, and then photopolymerized to form a positive A plate (paragraphs 0025 and 0026).

In Examples 1 and 2 of Patent Document 1, only one type of photopolymerizable liquid crystal is used as the photopolymerizable liquid crystal of the material for the positive A plate.

In Example 8 of Patent Document 2, polyimide is coated on a substrate, and the obtained coating film is subjected to heat drying and firing to form a negative C plate. After forming an alignment film on the negative C plate and rubbing treatment, bifunctional photopolymerizable liquid crystal is applied, dried, and then photopolymerized to form a positive A plate (paragraphs 0098 to 0100).

In Examples 1 to 12 of Patent Document 2, only bifunctional photopolymerizable liquid crystals are used as photopolymerizable liquid crystals of the material for the positive A plate.

Japanese Patent Application Laid-Open No. 2010-230823 Japanese Patent Application Laid-Open No. 2009-223304 Japanese Patent Publication No. 4725516 Japanese Patent Publication No. 4998269 Japanese Patent Publication No. 5012020

When the optical compensation laminated film is formed inside the liquid crystal cell, it is required that the optical compensation laminated film is not deteriorated or its optical characteristic is not changed in the manufacturing process after the film formation. For example, an electrode such as ITO (indium tin oxide) may be formed directly on the optical compensation laminated film by a sputtering method. In this case, the optical compensation laminated film needs to have resistance to sputtering which does not cause cracking even when sputtering the upper layer directly, and does not change optical characteristics.

In the optical compensation laminated film (iv) in which the positive A plate is directly laminated on the negative C plate functioning as the alignment film, it is also necessary that the adhesiveness between the films is good.

As a result of the investigation by the present inventors, it has been found that when only one kind of photopolymerizable liquid crystal is used as the positive A plate material as described in Patent Documents 1 and 2, a positive A plate having excellent resistance to sputtering and adhesion to a negative C plate is obtained .

An object of the present invention is to provide a photopolymerizable liquid crystal composition capable of forming a positive A plate having good anti-sputtering property and good adhesion to a negative C plate, and an optical compensation film comprising the positive A plate.

The present invention also provides an electrode substrate, a substrate for a liquid crystal device, and a liquid crystal device capable of providing an optical compensated laminated film having good anti-sputtering property and good adhesion between a negative C plate and a positive A plate, The purpose.

The present invention provides a photopolymerizable liquid crystal composition, an optical compensatory film, an optical compensatory laminated film, an electrode substrate, a substrate for a liquid crystal device, and a liquid crystal device, each of which has the following structures [1] to [15].

[1] A photopolymerizable liquid crystal composition for forming an optical compensatory film exhibiting positive uniaxial anisotropy,

A photopolymerizable liquid crystal composition comprising a monofunctional photopolymerizable liquid crystal (A) having one photopolymerizable reactive group and a bifunctional photopolymerizable liquid crystal (B) having two photopolymerizable reactive groups.

[2] The photopolymerizable liquid crystal composition according to the above [1], wherein the monofunctional photopolymerizable liquid crystal (A) and the bifunctional photopolymerizable liquid crystal (B) have a mass ratio of 95/5 to 30/70.

[3] The monofunctional photopolymerizable liquid crystal (A) is the photopolymerizable liquid crystal composition according to [1] or [2], which is represented by the following formula (1-1).

^{_{CH 2 = CR 11 -COO- (E}} 11) m1 -Cy-Y 1 -Cy-E 12 -R 12 ... (1-1)

(Wherein R ^{11 is a} hydrogen atom or a methyl group, R ¹² is an alkyl group having 1 to 8 carbon atoms, Y ^{1 is} -OCO- or -COO-, m ^{1 is} 0 or 1. E ¹¹ and E ¹² are each independently 1,4 A phenylene group or a trans-1,4-cyclohexylene group, Cy: a trans-1,4-cyclohexylene group, provided that the 1,4- A hydrogen atom in the group may be substituted with a fluorine atom, a chlorine atom or a methyl group.

[4] The photopolymerizable liquid crystal composition according to [1] or [2], wherein the monofunctional photopolymerizable liquid crystal (A) is represented by the following formula (1-2).

CH ₂ = CR ²¹ -COO- (L 2) _{k 2} -E ²¹ -E ²² -E ²³ -E ²⁴ -R ²² (1-2)

(Where, R ^21: a hydrogen atom or a methyl group, R ^22: an alkyl group or a fluorine atom k2 having a carbon number of 1-8: 0 or 1. L2: -.. (CH 2) p2 O- or - (CH _{2) q2} - (where , p2 and q2 are each independently an integer of ^{2 ~ 8) E 21:.} . 1,4- phenylene group, E ^22, E ²³ and E ^24:. each independently a 1,4-phenylene group or trans-1,4 -Cyclohexylene group, and at least one of E ²² and E ²³ is a trans-1,4-cyclohexylene group, provided that the 1,4-phenylene group and the trans-1,4-cyclohexylene group are , The hydrogen atom bonded to the carbon atom in the group may be substituted with a fluorine atom, a chlorine atom or a methyl group.)

(5) The photopolymerizable liquid crystal composition according to [1] or [2], wherein the monofunctional photopolymerizable liquid crystal (A) is represented by the following formula (1-3).

^{_{CH 2 = CR 31 -COO- (L3}} ) k3 -E 31 -E 32 -E 33 -R 32 ... (1-3)

(Wherein R ^{31 is a} hydrogen atom or a methyl group, R ³² is an alkyl group having 1 to 8 carbon atoms, k ₃ is 0 or 1. L ₃ is - (CH ₂ ) p ₃ O-, -Cy-COO- . 4-cyclohexylene group), or -Cy-OCO- (However, p3 is an integer of ^{2 ~ 8) E 31, E} 32 and E ^33:.. each independently represent a 1,4-phenylene group or trans -1 , 4-cyclohexylene group (where, E ^31, E ³² and E ³³ at least one of trans-1,4-cyclohexylene group, and E ³¹ also in the case where L3 is -Cy-OCO- trans 1,4-cyclohexylene group and, L3 is - (CH ₂₎ a O- or _p3 or k3 each, E ³¹ and E ³³ in the case where 0 is 1,4-phenylene group, E ³² is trans -1,4-cyclohexylene group. However, the 1,4-phenylene group and the trans-1,4-cyclohexylene group are groups in which the hydrogen atom bonded to the carbon atom in the group is a fluorine atom, a chlorine atom or a methyl group . ≪ / RTI >

[6] The bifunctional photopolymerizable liquid crystal (B) is the photopolymerizable liquid crystal composition according to any one of [1] to [5], which is represented by the following formula (2).

Q ¹ -Z ¹ -A ¹ -Z ³ -MZ ⁴ -A ² -Z ² -Q ² ... (2)

(Wherein Q ¹ and Q ² are each independently a photopolymerizable reactive group, Z ¹ , Z ² , Z ³ and Z ⁴ are each independently a single bond or a divalent linking group, A ¹ and A ² : Spacer group of 2 to 20 M: Mesogenic group.)

[7] The bifunctional photopolymerizable liquid crystal (B) is the photopolymerizable liquid crystal composition according to [6], which is represented by the following formula (2-1).

^{_{CH 2 = CR 41 -COO- (E}} 41) m4 -Cy-Y 4 -Cy- (E 42) n4 -OOC-CR 42 = CH 2 ... (2-1)

(Wherein R ⁴¹ and R ⁴² are each independently a hydrogen atom or a methyl group, Y ^{4 is} -OCO- or -COO-, m ⁴ and n ⁴ are each independently 0 or 1. E ⁴¹ and E ⁴² are each independently 1, A 4-phenylene group or a trans-1,4-cyclohexylene group, Cy: a trans-1,4-cyclohexylene group, provided that the 1,4-phenylene group and the trans- , The hydrogen atom in the group may be substituted with a fluorine atom, a chlorine atom or a methyl group.

[8] The bifunctional photopolymerizable liquid crystal (B) is the photopolymerizable liquid crystal composition according to [6], which is represented by the following formula (2-2).

^{_{CH 2 = CR 51 -COO- (L5}} ) k5 -E 51 -E 52 -E 53 -E 54 - (M5) n5 -OOC-CR 52 = CH 2 ... (2-2)

(Where, R ⁵¹ and R ^52: each independently represent a hydrogen atom or a methyl group and k5 n5: each independently 0 or 1. L5 and M5:. Are each independently - (CH _{2) p5} O- or - (CH _{2) q5} - (wherein each of p5 and q5 is independently an integer of 2 to 8.) E ⁵¹ : 1,4-phenylene group E ⁵² , E ⁵³ and E ⁵⁴ : each independently 1,4-phenylene group or trans- Cyclohexylene group, and at least one of E ⁵² and E ⁵³ is a trans-1,4-cyclohexylene group, provided that the 1,4-phenylene group and the trans-1,4-cyclo In the hexylene group, the hydrogen atom bonded to the carbon atom in the group may be substituted with a fluorine atom, a chlorine atom or a methyl group.)

[9] The bifunctional photopolymerizable liquid crystal (B) is the photopolymerizable liquid crystal composition according to [6], which is represented by the following formula (2-3).

^{_{CH 2 = CR 61 -COO- (L6}} ) k6 -E 61 -E 62 -E 63 - (M6) n6 -COO-CR 62 = CH 2 ... (2-3)

(Where, R ⁶¹ and R ^62: each independently represent a hydrogen atom or a methyl group and k6 n6: each independently 0 or 1. L6 and M6:. Are each independently _{- (CH 2) p6 O-,} -Cy-COO- ( Cy is a trans-1,4-cyclohexylene group), or -Cy-OCO- (wherein p6 is an integer of 2 to 8) E ⁶¹ , E ⁶² and E ⁶³ : A phenylene group or a trans-1,4-cyclohexylene group (provided that at least one of E ⁶¹ , E ⁶² and E ⁶³ is a trans-1,4-cyclohexylene group and L 6 is -Cy-OCO- in the case of E ⁶¹ are trans-1,4-cyclohexylene group and, L6 is - (CH ₂₎ each of E ⁶¹ and E ⁶³ when the _p6 or O-, or k6 is 0, 1,4-phenylene group And E ⁶² is a trans-1,4-cyclohexylene group.) However, the 1,4-phenylene group and the trans-1,4-cyclohexylene group are groups in which the hydrogen atom bonded to the carbon atom in the group is fluorine An atom, a chlorine atom or a methyl group.

[10] An optical compensation film exhibiting positive uniaxial anisotropy obtained by photo-curing a coating film of the photopolymerizable liquid crystal composition according to any one of [1] to [9].

[11] An optical compensation laminated film comprising an optical compensating film exhibiting negative uniaxial anisotropy and an optical compensation film exhibiting positive uniaxial anisotropy described in [10] above.

[12] The optical compensation multilayer film according to [11], wherein the optical compensation film exhibiting negative uniaxial anisotropy contains polyimide having an alicyclic structure in the skeleton.

[13] An electrode substrate having the optical compensation laminated film described in [12] above and an electrode formed on the optical compensation laminated film on a substrate.

[14] A substrate for a liquid crystal device having an electrode substrate according to [13] and an alignment film formed on the electrode substrate.

[15] A liquid crystal device comprising the liquid crystal substrate described in [14] above, an opposing substrate, and a liquid crystal layer sandwiched between the liquid crystal substrate and the opposing substrate.

The photopolymerizable liquid crystal composition of the present invention can form a positive A plate having excellent resistance to sputtering and adhesion to a negative C plate, and an optical compensation film comprising the positive A plate.

The optical compensation laminated film comprising the lamination of the positive A plate and the negative C plate of the present invention is excellent in the adhesion between the negative C plate and the positive A plate with good sputter resistance and is excellent in adhesion to the electrode substrate having the optical compensation laminated film, The substrates for use and the liquid crystal device can be thinned and reduced in cost because the optical characteristics and adhesion between the films are good and the optical compensation laminated film is provided in the liquid crystal cell.

BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a exploded schematic cross-sectional view of a liquid crystal device according to one embodiment of the present invention. FIG.
2 is a cross-sectional view illustrating a modification of the design.
3 is a schematic cross-sectional view showing the structure of the optical compensation laminated film.

In the present specification, the group represented by the formula (x) may be simply referred to as a group (x).

In the present specification, the compound represented by formula (y) may be simply referred to as compound (y).

Here, the expressions (x) and (y) represent arbitrary expressions.

In the present specification, the refractive indexes in the x direction, the y direction and the z direction are nx, ny, and nz, respectively, with the plane parallel to the film plane of the optical compensation laminated film as xy plane and the film thickness direction as the z direction .

In the negative C plate, nx = ny > nz.

In the positive A plate, nx > ny = nz.

Hereinafter, embodiments of the present invention will be described.

In the present specification, "%" represents mass% unless otherwise specified.

[Photopolymerizable liquid crystal composition]

The photopolymerizable liquid crystal composition of the present invention (hereinafter also referred to as composition (Y)) is a material for forming an optical compensation film (positive A plate) exhibiting positive uniaxial anisotropy.

The composition (Y) contains a monofunctional photopolymerizable liquid crystal (A) containing one photopolymerizable reactive group and a bifunctional photopolymerizable liquid crystal (B) containing two photopolymerizable reactive groups.

The composition (Y) of the present invention is an optical compensation laminate film (positive A plate) in which an optical compensation film (positive A plate) exhibiting positive uniaxial anisotropy is laminated on an optical compensation film (negative C plate) exhibiting negative uniaxial anisotropy functioning as an orientation film Can be suitably used for production.

When a positive A plate is formed using only the monofunctional photopolymerizable liquid crystal (A), if an electrode such as ITO is formed by sputtering directly on the positive A plate, there is a possibility that cracks will occur in the positive A plate or optical properties will change have.

When the positive A plate is formed using only the bifunctional photopolymerizable liquid crystal (B), the adhesion between the negative C plate serving as the alignment film and the positive A plate is poor, which may cause peeling of the film in the manufacturing process.

On the other hand, by using the monofunctional photopolymerizable liquid crystal (A) and the bifunctional photopolymerizable liquid crystal (B) in combination, a positive A plate having excellent resistance to sputtering and adhesion to the negative C plate can be obtained.

As the monofunctional photopolymerizable liquid crystal (A), a compound represented by the following formula (1-1), (1-2) or (1-3) is preferable. These compounds are described in Patent Documents 3 to 5 exemplified in the section of "BACKGROUND ART", and those patents can be referred to for details of preferred embodiments and specific examples.

By using these monofunctional photopolymerizable liquid crystals (A) as the positive A plate material, they have heat resistance against the liquid crystal device manufacturing process temperature after film formation. For example, it has heat resistance to a heat treatment at about 230 캜 at the time of forming a polyimide alignment film.

^{_{CH 2 = CR 11 -COO- (E}} 11) m1 -Cy-Y 1 -Cy-E 12 -R 12 ... (1-1)

In the formula (1-1), R ¹¹ is a hydrogen atom or a methyl group, and a hydrogen atom is preferable. When R < ¹¹ > is a hydrogen atom, the photopolymerization reaction of the composition (Y) proceeds rapidly. In addition, there is an advantage that the obtained optical compensation film is not well affected by the external environment (temperature, etc.), and the in-plane distribution of retardation is small.

R ¹² is an alkyl group having 1 to 8 carbon atoms. This makes it possible to lower the melting point (T _m ) of the composition (Y) (that is, the phase transition point of the crystalline phase-nematic phase). As R ¹² , an alkyl group having 2 to 6 carbon atoms is preferable. R ¹² is preferably a linear chain structure since the compound (1-1) can broaden the temperature range in which it exhibits liquid crystallinity.

Y ¹ is -COO- or -OCO-. -OCO- is preferable in that the melting point ( _Tm ) can be lowered, and -COO- is preferable in the point that a large Δn can be exhibited when the film is made into an optical compensation film. Here,? N is an anisotropic refractive index.

m1 is 0 or 1, and when the Y ¹ is -COO- is 0 are preferred when the preferred 1, Y ^1, and is -OCO-.

E ¹¹ and E ¹² each independently represent a 1,4-phenylene group (hereinafter referred to as Ph) or a trans-1,4-cyclohexylene group (hereinafter referred to as Cy). When E ¹¹ and E ¹² are 1,4-phenylene groups (Ph),? N of the compound (1-1) can be increased. Therefore, preparation of the composition (Y) exhibiting a large? N is facilitated. When E ¹¹ and E ¹² are trans-1,4-cyclohexylene group (Cy), compatibility with other compounds is good.

The compound (1-1) preferably has at least one 1,4-phenylene group (Ph). When m = 0, E ¹¹ is preferably 1,4-phenylene group (Ph), and when m = 1, at least one of E ¹¹ and E ¹² is preferably 1,4-phenylene group (Ph).

The 1,4-phenylene group (Ph) and the trans-1,4-cyclohexylene group (Cy) in the compound (1-1) may be an unsubstituted group or a hydrogen atom bonded to the carbon atom in the group A fluorine atom, a chlorine atom or a group substituted with a methyl group, and an unsubstituted group is preferable.

As the compound (1-1), the following compound (1-1A) wherein R ¹¹ is a hydrogen atom (wherein the symbols have the same meanings as defined above) are preferable.

_{CH 2 = CH-COO- (E} 11) m1 -Cy-Y 1 -Cy-E 12 -R 12 ... (1-1A)

Specific examples of the compound (1-1) include the following compounds. Among them, the compounds (1-1Aa2) to (1-1Aa6), (1-1Ab2) to (1-1Ab6), (1-1Ac2) (1-1Aa6), (1-1Ac2) to (1-1Ac6) are particularly preferable.

However, when a group having a structural isomer exists in the alkyl group in the following formula, all of the groups are included, and a linear alkyl group is preferable.

CH ₂ = CR ²¹ -COO- (L 2) _{k 2} -E ²¹ -E ²² -E ²³ -E ²⁴ -R ²² (1-2)

In the formula (1-2), R ²¹ is a hydrogen atom or a methyl group, and a hydrogen atom is preferable. This is the same as in the case of R < ¹¹ > in the compound (1-1).

R ²² is an alkyl group having 1 to 8 carbon atoms or a fluorine atom. This makes it possible to lower the melting point (T _m ) of the composition (Y) (that is, the phase transition point of the crystalline phase-nematic phase). As R ²² , an alkyl group having 2 to 6 carbon atoms or a fluorine atom is preferable. From the viewpoint that the compound (1-2) can broaden the temperature range in which liquid crystallinity is exhibited, R ²² is preferably a linear chain structure.

k2 is 0 or 1, and 1 is preferred.

L2 is - (CH ₂ ) _{p 2} O- or - (CH ₂ ) _{q 2} - (in which p ₂ and q 2 are each independently an integer of 2 to 8), and - (CH ₂ ) _{p 2} O- is preferable.

If general, the polymerization of the polymerizable liquid crystal, there is a tendency that the value of Δn in the polymerization before or after lowering, L2 is - (CH _{2) p2} O- and - (CH _{2) q2} - if group having a polymethylene group such as a , It is possible to suppress the decrease of the value of? N before and after the polymerization.

E ²¹ is a 1,4-phenylene group (Ph), E ²² , E ²³ and E ²⁴ are each independently a 1,4-phenylene group (Ph) or a trans-1,4-cyclohexylene group (Cy) .

The number of cyclic groups in the compound (1-2) is 4, and at least one of E ²² and E ²³ is Cy. At least one of E ²² , E ²³ and E ²⁴ is preferably Ph. When a plurality of Phs are included, it is preferable that two Phs are adjacent to each other since the value of? N can be increased.

"E ²¹ -E ²² -E ²³ -E ²⁴ 'is of a structure," Ph-Ph-Cy-Ph "," Ph-Cy-Ph-Ph "," Ph-Ph-Cy-Cy "," Ph Ph-Cy-Ph-Cy "and" Ph-Cy-Cy-Cy ". Among these, "Ph-Cy-Ph-Ph", "Ph-Ph-Cy-Cy" and "Ph-Ph-Cy-Ph" are preferable in that Δn of the compound . This facilitates the preparation of the composition (Y) exhibiting a large? N.

As the compound (1-2), the following compounds (1-2A) to (1-2C) are preferable.

Of said compound, wherein R ²¹ is a hydrogen atom, R ²² having the carbon number of the straight chain alkyl group or a fluorine atom, a compound of 2 to 6 are preferred, and also the _{-L2- - (CH 2) p2 O-} (p2 is 4-6 Is preferable) is particularly preferable.

The 1,4-phenylene group (Ph) and the trans-1,4-cyclohexylene group (Cy) in E ²¹ to E ²⁴ are groups in which the hydrogen atom bonded to the carbon atom in the group is a fluorine atom, Or may be substituted.

The 1,4-phenylene group (Ph) is preferably an unsubstituted group, a group substituted with one fluorine atom, or a group substituted with one methyl group. When the 1,4-phenylene group (Ph) has these substituents, there is an effect of lowering the melting point of the compound (1-2) and an effect of lowering the viscosity. The position of the substituent is preferably 2-position or 3-position. The trans-1,4-cyclohexylene group (Cy) is preferably an unsubstituted group.

The compound (1-2) is preferably the compound shown below, and the compound (1-2A-1), (1-2A-3), (1-2A-5) -2B-3) to (1-2B-5), (1-2C-1), and (1-2C-2).

[Chemical Formula 1]

^{_{CH 2 = CR 31 -COO- (L3}} ) k3 -E 31 -E 32 -E 33 -R 32 ... (1-3)

In the formula (1-3), R ³¹ is a hydrogen atom or a methyl group, preferably a hydrogen atom. This is the same as in the case of R < ¹¹ > in the compound (1-1).

R ³² is an alkyl group having 1 to 8 carbon atoms. This is the same as the case of R ^{12 in} the compound (1-1).

L 3 is - (CH ₂ ) p ₃ O-, -Cy-COO- or -Cy-OCO- (p3 is an integer of 2 to 8).

k3 is 0 or 1, and 1 is preferred.

E ³¹ , E ³² and E ³³ each independently represent a 1,4-phenylene group (Ph) or a trans-1,4-cyclohexylene group (Cy). Provided that at least one of E ³¹ , E ³² and E ³³ is a trans-1,4-cyclohexylene group (Cy). E ³¹ in the case where L 3 is -Cy-OCO- is trans-1,4-cyclohexylene group (Cy), L 3 is - (CH ₂ ) _{p 3} O-, or E ³¹ in the case of k is 0 Each of E ³³ is a 1,4-phenylene group (Ph) and E ³² is a trans-1,4-cyclohexylene group (Cy).

The bifunctional photopolymerizable liquid crystal (B) is preferably a compound represented by the following formula (2-1), (2-2) or (2-3).

These compounds correspond to compounds (1-1), (1-2) and (1-3) which are examples of the monofunctional photopolymerizable liquid crystal (A), respectively.

^{_{CH 2 = CR 41 -COO- (E}} 41) m4 -Cy-Y 4 -Cy- (E 42) n4 -OOC-CR 42 = CH 2 ... (2-1)

In the formula (2-1), R ⁴¹ and R ⁴² are each independently a hydrogen atom or a methyl group, and are the same as R ¹¹ in the compound (1-1).

Y ⁴ is -OCO- or -COO-, and is the same as Y ¹ in the compound (1-1). m4 and n4 are each independently 0 or 1 and are the same as m1 in the compound (1-1).

E ⁴¹ and E ⁴² each independently represent a 1,4-phenylene group (Ph) or a trans-1,4-cyclohexylene group (Cy) and are the same as E ¹¹ and E ¹² in the compound (1-1) .

The 1,4-phenylene group (Ph) and the trans-1,4-cyclohexylene group (Cy) may be substituted with a hydrogen atom in the group by a fluorine atom, a chlorine atom or a methyl group.

^{_{CH 2 = CR 51 -COO- (L5}} ) k5 -E 51 -E 52 -E 53 -E 54 - (M5) n5 -OOC-CR 52 = CH 2 ... (2-2)

In the formula (2-2), R ⁵¹ and R ⁵² are each independently a hydrogen atom or a methyl group, and are the same as R ²¹ in the compound (1-2).

k5 and n5 are each independently 0 or 1 and are the same as k2 in the compound (1-2).

In (but, p5 and q5 are each independently an integer of 2-8.), And the compound (1-2) - L5 and M5 are each independently - (CH _{2) p5} O- or - (CH _{2) q5} L2.

E ⁵¹ is a 1,4-phenylene group (Ph), and is the same as E ²¹ in the compound (1-2).

E ⁵² , E ⁵³ and E ⁵⁴ each independently represent a 1,4-phenylene group (Ph) or a trans-1,4-cyclohexylene group (Cy), and at least one of E ⁵² and E ⁵³ is a trans- Cyclohexylene group (Cy). These are the same as E ²² , E ²³ and E ²⁴ in the compound (1-2).

In the 1,4-phenylene group (Ph) and the trans-1,4-cyclohexylene group (Cy), the hydrogen atom bonded to the carbon atom in the group may be substituted with a fluorine atom, a chlorine atom or a methyl group.

^{_{CH 2 = CR 61 -COO- (L6}} ) k6 -E 61 -E 62 -E 63 - (M6) n6 -COO-CR 62 = CH 2 ... (2-3)

In the formula (2-3), R ⁶¹ and R ⁶² are each independently a hydrogen atom or a methyl group, and are the same as R ³¹ in the compound (1-3).

k6 and n6 are each independently 0 or 1, and are the same as k3 in the compound (1-3).

L6 and M6 are each independently _{- (CH 2) p6 O-,} -Cy-COO- , or -Cy-OCO- (. However, p6 is an integer of 2-8), and, L3 in the compound (1-3) .

E ⁶¹ , E ⁶² and E ⁶³ each independently represent a 1,4-phenylene group (Ph) or a trans-1,4-cyclohexylene group (Cy), provided that at least one of E ⁶¹ , E ⁶² and E ⁶³ E ⁶¹ in the case where L6 is -Cy-OCO- is trans-1,4-cyclohexylene group (Cy) and L6 is - ( CH ₂₎ each of E ⁶¹ and E ⁶³ when the _p6 O-, or k6 is 0 or is a 1,4-phenylene group (Ph), E ⁶² is trans-1,4-cyclohexylene group (Cy) to be). These are the same as E ³¹ , E ³² and E ³³ in the compound (1-3).

In the 1,4-phenylene group (Ph) and the trans-1,4-cyclohexylene group (Cy), the hydrogen atom bonded to the carbon atom in the group may be substituted with a fluorine atom, a chlorine atom or a methyl group.

The mass ratio of the monofunctional photopolymerizable liquid crystal (A) to the bifunctional photopolymerizable liquid crystal (B) in the composition (Y) is preferably 95/5 to 30/70, and particularly preferably 70/30 to 30/70.

The composition (Y) may contain known photopolymerization initiators (C), known surfactants (D), known solvents (E) or other optional components (B) in addition to the monofunctional photopolymerizable liquid crystal (A) ≪ / RTI >

Examples of the photopolymerization initiator (C) include oxime esters, benzophenones such as acetophenones, acylphosphine oxides, benzoins, benzyls, Michler's ketones, benzoin alkyl ethers and benzyl dimethyl ketal. One kind or two or more kinds may be appropriately selected and used from the above.

Examples of oxime esters include 1,2-octanedione, 1- [4- (phenylthio) -, 2- (ortho-benzoyloxime)], ethanone, 1- [ Benzoyl) -9H-carbazol-3-yl] -, 1- (ortho-acetyloxime).

Acetophenones include 2,2-dimethoxy-1,2-diphenylethan-1-one, 1 -hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy- 2-methyl-1-propan-1-one, 2-benzyl-2-dimethylamino- - (4-morpholinophenyl) -butanone-12- (dimethylamino) -2 - [(4- methylphenyl) methyl] Methyl-propan-1-one, 2-methyl-1 - ((2-hydroxy- Methyl-thiophenyl) -2-morpholinopropane-1-one, 2-hydroxy-1- {4- [4- (2- Methyl-propan-1-one, and the like.

Examples of acylphosphine oxides include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis (2,4,6-trimethylbenzoyl) -diphenyl-phosphine oxide.

Examples of the surfactant (D) include sodium lauryl sulfate, ammonium lauryl sulfate, triethanolamine lauryl sulfate, polyoxyethylene alkyl ether sulfate, alkyl ether phosphate, sodium oleyl succinate, potassium myristate, potassium cocoyl fatty acid, sodium Anionic surfactants such as lauroyl sarcosinate;

Nonionic surfactants such as polyethylene glycol monolaurate, stearic oxygen leitan, myristyl glyceryl, dioleate glyceryl, sorbitan stearate, and sorbitan oleate;

Cationic surfactants such as stearyltrimethylammonium chloride, behenyltrimethylammonium chloride, stearyldimethylbenzylammonium chloride, and cetyltrimethylammonium chloride;

Amphoteric surfactants such as alkyl betaines such as lauryl betaine, alkyl sulfobetaine, cocamide propyl betaine and alkyldimethyl amino acetic acid betaine, alkyl imidazoline, sodium lauroyl sarcosinate, sodium cocoamphopropanoate and the like, ;

Surfactants such as BYK-361, BYK-306, BYK-307 (manufactured by Big Chemical Japan), Fluorad FC430 (manufactured by Sumitomo 3M Ltd.), Megafac F171 and R08 (manufactured by Dainippon Ink and Chemicals, Incorporated); .

Any of these surfactants may be used alone, or two or more surfactants may be used in combination.

Examples of the solvent (E) include, but are not limited to, cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, 1-methoxy-2-propyl acetate, diethylene glycol dimethyl ether, ethylbenzene, ethylene glycol diethyl ether, Ethyl cellosolve, methyl-n-amyl ketone, propylene glycol monomethyl ether, toluene, methyl ethyl ketone, ethyl acetate, methanol, ethanol, isopropyl alcohol, butanol and isobutyl ketone. Either one of these solvents may be used alone, or two or more solvents may be used in combination.

Other optional components include antioxidants, ultraviolet absorbers, silane coupling agents, and light stabilizers.

The total amount of the monofunctional photopolymerizable liquid crystal (A) and the bifunctional photopolymerizable liquid crystal (B) in the composition (Y) in the composition (Y) is 80% by mass or more It is preferably less than 100% by mass, particularly preferably 90% by mass or more and less than 100% by mass.

[Optical compensation film]

The optical compensation film of the present invention is an optical compensation film (positive A plate) exhibiting positive uniaxial anisotropy, obtained by photo-curing a coating film of the photopolymerizable liquid crystal composition of the present invention.

The manufacturing process of the optical compensation film is described in the following formation of the optical compensation laminated film.

[Optical compensation laminated film]

The optical compensation laminated film of the present invention is obtained by laminating an optical compensation film (negative C plate) exhibiting negative uniaxial anisotropy and an optical compensation film (positive A plate) exhibiting positive uniaxial anisotropy according to the present invention.

In the optical compensation laminated film of the present invention, the order of lamination of the optical compensation film is not limited. An alignment film may be formed between the negative C plate and the positive A plate. That is, the optical compensation film of the present invention can form the optical compensation laminated film in any of the above-mentioned (ii) to (iv). Among them, from the viewpoint of thinning of the optical compensation laminated film, (iv), that is, the form in which the positive A plate is laminated directly on the negative C plate having the orientation is preferable.

(PI) or its precursor polyamic acid (PAA) is preferably used as the composition of the negative C plate forming material (hereinafter also referred to as the composition (X)) having the orientation property. Since the birefringence in the thickness direction is exhibited at the time of thermal imidization, the composition (X) preferably contains polyamic acid (PAA).

Here, the polyimide film basically has an orientation property. Therefore, preferably, among the polyimide (PI) or the polyamic acid (PAA) for forming an orientation film of the liquid crystal device, a material which becomes a negative C plate, that is, a material exhibiting birefringence in the thickness direction is selected.

Polyimides are obtained by polymerization of acid anhydrides with diamines. From the viewpoint of improving the light transmittance of the polyimide, it is preferable to have an alicyclic ring in the skeleton. In this case, an acid anhydride or diamine having an alicyclic ring in the skeleton may be selected.

When the acid anhydride has an alicyclic acid, examples of the acid anhydride include 1,2,3,4-butanetetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid 2 Anhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, 3,3 ', 4,4'-dicyclohexanetetracarboxylic acid dianhydride, and the like.

Examples of diamines include 2,2'-bis (trifluoromethyl) benzidine, p-phenylenediamine, and the like.

When the diamine has an alicyclic ring, examples of the acid anhydride include 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride, 2,3,3', 4'-biphenyltetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, and the like.

Examples of the diamine include trans-1,4-diaminocyclohexane, cis-1,4-diaminocyclohexane and 4,4'-diamino-1,1'-bicyclohexanoic acid.

The composition (X) may contain one or more known solvents, or one or more other optional components.

The content of the polyimide (PI) or the polyamic acid (PAA) is preferably 10 to 30 mass%, more preferably 10 to 15 mass%, with respect to the whole composition (X).

The step of forming the negative C plate having the orientation property is, for example, as follows.

(S1) of forming a first coating film by coating a composition (X) containing a polyamic acid (PAA) and a solvent on a substrate by a spin coating method or the like,

(S2) of removing the solvent in the first coating film by heat drying (prebaking) at about 150 deg. C, drying under reduced pressure, or drying under reduced pressure,

A step (S3) of firing (post-baking) the polyamic acid in the coating film at about 230 DEG C to form a polyimide film,

And a step (S4) of rubbing the polyimide film.

The process for forming the positive A plate is, for example, as follows.

The photopolymerizable liquid crystal composition (Y) of the present invention containing the monofunctional photopolymerizable liquid crystal (A) and the bifunctional photopolymerizable liquid crystal (B) is coated on the negative C plate to form the second coated film Step S5,

(S6) of removing the solvent in the second coating film by heating and drying (prebaking) at about 80 deg. C, drying under reduced pressure, or drying under reduced pressure,

And a step (S7) of irradiating the second coating film with light such as ultraviolet light (UV) to perform photopolymerization of the photopolymerizable liquid crystals (A) and (B).

Unreacted photopolymerizable liquid crystals (A) and (B) may be left only by light irradiation. In this case, after the step (S7), a step (S8) of baking at about 230 deg.

Examples of the application method in step (S5) include spin coating, micro gravure coating, die coating and the like.

As the step (S6) for removing the solvent, heat drying, vacuum drying, and heating and drying under reduced pressure are preferable.

The light source in the step S7 may be a low-pressure mercury lamp, a high-pressure mercury lamp, or a UV-LED. The wavelength of the irradiation light is 180 to 450 nm, preferably 250 to 400 nm, To 30000 mJ / cm2, preferably 1000 to 10000 mJ / cm2.

The optical compensation laminated film of the present invention is preferable for a liquid crystal device of a VA (Vertical Alignment) mode.

In the optical compensation laminated film, the retardation (Rth), which is an index of the retardation in the z direction, is preferably 100 to 500 nm, and particularly preferably 200 to 300 nm.

In the optically compensated laminated film, the retardation Rd, which is an index of the phase difference in the x-y plane, is preferably from 0 to 100 nm, more preferably from 40 to 60 nm.

Rth = P 占 da.

Where da is the thickness of the negative C plate and P = ((nx + ny) / 2 - nz).

Rd = (nx - ny) x db.

Where db is the thickness of the positive A plate.

The optical compensated laminated film in the present invention makes the base film unnecessary, so that it is possible to make the liquid crystal device thinner.

Particularly, in an optical compensation laminated film composed of a negative C plate having an orientation and a positive A plate laminated directly thereon, since an orientation film is not required in the optical compensation laminated film, further thinning can be achieved. In addition, if the number of films is small, the number of steps can be reduced, and the manufacturing cost can be reduced.

In the present invention, both the thicknesses of the negative C plate and the positive A plate, da and db, can be less than 10 mu m, and furthermore, 5 mu m or less. In particular, it is preferably 0.1 to 4.5 mu m. Therefore, the thickness d of the optical compensation laminated film can be made less than 20 탆, and further, 10 탆 or less.

In the optical compensation laminated film of the present invention, the average transmittance at a wavelength of 400 to 800 nm is preferably 80% or more, more preferably 85% or more, and further preferably 86 to 92%. In the present specification, the " average transmittance " is a value measured in accordance with JIS K 7361-1.

[Liquid crystal device]

A liquid crystal device according to one embodiment of the present invention is a color transmissive TFT liquid crystal device in VA mode.

This embodiment is also applicable to black and white liquid crystal devices.

The present embodiment is also applicable to a reflective or transflective liquid crystal device.

The present embodiment is also applicable to other active matrix type or passive matrix type such as a TFD liquid crystal device.

As shown in Fig. 1, the liquid crystal device 1 of the present embodiment includes a liquid crystal cell 1A, polarizers 51 and 52 mounted on the liquid crystal cell 1A, and a backlight BL.

The liquid crystal cell 1A includes a color filter substrate 10, a TFT substrate 20 as a counter substrate, and a liquid crystal layer 30 sandwiched between the pair of substrates.

A color filter substrate 10 (substrate for an electrode substrate and a liquid crystal device) 10 includes a transparent substrate 11, a black matrix layer BM sequentially stacked on the liquid crystal layer 30 side, a color filter layer CF, A laminate film 12, a common electrode 13, and an alignment film 14. [

The TFT substrate 20 includes a pixel electrode substrate 21 on which a plurality of pixel electrodes and a plurality of TFTs (thin film transistors), which are switching elements of the pixel electrodes, are formed in a matrix on the liquid crystal layer 30 side of the transparent substrate, And an alignment film 22 formed on the liquid crystal layer 30 side.

As the translucent substrate used for the color filter substrate 10 and the TFT substrate 20, a glass substrate is preferable.

In the transmissive liquid crystal device 1, a transparent conductive material such as ITO (indium tin oxide) is used as the material of the common electrode 13 and the pixel electrode.

The black matrix layer (BM) is a light shielding layer that shields light between adjacent dots.

The color filter layer CF includes, for example, red (R), green (G) and blue (B) colored layers. In this case, three pixel electrodes and three colored layers are formed in one pixel (one pixel = three dots).

The optical compensation laminated film 12 is the above-mentioned optical compensation laminated film of the present invention and is a laminated film of a negative C plate 12A and a positive A plate 12B as shown in Fig.

In this embodiment, the common electrode 13 is formed directly on the optical compensation laminated film 12, and the alignment film 14 is formed thereon.

The lamination structure of the color filter substrate 10 can be suitably changed in design.

For example, as shown in the color filter substrate 40, the liquid crystal cell 2A and the liquid crystal device 2 of the design modification shown in Fig. 2, the optical compensation laminated film 12, The black matrix layer BM, the color filter layer CF, the common electrode 13, and the alignment film 14 may be sequentially formed.

The color filter substrate (electrode substrate, substrate for a liquid crystal device) 10 and the liquid crystal device 1 of the present embodiment have good optical characteristics and adhesion to each other. Since the color filter substrate 10 and the liquid crystal device 1 of the present embodiment are provided with the optical compensation laminated film 12 in the liquid crystal cell 1A, it is possible to reduce the thickness and cost.

Example

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. Example 11 is an example, and Example 21 is a comparative example.

(Preparation of coating liquid (Y1) for positive A plate)

(A1), the following compound (A2) in an amount of 47.7% by mass, the following compound (B1) as a bifunctional photopolymerizable liquid crystal in an amount of 29.4% by mass, a photopolymerization initiator (C1) (Irgacure907 , BASF Co., Ltd.) in an amount of 1.3% by mass and a surfactant (D1) (Surplon S382, manufactured by AGC Seiyaku Chemical Co., Ltd.) in an amount of 0.7% by mass. Thereafter, the solvent (E1) (cyclopentanone) was added and mixed so that the total concentration of the components (A1), (A2), (B1), (C1) and (D1) relative to the entire coating liquid (100 mass% Was 15% by mass. This was filtered with a filter having an opening diameter of 0.5 mu m to obtain a coating liquid (Y1).

(2)

(Preparation of Coating Solution (Z1) for Positive A Plate)

, 97.1% by mass of the following compound (B2) as the bifunctional photopolymerizable liquid crystal, 1.9% by mass of the photopolymerization initiator (C1) and 1.0% by mass of the surfactant (D1) were respectively weighed and mixed. Thereafter, the solvent (E1) was added and mixed to obtain a solution having a concentration of components (B2), (C1) and (D1) of 15% by mass with respect to the entire coating liquid (100% by mass). This was filtered with a filter having an opening diameter of 0.5 mu m to obtain a coating liquid (Z1).

(3)

(Preparation of Negative C plate (NCP1)) [

1.14 g of trans-1,4-diaminocyclohexane was dissolved in 17.44 g of N-methyl-2-pyrrolidone, and 2.83 g of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and N -Methyl-2-pyrrolidone (4.00 g), and the mixture was stirred at 60 占 폚 for 3 hours. Further, 0.12 g of phthalic anhydride was added, followed by stirring at 60 ° C for 3 hours to obtain a solution of polyamic acid (PAA1). This was filtered through a filter having an opening diameter of 0.5 mu m to obtain a coating liquid (X1). The coating liquid was coated on a glass substrate by a spin coater (3000 rpm, 30 sec) and dried on a hot plate at 90 캜 for 2 minutes. Further, after heating at 230 占 폚 for 30 minutes, rubbing treatment was performed to produce a negative C plate (NCP1) having the function of an alignment film. The film thickness was 3.1 mu m, the birefringence P at 589 nm in the thickness direction was 0.090, and Rth = 279 nm.

(Production of optical compensation laminated film)

<Example 11>

On the negative C plate (NCP1), the coating liquid (Y1) was coated with a spin coater and dried at 80 DEG C for 2 minutes to align the alignment. Thereafter, ultraviolet rays were irradiated from the direction perpendicular to the substrate surface for 30 seconds to cure the coating film. The illuminance of the high-pressure mercury lamp used for photo-curing was 40 mW / cm 2 at a wavelength of 365 nm. And further baked at a temperature of 230 DEG C for 30 minutes to obtain an optical compensation laminated film.

<Example 21>

An optical compensated laminated film was obtained in the same manner as in Example 1 except that the coating liquid (Z1) was used instead of the coating liquid (Y1).

(Evaluation of optical compensated laminated film)

&Lt; Tape peeling test &

In each of the examples described above, a tape peeling test was performed in which an adhesive tape having an adhesive strength of 0.25 N / mm was attached to the surface of the obtained optical compensation laminated film, and then peeled off slowly. Evaluation was carried out based on the following criteria. ?: No adherence to the adhesive tape,?: Adhesion of the A plate component to the adhesive tape.

(Evaluation result of optical compensated laminated film)

Table 1 shows the main production conditions and evaluation results in each of the examples. In Table 1,% is mass%.

In Example 11 in which the monofunctional photopolymerizable liquid crystal (A) and the bifunctional photopolymerizable liquid crystal (B) were used in combination as the photopolymerizable liquid crystal of the positive A plate, there was no adherence to the adhesive tape in the tape peeling test and the negative C plate and the positive A The adhesion of the plate was good.

In Example 21 using only the bifunctional photopolymerizable liquid crystal (B) as the photopolymerizable liquid crystal of the positive A plate, adherence was observed on the adhesive tape in the tape peeling test, and the adhesion between the negative C plate and the positive A plate was poor.

Industrial availability

The optical compensation film and the optical compensation laminated film obtained from the photopolymerizable liquid crystal composition of the present invention can be used as a thin-type electrode substrate, a substrate for a liquid crystal device, and a liquid crystal device which are excellent in sputtering resistance, heat resistance and adhesion, low in cost, It is available.

The entire contents of the specification, claims, drawings and summary of Japanese Patent Application No. 2012-245073 filed on November 7, 2012 are hereby incorporated herein by reference and the disclosure of the specification of the present invention.

1, 2: liquid crystal device
1A, 2A: liquid crystal cell
10, 40: Color filter substrate (electrode substrate, substrate for liquid crystal device)
11: Transparent substrate
12: Optical compensation laminated film
12A: Negative C plate (optical compensation film showing negative uniaxial anisotropy)
12B: Positive A plate (optical compensation film showing positive uniaxial anisotropy)
13: common electrode
14:
20: TFT substrate
21: pixel electrode substrate
22: Orientation film
30: liquid crystal layer
51, 52: Polarizer
BM: Black Matrix
CF: color filter
BL: Backlight

Claims (15)

1. A photopolymerizable liquid crystal composition for forming an optical compensation film exhibiting positive uniaxial anisotropy,
A photopolymerizable liquid crystal composition comprising a monofunctional photopolymerizable liquid crystal (A) having one photopolymerizable reactive group and a bifunctional photopolymerizable liquid crystal (B) having two photopolymerizable reactive groups. The method according to claim 1,
Wherein said monofunctional photopolymerizable liquid crystal (A) and said bifunctional photopolymerizable liquid crystal (B) have a mass ratio of 95/5 to 30/70. 3. The method according to claim 1 or 2,
The monofunctional photopolymerizable liquid crystal (A) is represented by the following formula (1-1).
^{_{CH 2 = CR 11 -COO- (E}} 11) m1 -Cy-Y 1 -Cy-E 12 -R 12 ... (1-1)
(Wherein R ^{11 is a} hydrogen atom or a methyl group, R ¹² is an alkyl group having 1 to 8 carbon atoms, Y ^{1 is} -OCO- or -COO-, m ^{1 is} 0 or 1. E ¹¹ and E ¹² are each independently 1,4 A phenylene group or a trans-1,4-cyclohexylene group, Cy: a trans-1,4-cyclohexylene group, provided that the 1,4- A hydrogen atom in the group may be substituted with a fluorine atom, a chlorine atom or a methyl group. 3. The method according to claim 1 or 2,
The monofunctional photopolymerizable liquid crystal (A) is represented by the following formula (1-2).
CH ₂ = CR ²¹ -COO- (L 2) _{k 2} -E ²¹ -E ²² -E ²³ -E ²⁴ -R ²² (1-2)
(Where, R ^21: a hydrogen atom or a methyl group, R ^22: an alkyl group or a fluorine atom k2 having a carbon number of 1-8: 0 or 1. L2: -.. (CH 2) p2 O- or - (CH _{2) q2} - (where , p2 and q2 are each independently an integer of ^{2 ~ 8) E 21:.} . 1,4- phenylene group, E ^22, E ²³ and E ^24:. each independently a 1,4-phenylene group or trans-1,4 -Cyclohexylene group, and at least one of E ²² and E ²³ is a trans-1,4-cyclohexylene group, provided that the 1,4-phenylene group and the trans-1,4-cyclohexylene group are , The hydrogen atom bonded to the carbon atom in the group may be substituted with a fluorine atom, a chlorine atom or a methyl group.) 3. The method according to claim 1 or 2,
The monofunctional photopolymerizable liquid crystal (A) is represented by the following formula (1-3).
^{_{CH 2 = CR 31 -COO- (L3}} ) k3 -E 31 -E 32 -E 33 -R 32 ... (1-3)
(Wherein R ^{31 is a} hydrogen atom or a methyl group, R ³² is an alkyl group having 1 to 8 carbon atoms, k ₃ is 0 or 1. L ₃ is - (CH ₂ ) p ₃ O-, -Cy-COO- . 4-cyclohexylene group), or -Cy-OCO- (However, p3 is an integer of ^{2 ~ 8) E 31, E} 32 and E ^33:.. each independently represent a 1,4-phenylene group or trans -1 , 4-cyclohexylene group (where, E ^31, E ³² and E ³³ at least one of trans-1,4-cyclohexylene group, and E ³¹ also in the case where L3 is -Cy-OCO- trans 1,4-cyclohexylene group and, L3 is - and (CH _{2) p3} O- or k3 or each of E ³¹ and E ^33, where 0 is a 1,4-phenylene group, E ³² is trans- Cyclohexylene group). However, the 1,4-phenylene group and the trans-1,4-cyclohexylene group are groups in which the hydrogen atom bonded to the carbon atom in the group is a fluorine atom, a chlorine atom, or a methyl group And may be substituted.) 6. The method according to any one of claims 1 to 5,
The bifunctional photopolymerizable liquid crystal (B) is represented by the following formula (2).
Q ¹ -Z ¹ -A ¹ -Z ³ -MZ ⁴ -A ² -Z ² -Q ² ... (2)
(Wherein Q ¹ and Q ² are each independently a photopolymerizable reactive group, Z ¹ , Z ² , Z ³ and Z ⁴ are each independently a single bond or a divalent linking group, A ¹ and A ² : Spacer group of 2 to 20 M: Mesogenic group.) The method according to claim 6,
The bifunctional photopolymerizable liquid crystal (B) is represented by the following formula (2-1).
^{_{CH 2 = CR 41 -COO- (E}} 41) m4 -Cy-Y 4 -Cy- (E 42) n4 -OOC-CR 42 = CH 2 ... (2-1)
(Wherein R ⁴¹ and R ⁴² are each independently a hydrogen atom or a methyl group, Y ^{4 is} -OCO- or -COO-, m ⁴ and n ⁴ are each independently 0 or 1. E ⁴¹ and E ⁴² are each independently 1, A 4-phenylene group or a trans-1,4-cyclohexylene group, Cy: a trans-1,4-cyclohexylene group, provided that the 1,4-phenylene group and the trans- , The hydrogen atom in the group may be substituted with a fluorine atom, a chlorine atom or a methyl group. The method according to claim 6,
The bifunctional photopolymerizable liquid crystal (B) is represented by the following formula (2-2).
^{_{CH 2 = CR 51 -COO- (L5}} ) k5 -E 51 -E 52 -E 53 -E 54 - (M5) n5 -OOC-CR 52 = CH 2 ... (2-2)
(Where, R ⁵¹ and R ^52: each independently represent a hydrogen atom or a methyl group and k5 n5: each independently 0 or 1. L5 and M5:. Are each independently - (CH _{2) p5} O- or - (CH _{2) q5} - (wherein each of p5 and q5 is independently an integer of 2 to 8.) E ⁵¹ : 1,4-phenylene group E ⁵² , E ⁵³ and E ⁵⁴ : each independently 1,4-phenylene group or trans- Cyclohexylene group, and at least one of E ⁵² and E ⁵³ is a trans-1,4-cyclohexylene group, provided that the 1,4-phenylene group and the trans-1,4-cyclo In the hexylene group, the hydrogen atom bonded to the carbon atom in the group may be substituted with a fluorine atom, a chlorine atom or a methyl group.) The method according to claim 6,
The bifunctional photopolymerizable liquid crystal (B) is represented by the following formula (2-3).
^{_{CH 2 = CR 61 -COO- (L6}} ) k 6 -E 61 -E 62 -E 63 - (M6) n6 -COO-CR 62 = CH 2 ... (2-3)
(Where, R ⁶¹ and R ^62: each independently represent a hydrogen atom or a methyl group and k6 n6: each independently 0 or 1. L6 and M6:. Are each independently _{- (CH 2) p6 O-,} -Cy-COO- ( Cy is a trans-1,4-cyclohexylene group), or -Cy-OCO- (wherein p6 is an integer of 2 to 8) E ⁶¹ , E ⁶² and E ⁶³ : A phenylene group or a trans-1,4-cyclohexylene group (provided that at least one of E ⁶¹ , E ⁶² and E ⁶³ is a trans-1,4-cyclohexylene group and L 6 is -Cy-OCO- in the case of E ⁶¹ are trans-1,4-cyclohexylene group and, L6 is - (CH ₂₎ each of E ⁶¹ and E ⁶³ when the _p6 or O-, or k6 is 0, 1,4-phenylene group And E ⁶² is a trans-1,4-cyclohexylene group.) However, the 1,4-phenylene group and the trans-1,4-cyclohexylene group are groups in which the hydrogen atom bonded to the carbon atom in the group is fluorine An atom, a chlorine atom or a methyl group. An optical compensation film exhibiting positive uniaxial anisotropy, obtained by photo-curing a coating film of the photopolymerizable liquid crystal composition according to any one of claims 1 to 9. An optical compensation laminated film comprising an optical compensation film exhibiting negative uniaxial anisotropy and an optical compensation film exhibiting positive uniaxial anisotropy according to claim 10. 12. The method of claim 11,
Wherein the optical compensation film exhibiting negative uniaxial anisotropy contains polyimide having alicyclic structure on its backbone. An electrode substrate having the optical compensation laminate film according to claim 12 and an electrode formed on the optical compensation laminate film on a substrate. A substrate for a liquid crystal device having the electrode substrate according to claim 13 and an alignment film formed on the electrode substrate. A liquid crystal device comprising the liquid crystal substrate according to claim 14, an opposing substrate, and a liquid crystal layer sandwiched between the liquid crystal substrate and the opposing substrate.

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