JP2006276203A - Retardation plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a retardation plate with fewer defects caused to orientation defects by using a new discotic liquid crystal compound. <P>SOLUTION: The retardation plate has on a transparent supporting body an orientation film and an optical anisotropic layer formed by a chemical compound represented by a general formula (DI) of at least one layer and has a characteristic that a major axial direction of a rod-like liquid crystal can be oriented in a direction almost at right angles to a rubbing direction when the rod-like liquid crystal is oriented. Here, Y11, Y12, and Y13 represent in the general formula (DI) a methine or nitrogen atom independently of one another. L1, L2, and L3 represent a single bond or bivalent linking group independently of one another. H1, H2, and H3 represent a general formula (DI-A) (in which YA1 and YA2 represent methine or nitrogen atom independently of each other; XA represents an oxygen atom, sulfur atom, methylene, or imino; * represents a position to be bonded to L1 to L3; and ** represents a position to be bonded to R1 to R3) or a general formula (DI-B) (in which YB1 and YB2 represent the methine or nitrogen atom independently of each other; XB represents an oxygen atom, sulfur atom, methylene, or imino; * represents a position to be bonded to L1 to L3; and ** represents a position to be bonded to R1 to R3). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a retardation plate formed from a discotic liquid crystalline compound.

  A liquid crystal display device is usually provided with a first polarizing plate and a second polarizing plate with a liquid crystal cell interposed therebetween, and the liquid crystal cell has a liquid crystal layer containing a rod-like liquid crystal between a pair of substrates. A phase difference generated in a liquid crystal cell using a rod-like liquid crystal is changed to a discotic compound (for example, 2,3,6,7,10,11-hexa {4- (4-acryloyloxyhexyloxy) benzoyloxy} triphenylene). In the case of canceling with an optical compensation sheet having an optically anisotropic layer formed from (for example, Patent Document 1), since the wavelength dispersibility of the rod-like liquid crystal and the discotic compound is different, the phase difference is simultaneously obtained for all light wavelengths. Cannot be offset and discoloration (black color does not appear) occurs.

  A trisubstituted benzene having a heterocyclic group has been reported (Non-patent Document 1). It is not easy to achieve a low wavelength dispersion by using this compound, and a compound having a smaller wavelength dispersion (Re (short wavelength (for example, 450 nm)) / Re (long wavelength (for example, 650 nm)) is small) Is desired.

  The retardation (Δnd) of the optical compensation sheet needs to be determined according to the optical properties of the liquid crystal cell to be compensated. Here, retardation (Δnd) is the product of the refractive index anisotropy (Δn) of the optically anisotropic layer and the thickness (d) of the optically anisotropic layer. If the refractive index anisotropy (Δn) of the optically anisotropic layer is large, the liquid crystal cell can be compensated even if the layer thickness (d) is small. On the other hand, when the refractive index anisotropy (Δn) becomes small, it is necessary to increase the thickness (d) of the layer, and as a result, there arises a problem that defects in the alignment of the liquid crystalline compound are likely to occur.

  In the conventional alignment film, for example, when the rubbing process is continuously performed with a rubbing cloth, the rubbing cloth is formed at the start point and the end point of the rubbing (one end portion and the other end portion of the long film). The rubbing strength changes due to wear or the like. Therefore, the alignment control ability of the alignment film becomes non-uniform, and depending on the region, it becomes impossible to control the alignment of the liquid crystal compound applied thereon to a desired alignment state. For example, alignment defects (brightness in the optical anisotropic layer) There is a problem that the number of points increases. In the case where an optically anisotropic layer is continuously formed on a long film, an alignment film that contributes to stably producing an optically anisotropic layer with few alignment defects is disclosed (Patent Document 2). ).

JP-A-8-50206 JP 2002-98828 A Molecular Crystals and Liquid Crystals, 2001, 370, 391

An object of the present invention is to provide a retardation plate using an alignment film capable of stably producing an optically anisotropic layer formed by fixing a novel liquid crystal compound in an aligned state.
Another object of the present invention is to provide a retardation plate with few defects due to alignment defects of liquid crystals.

According to the present invention, the following retardation plate is provided to achieve the above object.
1. A retardation plate having an alignment film and an optically anisotropic layer formed of at least one layer of a compound represented by the following general formula (DI) on a transparent support, the alignment film comprising: A retardation film characterized by having a characteristic that a major axis direction of a rod-like liquid crystal can be oriented in a direction substantially orthogonal to a rubbing direction when the rod-like liquid crystal is oriented.
General formula (DI)

In formula (DI), Y ₁₁ , Y ₁₂ and Y ₁₃ each independently represent a methine or nitrogen atom. L ₁ , L ₂ and L ₃ each independently represents a single bond or a divalent linking group. To H _1, H _2, H ₃ each independently represent the following general formula (DI-A) or the following general formula (DI-B).
General formula (DI-A)

[YA ₁ and YA ₂ each independently represents a methine group or a nitrogen atom. XA represents an oxygen atom, a sulfur atom, methylene or imino. * Represents a position where L _{1 to} L ₃ are bonded, and ** represents a position where R _{1 to} R ₃ are bonded. ]
General formula (DI-B)

[YB ₁ and YB ₂ each independently represent a methine group or a nitrogen atom. XB represents an oxygen atom, a sulfur atom, methylene, or imino. * Represents a position where L _{1 to} L ₃ are bonded, and ** represents a position where R _{1 to} R ₃ are bonded. ]
In general formula (DI), R < ₁ >, R < ₂ >, R < ₃ > represents the following general formula (DI-R) each independently.
Formula (DI-R): * - (- L 21 - divalent cyclic group) _n1 -L ₂₂ -L ₂₃ -Q1
[* Represents a position bonded to a 5-membered ring in the general formula (DI). L ₂₁ represents a single bond or a divalent linking group, and the divalent cyclic group represents a divalent linking group having at least one cyclic structure. n1 represents an integer of 0 to 4. L ₂₂ is * —O—, * —O—CO—, * —CO—O—, * —O—CO—O—, * —S—, * —N (R) H—, * —SO ₂ —. , * —CH ₂ —, * —CH═CH—, * —C≡C— (wherein, * represents a position bonded to a benzene ring in formula (DI-R)), In the formula (DI-R), L ₂₃ represents —O—, —S—, —C (═O) —, —SO ₂ —, —NH—, —CH ₂ —, —CH═CH—, —C≡. C— represents a divalent linking group selected from the group consisting of these and combinations thereof. When the above group is a group containing a hydrogen atom, the hydrogen atom may be replaced with a substituent. Q ₁ each independently represents a polymerizable group or a hydrogen atom. ]
2. A retardation plate having, on a transparent support, an alignment film and at least one optically anisotropic layer formed from the compound represented by the general formula (DI) described in 1 above, The alignment film is an acrylic acid copolymer or a methacrylic acid copolymer containing a repeating unit represented by the following general formula (I) and a repeating unit represented by the following general formula (II) or (III): A phase difference plate.

In general formulas (I) to (III):
R ₁ and R ₂ are each independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms; M is a proton, an alkali metal ion or an ammonium ion; L0 is —O— , -CO -, - NH -, - SO 2 -, an alkylene group, an alkenylene group, a divalent linking group selected from the group consisting of arylene groups and combinations thereof; R ₀ is the number of carbon atoms is 10 to 100 is a hydrocarbon group or a fluorine atom-substituted hydrocarbon group having 1 to 100 carbon atoms; Cy is an aliphatic ring group, an aromatic group or a heterocyclic group; m is 10 to 99 mol% Yes; and n is from 1 to 90 mol%.
3. A retardation plate having an alignment film and an optically anisotropic layer formed of at least one compound represented by the general formula (DI) described in 1 above on a transparent support, The alignment film is an alignment film including a polymer having at least one structural unit represented by any one of the following general formula (I-TH), general formula (II-TH), and general formula (III-TH). A retardation film characterized by that.

General formula (I-TH)

(Wherein R ¹ represents a hydrogen atom, a methyl group, a halogen atom or a cyano group, P ¹ represents an oxygen atom, —CO— or —NR ¹² —, and R ¹² represents a hydrogen atom or a substituted or unsubstituted carbon. Represents an alkyl group having 1 to 6 atoms, and L1 is a substituted or unsubstituted alkylene group, divalent cycloaliphatic group, divalent aromatic group, divalent heterocyclic group and combinations thereof. A divalent linking group selected from the group consisting of X ¹ represents a hydrogen bonding group, and n 1 represents an integer of 1 to 3.)

General formula (II-TH)

(In the formula, R ² represents a hydrogen atom, a methyl group, a halogen atom or a cyano group, L ²¹ represents a substituted or unsubstituted divalent aromatic group or divalent heterocyclic group, and P ²¹ represents a single atom. Represents a bond or a divalent linking group selected from the group consisting of —O—, —NR ²¹ —, —CO—, —S—, —SO—, —SO ₂ — and combinations thereof, and R ²¹ represents hydrogen. Represents an atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and L ²² represents a substituted or unsubstituted alkylene group, divalent cycloaliphatic group, divalent aromatic group, divalent group A divalent linking group selected from the group consisting of a heterocyclic group and a combination thereof is represented, X ² represents a hydrogen bonding group, and n2 is an integer of 0 to ^3. )

General formula (III-TH)

(In the formula, L ³¹ represents a substituted or unsubstituted divalent aromatic group or divalent heterocyclic group, and P ³¹ represents a single bond, —O—, —NR ³¹ —, —CO—, — Represents a divalent linking group selected from the group consisting of S—, —SO—, —SO ₂ — and combinations thereof, and R ³¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. L ³² represents a substituted or unsubstituted divalent linkage selected from the group consisting of an alkylene group, a divalent cycloaliphatic group, a divalent aromatic group, a divalent heterocyclic group, and combinations thereof. Represents a group, X ³ represents a hydrogen bonding group, and n3 is an integer of 0 to ^3. )
4). 4. The phase difference plate according to any one of the above 1, 2 and 3, wherein the optically anisotropic layer is formed from a liquid crystal compound with hybrid alignment.

  ADVANTAGE OF THE INVENTION According to this invention, the phase difference plate with few defects resulting from an alignment defect can be provided using a novel discotic liquid crystal compound.

Hereinafter, the retardation plate of the present invention will be sequentially described.
[Compound represented by the general formula (DI)]
The compound represented by the general formula (DI) used in the present invention preferably exhibits discotic liquid crystallinity, and particularly preferably exhibits a discotic nematic phase.

General formula (DI)

In general formula (DI), Y ₁₁ , Y ₁₂ , and Y ₁₃ each independently represent a methine or nitrogen atom.

When Y ₁₁ , Y ₁₂ , and Y ₁₃ are methine, the methine may have a substituent. Examples of methine substituents include alkyl groups, alkoxy groups, aryloxy groups, acyl groups, alkoxycarbonyl groups, acyloxy groups, acylamino groups, alkoxycarbonylamino groups, alkylthio groups, arylthio groups, halogen atoms, and cyano groups. be able to. Among these, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an acyloxy group, a halogen atom and a cyano group are more preferable, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and a carbon number of Most preferred are 2 to 12 alkoxycarbonyl groups, 2 to 12 acyloxy groups, halogen atoms and cyano groups.

Y ₁₁ , Y ₁₂ and Y ₁₃ are most preferably all methine, and methine is most preferably unsubstituted.

In the general formula (DI), L ₁ , L ₂ and L ₃ are each independently a single bond or a divalent linking group. When L ₁ , L ₂ , and L ₃ are divalent linking groups, each independently represents —O—, —S—, —C (═O) —, —NH—, —SO ₂ —, —CH═CH. A divalent linking group selected from the group consisting of — and —C≡C— and combinations thereof is preferred. When the above group is a group containing a hydrogen atom, the hydrogen atom may be replaced with a substituent. Examples of such a substituent include a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms, an alkyl group substituted with a halogen having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. , An acyl group having 2 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, an acyloxy group having 2 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, a carbamoyl group, and 2 to 2 carbon atoms Preferred examples include a carbamoyl group substituted with 6 alkyls and an acylamino group having 2 to 6 carbon atoms, and a halogen atom and an alkyl group having 1 to 6 carbon atoms are more preferred.

The divalent cyclic group represented by L ₁ , L ₂ , and L ₃ is a divalent linking group having at least one cyclic structure. The divalent cyclic group is preferably a 5-membered ring, 6-membered ring, or 7-membered ring, more preferably a 5-membered ring or 6-membered ring, and most preferably a 6-membered ring. The ring contained in the cyclic group may be a condensed ring. However, it is more preferably a monocycle than a condensed ring. The ring contained in the cyclic group may be any of an aromatic ring, an aliphatic ring, and a heterocyclic ring. Examples of the aromatic ring include a benzene ring and a naphthalene ring. Examples of the aliphatic ring include a cyclohexane ring. Examples of the heterocyclic ring include a pyridine ring and a pyrimidine ring. The cyclic group is preferably an aromatic ring or a heterocyclic ring.

Of the divalent cyclic groups represented by L ₁ , L ₂ and L ₃ , 1,4-phenylene is preferred as the cyclic group having a benzene ring. As the cyclic group having a naphthalene ring, naphthalene-1,5-diyl and naphthalene-2,6-diyl are preferable. The cyclic group having a cyclohexane ring is preferably 1,4-cyclohexylene. As the cyclic group having a pyridine ring, pyridine-2,5-diyl is preferable. The cyclic group having a pyrimidine ring is preferably pyrimidine-2,5-diyl.

The divalent cyclic group represented by L ₁ , L ₂ and L ₃ may have a substituent. Examples of the substituent include a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 16 carbon atoms, an alkenyl group having 1 to 16 carbon atoms, an alkynyl group having 1 to 16 carbon atoms, carbon A halogen-substituted alkyl group having 1 to 16 atoms, an alkoxy group having 1 to 16 carbon atoms, an acyl group having 2 to 16 carbon atoms, an alkylthio group having 1 to 16 carbon atoms, and 2 carbon atoms And an acyloxy group having 2 to 16 carbon atoms, an alkoxycarbonyl group having 2 to 16 carbon atoms, a carbamoyl group, an alkyl-substituted carbamoyl group having 2 to 16 carbon atoms, and an acylamino group having 2 to 16 carbon atoms.

L ₁ , L ₂ , and L ₃ are each a single bond, * —O—CO—, * —CO—O—, * —CH═CH—, * —C≡C—, * —divalent cyclic group— * -O-CO-divalent cyclic group-, * -CO-O-divalent cyclic group-, * -CH = CH-divalent cyclic group-, * -C≡C-divalent cyclic group Group-, * -divalent cyclic group-O-CO-, * -divalent cyclic group-CO-O-, * -divalent cyclic group-CH = CH-, * -divalent cyclic group- C≡C— is preferred. In particular, a single bond, * —CH═CH—, * —C≡C—, * —CH═CH—a divalent cyclic group—, * —C≡C—a divalent cyclic group— is preferable, and a single bond is Most preferred. (Here, * represents a position bonded to a 6-membered ring containing Y ₁₁ , Y ₁₂ and Y ₁₃ in the general formula (DI).)

To H _1, H _2, H ₃ each independently represent the following general formula (DI-A) or the following general formula (DI-B).

General formula (DI-A)

In general formula (DI-A), YA < ₁ > and YA < ₂ > represent a methine or a nitrogen atom each independently. As YA ₁ and YA ₂ , at least one is preferably a nitrogen atom, and most preferably both are nitrogen atoms. XA represents an oxygen atom, a sulfur atom, methylene or imino. XA is most preferably an oxygen atom. * Represents a position where L _{1 to} L ₃ are bonded, and ** represents a position where R _{1 to} R ₃ are bonded.

General formula (DI-B)

In the general formula (DI-B), YB ₁ and YB ₂ each independently represent a methine or nitrogen atom. As YB ₁ and YB ₂ , at least one is preferably a nitrogen atom, and most preferably both are nitrogen atoms. XB represents an oxygen atom, a sulfur atom, methylene, or imino. XB is most preferably an oxygen atom. * Represents a position where L _{1 to} L ₃ are bonded, and ** represents a position where R _{1 to} R ₃ are bonded.

R ₁ , R ₂ and R ₃ each independently represents the following general formula (DI-R).

General formula (DI-R): *-(-L ₂₁ -divalent cyclic group) n1-L ₂₂ -L ₂₃ -Q ₁

  In the general formula (DI-R), * represents a position bonded to the 5-membered ring in the general formula (DI).

L ₂₁ is a single bond or a divalent linking group. When L ₂₁ is a divalent linking group, —O—, —S—, —C (═O) —, —NH—, —SO ₂ —, —CH═CH— and —C≡C— and these A divalent linking group selected from the group consisting of combinations is preferred. When the above group is a group containing a hydrogen atom, the hydrogen atom may be replaced with a substituent. Examples of such a substituent include a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms, an alkyl group substituted with a halogen having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. , An acyl group having 2 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, an acyloxy group having 2 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, a carbamoyl group, and 2 to 2 carbon atoms Preferred examples include a carbamoyl group substituted with 6 alkyls and an acylamino group having 2 to 6 carbon atoms, and a halogen atom and an alkyl group having 1 to 6 carbon atoms are more preferred.

L ₂₁ represents a single bond, and ** — O—CO—, ** — CO—O—, ** — CH═CH—, ** — C≡C— (where ** represents a general formula (DI indicates the left side of L ₂₁ in -R)) are preferred. A single bond is particularly preferable.

  The divalent cyclic group in the general formula (DI-R) is a divalent linking group having at least one cyclic structure. The divalent cyclic group is preferably a 5-membered ring, 6-membered ring, or 7-membered ring, more preferably a 5-membered ring or 6-membered ring, and most preferably a 6-membered ring. The ring contained in the cyclic group may be a condensed ring. However, it is more preferably a monocycle than a condensed ring. The ring contained in the cyclic group may be any of an aromatic ring, an aliphatic ring, and a heterocyclic ring. Examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring. Examples of the aliphatic ring include a cyclohexane ring. Examples of the heterocyclic ring include a pyridine ring and a pyrimidine ring.

  Of the divalent cyclic groups, 1,4-phenylene and 1,3-phenylene are preferred as the cyclic group having a benzene ring. Examples of the cyclic group having a naphthalene ring include naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-2,5-diyl, and naphthalene-2,6-diylnaphthalene. -2,7-diyl is preferred. The cyclic group having a cyclohexane ring is preferably 1,4-cyclohexylene. As the cyclic group having a pyridine ring, pyridine-2,5-diyl is preferable. The cyclic group having a pyrimidine ring is preferably pyrimidine-2,5-diyl. As the divalent cyclic group, 1,4-phenylene, 1,3-phenylene and naphthalene-2,6-diyl are particularly preferable.

  The divalent cyclic group may have a substituent. Examples of the substituent include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a cyano group, a nitro group, an alkyl group having 1 to 16 carbon atoms, and an alkenyl group having 1 to 16 carbon atoms. , An alkynyl group having 1 to 16 carbon atoms, a halogen-substituted alkyl group having 1 to 16 carbon atoms, an alkoxy group having 1 to 16 carbon atoms, an acyl group having 2 to 16 carbon atoms, and the number of carbon atoms Is an alkylthio group having 1 to 16 carbon atoms, an acyloxy group having 2 to 16 carbon atoms, an alkoxycarbonyl group having 2 to 16 carbon atoms, a carbamoyl group, an alkyl-substituted carbamoyl group having 2 to 16 carbon atoms, and the number of carbon atoms Includes 2 to 16 acylamino groups. As the substituent of the divalent cyclic group, a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, and a halogen-substituted alkyl group having 1 to 6 carbon atoms are preferable, and further, a halogen atom or a carbon atom An alkyl group having 1 to 4 carbon atoms and a halogen-substituted alkyl group having 1 to 4 carbon atoms are preferable. In particular, a halogen atom, an alkyl group having 1 to 3 carbon atoms, and a trifluoromethyl group are preferable.

  n1 represents an integer of 0 to 4. n1 is preferably an integer of 1 to 3. In particular, 1 or 2 is preferable.

L ₂₂ is * -O-, * -O-CO-, * -CO-O-, * -O-CO-O-, * -S-, * -N (R) H-, * -SO _{2. -, * - CH 2 -,} * - CH = CH -, * - C≡C-, are expressed (here, * represents a formula (DI-R) position bonding to the benzene ring in.). Preferably, * —O—, * —O—CO—, * —CO—O—, * —O—CO—O—, * —CH ₂ —, * —CH═CH—, * —C≡C— In particular, * —O—, * —O—CO—, * —O—CO—O—, and * —CH ₂ — are preferable. When the above group is a group containing a hydrogen atom, the hydrogen atom may be replaced with a substituent. Examples of such a substituent include a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms, an alkyl group substituted with a halogen having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. , An acyl group having 2 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, an acyloxy group having 2 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, a carbamoyl group, and 2 to 2 carbon atoms Preferred examples include a carbamoyl group substituted with 6 alkyls and an acylamino group having 2 to 6 carbon atoms, and a halogen atom and an alkyl group having 1 to 6 carbon atoms are more preferred.

L ₂₃ consists of —O—, —S—, —C (═O) —, —SO ₂ —, —NH—, —CH ₂ —, —CH═CH—, —C≡C— and combinations thereof. A divalent linking group selected from the group; Here, the hydrogen atoms of —NH—, —CH ₂ —, and —CH═CH— may be replaced with other substituents. Examples of other substituents include halogen atoms, cyano groups, nitro groups, alkyl groups having 1 to 6 carbon atoms, halogen-substituted alkyl groups having 1 to 6 carbon atoms, and 1 to 6 carbon atoms. Alkoxy group, acyl group having 2 to 6 carbon atoms, alkylthio group having 1 to 6 carbon atoms, acyloxy group having 2 to 6 carbon atoms, alkoxycarbonyl group having 2 to 6 carbon atoms, carbamoyl group , An alkyl-substituted carbamoyl group having 2 to 6 carbon atoms and an acylamino group having 2 to 6 carbon atoms. In particular, a halogen atom and an alkyl group having 1 to 6 carbon atoms are preferable. By substituting with these substituents, when preparing a liquid crystalline composition from the liquid crystalline compound of the present invention, solubility in a solvent to be used can be improved.

L ₂₃ preferably comprises a combination of —O—, —C (═O) —, —CH ₂ —, —CH═CH—, —C≡C—. L23 preferably contains 1 to 20 carbon atoms, particularly preferably 2 to 14 carbon atoms. Further, L ₂₃ preferably contains 1 to 16 —CH ₂ —, and particularly preferably ₂ to 12 —CH ₂ —.

Q ₁ is independently a polymerizable group or a hydrogen atom. When the liquid crystalline compound of the present invention is used for an optical film or the like that preferably has a phase difference that does not change due to heat, such as an optical compensation film, Q ₁ is preferably a polymerizable group. The polymerization reaction is preferably addition polymerization (including ring-opening polymerization) or condensation polymerization. In other words, the polymerizable group is preferably a functional group capable of addition polymerization reaction or condensation polymerization reaction. Examples of polymerizable groups are shown below.

  Furthermore, the polymerizable group is particularly preferably a functional group capable of addition polymerization reaction. Such a polymerizable group is preferably a polymerizable ethylenically unsaturated group or a ring-opening polymerizable group.

  Examples of the polymerizable ethylenically unsaturated group include the following formulas (M-1) to (M-6).

In formulas (M-3) and (M-4), R represents a hydrogen atom or an alkyl group. R is preferably a hydrogen atom or a methyl group.
Among the above (M-1) to (M-6), (M-1) or (M-2) is preferable, and (M-1) is most preferable.

  The ring-opening polymerizable group is preferably a cyclic ether group, and more preferably an epoxy group or an oxetanyl group, and most preferably an epoxy group.

  As the liquid crystal compound of the present invention, a compound represented by the following general formula (DII) is preferable.

General formula (DII)

In the general formula (DII), Y ₃₁ , Y ₃₂ and Y ₃₃ are the same as the definitions of Y ₁₁ , Y ₁₂ and Y _{13 in} the general formula (DI).

In the general formula (DII), R ₃₁ , R ₃₂ and R ₃₃ are each independently represented by the following general formula (DII-R).

General formula (DII-R)

In the general formula (DII-R), A ₃₁ and A ₃₂ each independently represents a methine group or a nitrogen atom. As A ₃₁ and A ₃₂ , at least one is preferably a nitrogen atom, and most preferably both are nitrogen atoms. X ₃ represents an oxygen atom, a sulfur atom, methylene, or imino. X ₃ is most preferably an oxygen atom.

  The divalent cyclic group in the general formula (DII-R) is a divalent linking group having a 6-membered cyclic structure. The ring contained in the cyclic group may be a condensed ring. However, it is more preferably a monocycle than a condensed ring. The ring contained in the cyclic group may be any of an aromatic ring, an aliphatic ring, and a heterocyclic ring. Examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring. Examples of the aliphatic ring include a cyclohexane ring. Examples of the heterocyclic ring include a pyridine ring and a pyrimidine ring.

  Of the divalent cyclic groups, 1,4-phenylene and 1,3-phenylene are preferred as the cyclic group having a benzene ring. Examples of the cyclic group having a naphthalene ring include naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-2,5-diyl, naphthalene-2,6-diyl and Naphthalene-2,7-diyl is preferred. The cyclic group having a cyclohexane ring is preferably 1,4-cyclohexylene. As the cyclic group having a pyridine ring, pyridine-2,5-diyl is preferable. The cyclic group having a pyrimidine ring is preferably pyrimidine-2,5-diyl. As the divalent cyclic group, 1,4-phenylene, 1,3-phenylene and naphthalene-2,6-diyl are particularly preferable.

  The divalent cyclic group may have a substituent. Examples of the substituent include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a cyano group, a nitro group, an alkyl group having 1 to 16 carbon atoms, and an alkenyl group having 1 to 16 carbon atoms. , An alkynyl group having 1 to 16 carbon atoms, a halogen-substituted alkyl group having 1 to 16 carbon atoms, an alkoxy group having 1 to 16 carbon atoms, an acyl group having 2 to 16 carbon atoms, and the number of carbon atoms Is an alkylthio group having 1 to 16 carbon atoms, an acyloxy group having 2 to 16 carbon atoms, an alkoxycarbonyl group having 2 to 16 carbon atoms, a carbamoyl group, an alkyl-substituted carbamoyl group having 2 to 16 carbon atoms, and the number of carbon atoms Includes 2 to 16 acylamino groups. As the substituent of the divalent cyclic group, a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, and a halogen-substituted alkyl group having 1 to 6 carbon atoms are preferable, and further, a halogen atom or a carbon atom An alkyl group having 1 to 4 carbon atoms and a halogen-substituted alkyl group having 1 to 4 carbon atoms are preferable. In particular, a halogen atom, an alkyl group having 1 to 3 carbon atoms, and a trifluoromethyl group are preferable.

N3 in the general formula (DII-R) represents an integer of 1 to 3. n3 is preferably 1 or 2.
L ₃₁ in the general formula (DII-R) is the same as the definition of L _{22 in} the general formula (DI-R).
L ₃₂ in the general formula (DII-R) is the same as the definition of L _{23 in} the general formula (DI-R).
Q ₃ in the general formula (DII-R) is the same as defined for Q _{1 in} the general formula (DI-R).

  Specific examples of the compound represented by the general formula (I) or the general formula (II) are shown below, but the present invention is not limited thereto.

  Examples of the liquid crystal phase exhibited by the liquid crystal compound of the present invention include a columnar phase and a discotic nematic phase (ND phase). Among these liquid crystal phases, a discotic nematic phase (ND phase) exhibiting good monodomain properties is preferable.

  The liquid crystalline compound of the present invention preferably exhibits a liquid crystal phase in the range of 20 ° C to 300 ° C. More preferably, it is 40 degreeC-280 degreeC, Most preferably, it is 60 degreeC-250 degreeC. Here, the expression of the liquid crystal phase at 20 ° C. to 300 ° C. means that the liquid crystal temperature range crosses 20 ° C. (specifically, for example, 10 ° C. to 22 ° C.) or 300 ° C. (specifically, for example, 298). ° C to 310 ° C). The same applies to 40 ° C to 280 ° C and 60 ° C to 250 ° C.

  The compound represented by the general formula (DI) used in the present invention can be synthesized by applying a known method. Although the specific synthesis example of the compound represented by general formula (DI) used for this invention below is described, a synthesis example is not limited to this.

Synthesis Example 1 [Synthesis of D-3]
Synthesized according to the following scheme.

(Synthesis of D-3A)
15.0 g of 4-cyanophenol was dissolved in 300 ml of dimethylformamide, 20.9 g of potassium carbonate and 18.5 ml of 1-bromohexane were added, and the mixture was stirred at 110 ° C. for 5 hours under a nitrogen atmosphere. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate and washed with saturated brine. The organic layer was concentrated under reduced pressure and purified by column chromatography to obtain 25.0 g of D-3A.

(Synthesis of D-3B)
25.0 g of D-3A was dissolved in 200 ml of ethanol, and 26.0 ml of 50% hydroxylamine solution was added, followed by stirring at 90 ° C. for 3 hours. After cooling, methanol was added to the reaction solution, and the precipitated crystals were separated by filtration and dried to obtain 29.0 g of D-3B crystals.

(Synthesis of D-3)
29.0 g of D-3B was dissolved in 300 ml of 1,4-dioxane, and 10.2 g of trimesic acid chloride and 10.9 ml of pyridine were added, followed by stirring at 90 ° C. for 7 hours. After cooling, methanol was added and the precipitated crystals were collected by filtration. Purification by column chromatography yielded 25 g of D-3. The NMR spectrum of D-3 obtained is as follows.

¹ H-NMR (solvent: CDCl ₃ , standard: tetramethylsilane) δ (ppm):
0.85 (9H, t)
1.25-1.35 (12H, m)
1.35-1.45 (6H, m)
1.70-1.80 (6H, m)
3.95 (6H, t)
6.95 (6H, d)
8.05 (6H, d)
9.10 (3H, s)

  The phase transition temperature of the obtained D-3 was measured by texture observation using a polarizing microscope. First, when the temperature was raised, the crystal phase changed to an isotropic liquid phase around 139 ° C. Next, when the temperature was gradually lowered from 139 ° C., it changed to a discotic nematic phase around 123 ° C., and when it was lowered to 98 ° C., it changed to a crystalline phase again. That is, it was found that D-3 exhibits a discotic nematic phase between 123 ° C. and 98 ° C. when the temperature is lowered.

Synthesis Example 2 [Synthesis of D-7]
Synthesized according to the following scheme.

The D-31 1.0 g was dissolved in CH ₂ Cl ₂ 100ml, was added boron tribromide (1.0M CH ₂ Cl ₂ solution) 135 ml. After stirring at 40 ° C. for 8 hours, water was added to the reaction solution, and the precipitated crystals were collected by filtration. This crystal was dried to obtain 7.5 g of a trihydroxy compound.
After dissolving 0.34 g of 2-bromobutanol in 5 ml of dimethylacetamide, 0.26 ml of acrylic acid chloride was added dropwise, and after stirring for 1 hour at room temperature, 20 ml of water and 20 ml of hexane were added to wash the organic layer. After separation, the hexane layer was distilled off, 0.3 g of the above trihydroxy compound, 0.44 g of potassium carbonate and dimethylformamide were added, and the mixture was stirred at 110 ° C. for 5 hours. Water was added to the reaction mixture, and the mixture was extracted with CH ₂ Cl _{2. The} organic layer was concentrated and purified using column chromatography to obtain 0.36 g of D-7 crystals.

¹ H-NMR (solvent: CDCl ₃ , standard: tetramethylsilane) δ (ppm):
4.33 (6H, t)
4.60 (6H, t)
5.89 (3H, dd)
6.20 (3H, dd)
6.50 (3H, dd)
7.05 (6H, d)
8.15 (6H, d)
9.20 (3H, s)

  The phase transition temperature of the obtained D-7 was measured by texture observation with a polarizing microscope. When the temperature was first raised, the crystal phase changed to an isotropic liquid phase at around 173 ° C. Next, when the temperature was gradually lowered from 173 ° C., it changed to a discotic nematic phase at around 89 ° C., and when it was lowered to room temperature, it changed to a crystalline phase again. That is, it was found that D-7 exhibits a discotic nematic phase between 123 ° C. and room temperature when the temperature is lowered.

Synthesis Example 3 [Synthesis of D-101]
Synthesized according to the following scheme.

  100 ml of tetrahydrofuran and 11.7 ml of hexanol are added to 5.18 g of sodium hydride. After stirring at room temperature for 20 minutes, a solution of 10 g of 3,4-difluorobenzonitrile dissolved in 80 ml of tetrahydrofuran is added dropwise under ice cooling. After stirring at room temperature for 5 hours, water was added dropwise to the reaction solution, extracted with ethyl acetate, the organic layer was concentrated and purified using column chromatography to obtain 15.5 g of D-101A crystals. It was. Thereafter, the reaction was conducted in the same manner as in Example 1 to obtain D-101. The NMR spectrum of D-101 obtained is as follows.

¹ H-NMR (solvent: CDCl ₃ , standard: tetramethylsilane) δ (ppm):
0.95 (9H, t)
1.30-1.40 (12H, m)
1.40-1.50 (6H, m)
1.85-1.95 (6H, m)
4.20 (6H, t)
7.10 (3H, dd)
7.90-8.00 (6H, m)
9.20 (3H, s)

  When the phase transition temperature of the obtained D-101 was observed by texture observation with a polarizing microscope, the temperature was increased and the crystal phase changed to a discotic nematic liquid crystal phase around 135 ° C. It turned into a phase. That is, it was found that D-101 exhibits a discotic nematic liquid crystal phase between 135 ° C. and 162 ° C.

Synthesis Example 4 [Synthesis of D-109]
Synthesized according to the following scheme.

  Synthesis was performed in the same manner as in Example 2 using 6-bromo-1-hexanol as a raw material, and 0.35 g of D-109 was obtained. The NMR spectrum of D-109 obtained is as follows.

¹ H-NMR (solvent: CDCl ₃ , standard: tetramethylsilane) δ (ppm):
1.40-1.60 (12H, m)
1.65-1.75 (6H, m)
1.75-1.85 (6H, m)
4.15 (6H, t)
4.25 (6H, t)
5.80 (3H, dd)
6.15 (3H, dd)
6.45 (3H, dd)
7.10 (3H, dd)
7.90-8.00 (6H, m)
9.25 (3H, s)

  When the phase transition temperature of the obtained D-109 was observed by texture observation with a polarizing microscope, the temperature was increased and the crystal phase changed to a discotic nematic liquid crystal phase around 79 ° C. It turned into a phase. That is, it was found that D-109 exhibits a discotic nematic liquid crystal phase between 79 ° C. and 120 ° C.

[Alignment film]
The alignment film used in the present invention preferably has a characteristic that when the rod-shaped liquid crystal is aligned, the major axis direction of the rod-shaped liquid crystal can be aligned in a direction substantially orthogonal to the rubbing direction. Here, the characteristic that the major axis direction of the rod-shaped liquid crystal can be aligned in a direction substantially orthogonal to the rubbing direction includes a state where the rod-shaped liquid crystal molecules are not uniformly aligned. As the characteristics of the alignment film, it is preferable that the long axis direction of the rod-shaped liquid crystal is uniformly aligned in the direction orthogonal to the rubbing direction. Since it is not oriented, it cannot be said that it is not preferable.
In addition, if the long axis direction of the rod-like liquid crystal is an alignment film that is intended to be aligned in a direction different from the rubbing direction, even if a discotic liquid crystal compound is aligned on the alignment film, the alignment defects are reduced. Can be expected.
Therefore, the characteristic that the major axis direction of the rod-shaped liquid crystal can be aligned in a direction substantially orthogonal to the rubbing direction is that the rod-shaped liquid crystal as shown below has a surface area of 20% or more when aligned on the alignment film. An alignment film in which the major axis direction can be aligned in the direction of 90 ° ± 10 ° with the rubbing direction is shown. More preferably, the alignment film has an area of 50% or more and the long axis direction of the rod-like liquid crystal can be aligned in the direction of 90 ° ± 10 ° with the rubbing direction.

Specific examples of the rod-like liquid crystal include D.I. Demus et al., Hand Book of Liquid Crystals, Vol. 1, Vol. 2A, Vol. Examples thereof include compounds described in 2B and compounds obtained by introducing a polymerizable group into these compounds. As the polymerizable group, the polymerizable group mentioned in Q ₁ can be used.

  Furthermore, as rod-like liquid crystalline compounds having a polymerizable group, Makromol. Chem. 190, 2255 (1989), Advanced Materials 5, 107 (1993), U.S. Pat. Nos. 4,683,327, 5,622,648 and 5,770,107, International Publications WO 95/22586, 95/24455, No. 97/00600, No. 98/23580, No. 98/52905, JP-A-1-272551, JP-A-6-16616, JP-A-7-110469, JP-A-11-80081, JP-A-2001-328773, etc. Can be used.

Examples of the alignment film having the characteristic that the long axis direction of the rod-like liquid crystal can be oriented in a direction substantially perpendicular to the rubbing direction when the rod-like liquid crystal is oriented include, for example, JP 2002-268068 A and JP 2002-62427 A. The reported polymer and polystyrene, and (i) an acrylic acid copolymer comprising a repeating unit represented by the following general formula (I) and a repeating unit represented by the following general formula (II) or (III) Or a methacrylic acid copolymer, (ii) a polymer having at least one repeating unit represented by any one of the following general formula (I-TH), general formula (II-TH) and general formula (III-TH) be able to.
However, (i) {acrylic acid copolymer or methacrylic acid copolymer containing a repeating unit represented by the following general formula (I) and a repeating unit represented by the following general formula (II) or (III)}, (ii ) {In the case where a polymer having at least one repeating unit represented by any one of the following general formula (I-TH), general formula (II-TH) and general formula (III-TH)} is used for the alignment film It is preferable that the major axis direction of the rod-like liquid crystal is oriented in a direction substantially perpendicular to the rubbing direction, but the major axis direction of the rod-like liquid crystal is not necessarily oriented in the direction substantially perpendicular to the rubbing direction when the rod-like liquid crystal is oriented. There is no need to have such a characteristic.

Hereinafter, the alignment films represented by (i) and (ii) will be described in detail.
{Acrylic acid copolymer or methacrylic acid copolymer containing a repeating unit represented by the following general formula (I) and a repeating unit represented by the following general formula (II) or (III)}

In general formulas (I) to (III);
R ¹ and R ² are each independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms; M is a proton, an alkali metal ion or an ammonium ion; L ⁰ is —O A divalent linking group selected from the group consisting of —, —CO—, —NH—, —SO ₂ —, an alkylene group, an alkenylene group, an arylene group, and combinations thereof; R ⁰ is a group having 10 carbon atoms; A hydrocarbon group having 1 to 100 carbon atoms or a fluorine atom-substituted hydrocarbon group having 1 to 100 carbon atoms; Cy is an aliphatic ring group, an aromatic group or a heterocyclic group; m is 10 to 99 mol% And n is 1 to 90 mol%.
More detailed explanations and preferred embodiments of R ¹ , R ² , M, L ⁰ , R ⁰ , Cy and n are the same as those described in JP-A-2002-9883.
As the acrylic acid copolymer or methacrylic acid copolymer, the compounds described in JP-A-2002-9883 can also be used.

{Polymer having at least one repeating unit represented by any one of the following general formula (I-TH), general formula (II-TH) and general formula (III-TH)}
The alignment film of the present invention is a polymer having at least one repeating unit represented by any one of the following general formula (I-TH), general formula (II-TH) and general formula (III-TH) (hereinafter, And may be referred to as “polymer for alignment film”). Hereinafter, the general formulas (I-TH) to (III-TH) will be described in detail.

General formula (I-TH)

In the formula, R ¹ represents a hydrogen atom, a methyl group, a halogen atom or a cyano group, preferably a hydrogen atom, a methyl group or a halogen atom, more preferably a hydrogen atom or a methyl group.
P ¹ represents an oxygen atom, —CO— or —NR ¹² —. R ¹² represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. The alkyl group may be linear, branched or cyclic. Preferably they are a hydrogen atom or a C1-C4 alkyl group, More preferably, they are a hydrogen atom, a methyl group, or an ethyl group.

L ¹ represents a divalent linking group selected from the group consisting of a substituted or unsubstituted alkylene group, divalent cycloaliphatic group, divalent aromatic group, divalent heterocyclic group, and combinations thereof. . As the alkylene group, an alkylene group having 1 to 10 carbon atoms is preferable, and an alkylene group having 1 to 6 carbon atoms is more preferable. For example, a methylene group, an ethylene group, a trimethylene group, etc. are mentioned. As the divalent cycloaliphatic group, cyclohexane-1,2-diyl, 1,4-cyclohexane-1,4-diyl, and cyclobutane-1,3-diyl are preferable, and 1,4-cyclohexane-1 is more preferable. , 4-diyl, cyclobutane-1,3-diyl. Examples of the aromatic ring of the divalent aromatic group include a benzene ring, an indene ring, a naphthalene ring, a fluorene ring, a phenanthrene ring, and an anthracene ring, and a benzene ring and a naphthalene ring are preferable. Examples of the divalent aromatic group include 1,4-phenylene, 1,3-phenylene, 1,2-phenylene, 1,2-naphthylene, 1,3-naphthylene, 1,4-naphthylene, and 1,5-naphthylene. 1,8-naphthylene and 2,6-naphthylene are preferable, and 1,4-phenylene, 1,3-phenylene, 1,4-naphthylene, 1,5-naphthylene and 2,6-naphthylene are more preferable. The hetero ring of the divalent heterocyclic group is preferably a 5-membered, 6-membered or 7-membered heterocycle, and more preferably a 5-membered ring or a 6-membered ring. As a hetero atom constituting the hetero ring, any of a nitrogen atom, an oxygen atom and a sulfur atom is preferable. Examples of heterocycles include furan ring, thiophene ring, pyrrole ring, pyrrolidine ring, oxadiazole ring, isoxadiazole ring, thiazole ring, isothiazole ring, imidazole ring, imidazoline ring, imidazolidine ring, pyrazole ring, Pyrazoline ring, pyrazolidine ring, triazole ring, furazane ring, pyran ring, thiane ring, oxadiazole ring, thiadiazole ring, pyridine ring, piperidine ring, oxazine ring, morpholine ring, thiazine ring, pyridazine ring, pyrimidine ring, pyrazine ring, Examples of the divalent heterocyclic group including a piperazine ring and a triazine ring include pyridine-2,5-diyl, pyridine-2,4-diyl, pyrimidine-2,5-diyl, and pyrimidine-2,4- Diyl and 1,3,5-triazine-2,4-diyl are preferred.

The alkylene group, divalent aromatic group or divalent heterocyclic group represented by L ¹ may have a substituent. Examples of substituents include aliphatic groups, aromatic groups, heterocyclic groups, halogen atoms, alkoxy groups (eg, methoxy, ethoxy, methoxyethoxy), aryloxy groups (eg, phenoxy) arylazo groups (eg, phenylazo), Alkylthio group (eg, methylthio, ethylthio, propylthio), alkylamino group (eg, methylamino, propylamino), arylamino group (eg, phenylamino), acyl group (eg, formyl, acetyl, propanoyl, octanoyl, benzoyl) , Acyloxy groups (for example, acetoxy, pivaloyloxy, benzoyloxy), hydroxy groups, mercapto groups, amino groups, carboxyl groups, sulfo groups, carbamoyl groups, sulfamoyl groups, and ureido groups.

X ¹ represents a hydrogen bonding group. As the hydrogen bonding group, a hydroxyl group, a carboxyl group, a carbamoyl group, a sulfamoyl group, a ureido group, an acylamino group, and a sulfo group are preferable, and a carboxyl group, a carbamoyl group, a sulfamoyl group, and a ureido group are more preferable.
n1 represents an integer of 1 to 3.

  Next, general formula (II-TH) will be described.

General formula (II-TH)

In the formula (II-TH), R ² represents a hydrogen atom, a methyl group, a halogen atom or a cyano group. L ²¹ represents a substituted or unsubstituted divalent aromatic group or divalent heterocyclic group, and the divalent aromatic group and divalent group represented by L ¹ in the general formula (I-TH). And the preferred range is also the same. P ²¹ represents a single bond or a divalent linking group selected from the group consisting of —O—, —NR ²¹ —, —CO—, —S—, —SO—, —SO ₂ — and combinations thereof, R ²¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and is the same as R ¹ in the general formula (I-TH), and the preferred range is also the same. L22 represents a substituted or unsubstituted divalent linking group selected from the group consisting of an alkylene group, a divalent cycloaliphatic group, a divalent aromatic group, a divalent heterocyclic group, and combinations thereof. L ²² has the same meaning as L ^{1 in} formula (I-TH), and the preferred range is also the same. X2 represents a hydrogen bonding group, has the same meanings as X ¹ in the general formula (I-TH), and preferred ranges are also the same. n2 is an integer of 0-3.

  Next, general formula (III-TH) will be described.

General formula (III-TH)

In the general formula (III-TH), L ³¹ represents a substituted or unsubstituted divalent aromatic group or divalent heterocyclic group, and the divalent fragrance of L 1 in the general formula (I-TH). It is synonymous with the group and the divalent heterocyclic group, respectively, and the preferred range is also the same. P ³¹ represents a single bond or a divalent linking group selected from the group consisting of —O—, —NR ³¹ —, —CO—, —S—, —SO—, —SO ₂ — and combinations thereof; R ³¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and is the same as R ¹ in the general formula (I-TH), and the preferred range is also the same.
L ³² represents a substituted or unsubstituted divalent linking group selected from the group consisting of an alkylene group, a divalent cycloaliphatic group, a divalent aromatic group, a divalent heterocyclic group, and combinations thereof. , L ³² has the same meaning as L ^{1 in} formula (I-TH), and the preferred range is also the same. X ³ represents a hydrogen bonding group and has the same meaning as X ¹ in the general formula (I-TH), and the preferred range is also the same. n3 is an integer of 0-3.

  Specific examples of the repeating unit represented by the general formula (I-TH), general formula (II-TH) or general formula (III-TH) of the present invention are shown below, but the present invention is not limited thereto. is not.

  The alignment film of the present invention may be a homopolymer consisting of only one type of structural unit represented by any one of the general formulas (I-TH), (II-TH) and (III-TH). I-TH), (II-TH) and (III-TH) may be a copolymer composed of two or more of the structural units represented by any one of formula (I-TH), It may be a copolymer of one or more of the structural units represented by any of (II-TH) and (III-TH) and one or more of the other structural units. The structural unit other than the structural unit represented by the general formula (I-TH), (II-TH) or (III-TH) is not particularly limited, but preferred copolymer structural units include, for example, vinyl monomers. (For example, acrylic acid, methacrylic acid, acrylic esters, methacrylic esters, acrylic amides, methacrylic amides, vinyl alcohol, acyloxy vinyls, styrenes, maleic acid, maleic esters, maleamides , Acrylonitrile, vinyl alkyl ketones, and the like) and a structural unit represented by the following general formula (IV-A) or).

General formula (IV-A), general formula (IV-B)

In the general formula (IV-A), R ⁴¹ has the same meaning as R ¹ in the general formula (I-TH), and the preferred range thereof is also the same. L ⁴¹ represents a single bond, —COO—, —OCO— or —CONHR ⁴² —, wherein R ⁴² represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or a heterocyclic group having 4 to 10 carbon atoms. To express. As the hydrocarbon group, methyl, ethyl, propyl, butyl, phenyl and the like are preferable. Preferred examples of the heterocyclic group include groups shown as the heterocyclic group for L ^{1 in} the general formula (I-TH). These groups may have a substituent. Z in the general formulas (IV-A) and (IV-B) represents a hydrogen atom, a halogen atom (for example, chloro atom), an alkyl group (for example, methyl group, ethyl group, etc.), an aryl group (for example, phenyl). group, a naphthyl group, ^{etc.), - OR 1 ', -NR} 2' R 3 ', -SR 4', -PR 5 'R 6', -SiR 7 'R 8' R 9 ', -C (= O) ^{R 10 ', -C (= O} ) OR 11', -C (= O) NR 12 'R 13', -OC (= O) OR 14 ', -OC (= O) NR 15' R 16 ', ^{-NR 17 'C (= O)} NR 18' R 19 '-, - N + R 21' R 22 represents a 'R ^23' or the like. R ¹ ′ to R ²³ ′ have the same meaning as the group represented by R ⁴² .

  A polymer having a structural unit represented by any one of the general formulas (I-TH), (II-TH) and (III-TH) is a water-soluble group (for example, a hydroxyl group, a carboxyl group, a sulfo group, a quaternary group). It preferably has an ammonium group, amino group, phospho group or the like. In particular, a polymer having a hydroxyl group or a carboxyl group is preferred. These water-soluble substituents may be substituents in the structural unit represented by any one of the general formulas (I-TH), (II-TH) and (III-TH), but other structural units It may be a substituent.

  Specific examples of the structural unit represented by the general formula (IV-A) or the general formula (IV-B) are shown below, but the present invention is not limited to the following specific examples.

  The total content of the structural units represented by the general formula (I-TH), (II-TH) or (III-TH) in the alignment film polymer is preferably 1% by mass to 100% by mass, 10 mass%-100 mass% are more preferable, and 20 mass%-100 mass% are still more preferable.

  It is preferable that the alignment film polymer further includes a structural unit having a crosslinkable group. When the alignment film polymer contains a polymerizable group, for example, when the liquid crystalline compound having a polymerizable group is aligned on the alignment film of the present invention and fixed in an alignment state by polymerization, the alignment film layer is fixed. In many cases, the adhesiveness with the optically anisotropic layer made of a liquid crystalline compound is improved. The crosslinkable group may be any of addition, condensation, substitution reactive group and the like, and is not particularly limited. On the other hand, as the liquid crystalline compound, a material having an ethylenically unsaturated group such as an acryloyl group or a methacryloyl group is preferably fixed by ultraviolet irradiation in the presence of a radical photopolymerization initiator. It is preferable that the polymer for use also has a crosslinkable group capable of undergoing a crosslinking reaction upon irradiation with ultraviolet rays. As a preferred example of a reaction that can be crosslinked by ultraviolet irradiation, a ring-opening polymerization reaction of a heterocyclic compound such as an epoxy ring or an oxetane ring that is combined with a compound that generates a cation by ultraviolet irradiation and a compound that generates a radical by ultraviolet irradiation are used in combination. The radical polymerization reaction of the compound which has an ethylenically unsaturated group is mentioned. Among these, the most preferable crosslinkable group contained in the polymer for alignment film is an ethylenically unsaturated group (for example, acryloyl group, methacryloyl group, styryl group, etc.). Moreover, there is no restriction | limiting in particular as a crosslinkable group introduction | transduction method in the polymer for said alignment films.

  Although the preferable specific example of the structural unit containing a crosslinkable group is shown below, this invention is not limited at all by the following specific examples.

The polymer for alignment film used in the present invention can be produced by various methods such as addition, condensation, and substitution reaction. It is most simple and preferable to produce by a radical polymerization reaction of an ethylenically unsaturated compound that is a structural unit represented by any one of the general formulas (I-TH) to (III-TH).
On the other hand, when the alignment film polymer includes a structural unit having a crosslinkable group, the polymer directly polymerizes a corresponding monomer (that is, a monomer having a substituent that becomes a crosslinkable group), Synthesized by a method of introducing an ethylenically unsaturated group; or (b) a method of introducing an ethylenically unsaturated group into a polymer obtained by polymerizing a monomer having an arbitrary functional group by a polymer reaction. it can. The method (b) is preferred. The polymer reaction includes the following: I) For example, after a polymer containing a functional group obtained by precuring an ethylenically unsaturated group that removes hydrochloric acid from a 2-chloroethyl group is generated, functional group conversion (elimination reaction, oxidation) A method of deriving an ethylenically unsaturated group by reaction, reduction reaction, deprotection reaction, etc.); and II) after forming a polymer containing any functional group, a bond formation reaction with the functional group in the polymer proceeds. And a method of reacting a compound having both a functional group capable of forming a covalent bond and an ethylenically unsaturated group (hereinafter referred to as “reactive monomer”). Further, the polymer may be synthesized by combining the methods I) and II). The bond formation reaction referred to here can be used without particular limitation as long as it is a reaction that forms a covalent bond in the bond formation reaction generally used in the field of organic synthesis. On the other hand, the ethylenically unsaturated group contained in the polymer may be thermally polymerized and gelled during the reaction, so that the reaction proceeds at the lowest possible temperature (preferably 60 ° C. or less, particularly preferably room temperature or less). Is preferred. A catalyst may be used for the purpose of promoting the progress of the reaction, and a polymerization inhibitor may be used for the purpose of suppressing gelation.

  When the alignment film polymer includes a structural unit having a crosslinkable group, the proportion of the structural unit is preferably 0.1% by mass to 60% by mass, more preferably 0.3% by mass to 50% by mass, and 0 More preferably, it is 5 mass%-40 mass%.

  A preferred molecular weight range of the polymer for alignment film is 1,000 to 1,000,000, more preferably 2,000 to 200,000 in terms of weight average molecular weight. Most preferably, it is 3000 or more and 100,000 or less.

  Although the preferable example of the polymer for alignment films used for this invention below is shown in Table 1, this invention is not limited at all by the following specific examples. In addition, about the structural unit represented by the said general formula (I-TH), (II-TH) or (III-TH), and the structural unit containing a crosslinkable substituent, it shows by the number of the above-mentioned specific example, The copolymer composition ratio is indicated by mass%.

  The alignment film used in the present invention can be easily synthesized by applying a known method. Although the specific synthesis example of the polymer used for this invention is described below, a synthesis example is not limited to this.

Synthesis example of (AL-1) N, N-dimethylacetamide (300 ml) was added to a 500 mL three-necked flask to dissolve 4-aminobenzoic acid (40.3 g, 0.294 mol) and cooled to 0 ° C. Acrylic acid chloride (30.0 g, 0.331 mol) was slowly added dropwise. After completion of the dropwise addition, the reaction solution was heated to 40 ° C., and further heated and stirred for 2 hours. Then, the reaction solution was added to 3 L of water, and the precipitated solid was separated by filtration under reduced pressure and dried by blowing (intermediate A). Was obtained quantitatively. N, N-dimethylformamide (10 ml) was placed in a 100 mL three-necked flask, heated to 65 ° C. while flowing nitrogen at a flow rate of 35 ml / min, and an initiator (V-65, 7 manufactured by Wako Pure Chemical Industries, Ltd.) was used. 0.5 mg) of N, N-dimethylformamide (4 ml) was added. Ten minutes later, a solution of intermediate A (7.5 g: 0.039 mol) and initiator (V-65, 18.5 mg, manufactured by Wako Pure Chemical Industries, Ltd.) in N, N-dimethylformamide (20 ml) was added over 3 hours. And dripped. After completion of the dropwise addition, an N, N-dimethylformamide (2 ml) solution of an initiator (V-65, 3.8 mg, manufactured by Wako Pure Chemical Industries, Ltd.) was added and reacted at the same temperature for 3 hours. After returning the reaction system to room temperature, it was slowly poured into stirred water (800 mL), and the precipitated polymer was taken out by suction filtration and further washed with water, and the resulting wet polymer was 8.9 g. By drying this polymer, 6.9 g of alignment film polymer AL-1 was obtained, and it was confirmed by 1H-NMR that the obtained solid was a polymer.

  The alignment film of the present invention is obtained by applying a coating solution prepared by dissolving the polymer for alignment film in a solvent to the support surface, and drying and removing the solvent contained in the coating solution at 25 ° C to 140 ° C. Can be produced. Moreover, although it can also form by vapor deposition if possible, formation by application | coating is more preferable. The thickness of the alignment film thus formed is preferably 0.01 to 5 μm, and more preferably 0.05 to 2 μm.

  Examples of the solvent used for the preparation of the alignment film forming coating solution include water, alcohols (eg, methanol, ethanol, isopropanol, etc.), amides (eg, N, N-dimethylformamide, etc.), acetonitrile, acetone. , Methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, and the like, preferably water, alcohols, and mixed solvents thereof. The concentration of the alignment film polymer in the coating solution is preferably 0.1% by mass to 40% by mass, more preferably 0.5% by mass to 20% by mass, and 2% by mass to 10% by mass. % Is more preferable. The viscosity of the coating solution is preferably 0.1 cp to 100 cp, and more preferably 0.5 cp to 50 cp.

  In addition to the alignment film polymer, an additive may be appropriately added to the coating solution. For example, when the alignment film polymer is difficult to dissolve in a water-soluble solvent, a basic compound (for example, sodium hydroxide, lithium hydroxide, triethylamine) or an acidic compound (for example, hydrochloric acid, acetic acid, succinic acid, etc.) ) May be added to promote dissolution.

  The alignment film formed by the above method is preferably given a liquid crystal alignment by rubbing the surface. The rubbing treatment can be performed by rubbing the surface of the polymer coating layer several times in a certain direction (usually the longitudinal direction) with paper or cloth. As a method other than rubbing, liquid crystal alignment can be imparted by applying an electric field, applying a magnetic field, or irradiating light. As a method for imparting liquid crystal alignment, an alignment film formed by a rubbing treatment of a polymer is particularly preferable.

[Phase difference plate]
The retardation plate of the present invention has an alignment film of the present invention on the support and an optically anisotropic layer containing a liquid crystal compound controlled in alignment by the alignment film and fixed in the alignment state. Features.
(1) Optically anisotropic layer The optically anisotropic layer of this invention contains the liquid crystalline compound fixed to the orientation state. Preferably, the liquid crystal compound is a compound represented by the general formula (DI). The optically anisotropic layer is formed of a coating liquid containing a liquid crystalline compound, preferably a discotic liquid crystalline compound, and optionally a polymerizable initiator and other additives, for example, the orientation of the present invention formed on a support. It can be formed by coating on the surface of the film and aligning and fixing the liquid crystalline compound. After aligning and fixing the liquid crystalline compound, the support may be peeled off.

(1) -a Forming Method The optically anisotropic layer is formed on the support as described above by applying a coating solution prepared by dissolving a discotic liquid crystalline compound or a rod-like liquid crystalline compound in a solvent capable of being dissolved. And it can produce by apply | coating on the orientation film | membrane of this invention to which orientation was provided. Further, if possible, formation by vapor deposition may be used, but formation by coating is preferably used. Examples of the coating method include known coating methods such as curtain coating, dip coating, spin coating, printing coating, spray coating, slot coating, roll coating, slide coating, blade coating, gravure coating, and wire bar method. Next, the solvent used at 25 ° C. to 130 ° C. is dried, and at the same time, the liquid crystalline compound is oriented and further fixed by ultraviolet irradiation or the like, thereby forming an optically anisotropic layer of the liquid crystalline compound. It is preferable to use ultraviolet rays for light irradiation for polymerization. The irradiation energy is preferably ^{20mJ / cm 2 ~50J / cm 2} , further preferably 100 to 800 mJ / cm ^2. In order to accelerate the photopolymerization reaction, light irradiation may be performed under heating conditions. The thickness of the optically anisotropic layer thus formed varies depending on the optimum retardation value depending on the use such as optical compensation, but is preferably 0.1 to 10 μm, preferably 0.5 to 5 μm. More preferably it is.

(1) -b Material used for forming optically anisotropic layer The optically anisotropic layer is formed from a compound represented by the general formula (DI). In particular, it is preferably formed from a compound represented by the general formula (DI) and exhibiting discotic liquid crystallinity. As the discotic liquid crystalline compound other than the compound represented by the general formula (DI) that can be used in the present invention, a discotic liquid crystalline compound having a polymerizable group is preferable. The discotic liquid crystalline compounds are disclosed in various documents (C. Destrade et al., Mol. Crysr. Liq. Cryst., Vol. 71, page 111 (1981); edited by the Chemical Society of Japan, Quarterly Chemical Review, No. 22, Liquid Crystal Chemistry, Chapter 5, Chapter 10 Section 2 (1994); B. Kohne et al., Angew. Chem. Soc. Chem. Comm., Page 1794 (1985); J. Zhang et al., J Am.Chem.Soc., Vol.116, page 2655 (1994)). The polymerization of the discotic liquid crystalline compound is described in JP-A-8-27284.

  These liquid crystalline compounds are preferably substantially uniformly oriented in the optically anisotropic layer, more preferably fixed in a substantially uniformly oriented state. It is most preferable that the liquid crystal compound is fixed by.

  The proportion of the polymer obtained from the compound represented by the general formula (DI) or the compound represented by the general formula (DI) occupying the optically anisotropic layer is preferably 10 to 100% by mass, More preferably, it is -99 mass%, and it is most preferable that it is 50-99 mass%.

  The optically anisotropic layer is formed by applying a coating liquid containing a liquid crystalline compound, preferably the discotic liquid crystalline compound, and, if desired, the following polymerization initiator and other additives onto the alignment film of the present invention. Is preferably formed. Hereinafter, materials other than the liquid crystalline compound that can be added to the coating solution will be described.

  The liquid crystalline molecules are preferably fixed while maintaining the alignment state, and the fixing is performed by a polymerization reaction of a polymerizable group (P in the general formula (V)) introduced into the liquid crystalline molecules. Is preferred. For that purpose, it is preferable to contain a polymerization initiator in the coating solution. The polymerization reaction includes a thermal polymerization reaction using a thermal polymerization initiator, a photopolymerization reaction using a photopolymerization initiator, and EB curing using an electron beam. Among these, photopolymerization reaction (photocuring) and EB curing are preferable. Examples of polymerization initiators that generate radicals by the action of light include α-carbonyl compounds (described in US Pat. Nos. 2,367,661 and 2,367,670), acyloin ether (described in US Pat. No. 2,448,828), α -Combination of hydrocarbon-substituted aromatic acyloin compound (described in US Pat. No. 2,722,512), polynuclear quinone compound (described in US Pat. Nos. 3,046,127 and 2,951,758), triarylimidazole dimer and p-aminophenyl ketone (Described in US Pat. No. 3,549,367), acridine and phenazine compounds (JP-A-60-105667, US Pat. No. 4,239,850) and oxadiazole compounds (described in US Pat. No. 4,212,970), acetophenone compounds , Benzoy Preferred are ether ether compounds, benzyl compounds, benzophenone compounds, thioxanthone compounds, and the like. Examples of the acetophenone compound include 2,2-diethoxyacetophenone, 2-hydroxymethyl-1-phenylpropan-1-one, 4′-isopropyl-2-hydroxy-2-methyl-propiophenone, 2-hydroxy -2-methyl-propiophenone, p-dimethylaminoacetone, p-tert-butyldichloroacetophenone, p-tert-butyltrichloroacetophenone, p-azidobenzalacetophenone and the like. Examples of the benzyl compound include benzyl, benzyl dimethyl ketal, benzyl-β-methoxyethyl acetal, 1-hydroxycyclohexyl phenyl ketone and the like. Examples of the benzoin ether compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin-n-propyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, and benzoin isobutyl ether. Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, and the like. Examples of the thioxanthone compound include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, and the like. Among such photosensitive radical polymerization initiators composed of aromatic ketones, acetophenone compounds and benzyl compounds are particularly preferable in terms of curing characteristics, storage stability, odor, and the like. The photosensitive radical polymerization initiators composed of these aromatic ketones can be used alone or in combination of two or more according to the desired performance. In addition to a polymerization initiator, a sensitizer may be used for the purpose of increasing sensitivity. Examples of the sensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, thioxanthone and the like.

  Multiple photopolymerization initiators may be combined, and the amount used is preferably 0.01 to 20% by mass, more preferably 0.5 to 5% by mass, based on the solid content of the coating solution. The amount of the photopolymerization initiator used is preferably 0.01 to 20% by mass, more preferably 0.05 to 5% by mass, based on the solid content of the coating solution. It is preferable to use ultraviolet rays for light irradiation for polymerization of liquid crystalline molecules.

In addition to the photopolymerization initiator, an additive may be appropriately added to the coating liquid for forming the optically anisotropic layer. For example, a plasticizer, a monomer, a surfactant, a cellulose ester, an alignment control agent, a chiral agent, and the like can be given. The orientation control agent will be described in detail below. The alignment control agent in the present invention is added to the liquid crystal compound coating solution, and after coating, the liquid crystal compound layer is unevenly distributed on the surface of the liquid crystal compound layer, that is, on the air interface side, thereby aligning the liquid crystal compound on the air interface side. Represents a compound capable of controlling Depending on the structure of the alignment control agent, the liquid crystalline compound can be aligned substantially vertically on the air interface side, or conversely, can be aligned substantially horizontally. For example, in the case of a discotic liquid crystalline compound, a compound represented by the following general formula (VI) described in JP-A No. 2000-344734 is exemplified.
Formula ^{(VI) :( Hb-L 2} -) nB 1
In the formula (VI), Hb represents an aliphatic group having 6 to 40 carbon atoms or an aliphatic substituted oligosiloxanoxy group having 6 to 40 carbon atoms, and L ² represents —O—, —S—, —CO. —, —NR ⁵ —, —SO ₂ —, a divalent linking group selected from the group consisting of an alkylene group, an alkenylene group, an arylene group, and combinations thereof, R ⁵ represents a hydrogen atom or a carbon number of 1-6. N represents an integer of 2 to 12, and B ¹ represents an n-valent group containing at least three ring structures. Details of Hb, L ² , B 1 and n in the general formula (VI) are described in JP-A No. 2002-129612, and the same applies to the alignment control agent used in the present invention.

Further, the alignment controller may be a polymer compound as shown below. The polymer orientation control agent to be added is not particularly limited as long as it is a polymer that can be dissolved in the coating liquid for forming the optically anisotropic layer. An example of a preferred polymer alignment controller is shown below.
Polypropylene oxide polytetramethylene oxide poly-ε-caprolactone poly-ε-caprolactone diol poly-ε-caprolactone triol polyvinyl acetate polymelamine poly (ethylene adipate)
Poly (1,4-butylene adipate)
Poly (1,4-butylene glutarate)
Poly (1,2-butylene glycol)
Poly (1,4-butylene succinate)
Poly (1,4-butylene terephthalate)
polyethylene terephthalate)
Poly (2-methyl-1,3-propylene adipate)
Poly (2-methyl-1,3-propylene glutarate)
Poly (neopentyl glycol adipate)
Poly (neopentyl glycol sebacate)
Poly (1,3-propylene adipate)
Poly (1,3-propylene glutarate)
Polyvinyl butyral polyvinyl formal polyvinyl acetal polyvinyl propanal polyvinyl hexanal polyvinyl pyrrolidone polyacrylic acid ester polymethacrylic acid ester poly (3-hydroxybutyric acid)

  The addition amount of the alignment control agent is preferably 0.01% by mass to 10% by mass and more preferably 0.05% by mass to 5% by mass with respect to the liquid crystal compound.

  Examples of the surfactant include conventionally known compounds, and fluorine compounds are particularly preferable. Specifically, for example, compounds described in paragraphs [0028] to [0056] in JP-A-2001-330725, paragraphs [0100] to [0118] in JP-A-2004-188333. And the compounds described. Preferable examples of the surfactant include the compounds X-1 to X-20 and X-61 to X-72 in Japanese Patent Application No. 2004-188333. The surfactant is generally used in an amount of 0.005 to 8% by mass (preferably 0.2 to 2.5% by mass) based on the discotic compound.

  As the solvent used for preparing the coating liquid for forming the optically anisotropic layer, an organic solvent is preferable. Examples of organic solvents include amides (eg, N, N-dimethylformamide), sulfoxides (eg, dimethyl sulfoxide), heterocyclic compounds (eg, pyridine), hydrocarbons (eg, toluene, hexane) alkyl halides (eg, Chloroform, dichloromethane), esters (eg, methyl acetate, butyl acetate), ketones (eg, acetone, 2-butanone, methyl isobutyl ketone, cyclohexanone), ethers (eg, tetrahydrofuran, 1,2-dimethoxyethane) and the like . Of these, alkyl halides and ketones are preferred. Two or more organic solvents may be used in combination.

  The solid content concentration of the liquid crystal compound and other additives in the coating solution is preferably 0.1% by mass to 60% by mass, more preferably 0.5% by mass to 50% by mass, and 2% by mass to 40% by mass. % Is more preferable. The viscosity of the coating solution is preferably 0.01 cp to 100 cp, and more preferably 0.1 cp to 50 cp.

(1) -c Alignment State When the optically anisotropic layer of the present invention is used as a phase difference plate in a liquid crystal display mode such as TN (Twisted Nematic), the state where the discotic nematic phase is hybrid-aligned is fixed. Is preferable. Here, the hybrid alignment represents a state in which the tilt angle of the liquid crystal compound continuously changes in the film thickness direction.

The liquid crystalline compound is coated on the support (more preferably on the alignment film) and then, for example, heated to develop a liquid crystal phase. Therefore, the liquid crystalline compound is formed on the support surface or the coating film interface (alignment film) at the support side interface. Is provided at the tilt angle (in other words, the angle formed by the direction of the transparent support surface and the disk surface direction of the liquid crystal compound (the liquid crystal compound of the present invention has a disk shape)). Orientation is performed at the tilt angle of the air interface at the interface with air.
In the present invention, the average tilt angle of the optically anisotropic layer (angle formed by the direction of the transparent support surface and the disc surface direction of the liquid crystalline compound) is preferably 10 to 70 °, and particularly preferably 20 to 60 °.
The tilt angle at each interface is a combination of the tilt angle at the air interface of 0 to 50 ° and the tilt angle of the support side interface of 20 to 90 °, or the tilt angle of the support side interface of 0 to 50 ° and the air. A combination in which the tilt angle of the interface is 20 to 90 ° is preferable. In particular, a combination in which the tilt angle of the air interface is 0 to 40 ° and the tilt angle of the support side interface is 40 to 80 °, or the tilt angle of the support side interface is 0 to 40 ° and the tilt angle of the air interface is 40 to 40 °. A combination of 80 ° is preferred.

(2) Support The retardation plate of the present invention has a support. The support is not necessarily the same as the support used at the time of production, and after the optically anisotropic layer is produced, it may be transferred from the temporary support used at the production to another support. The support used in the retardation plate of the present invention is preferably a polymer film that is transparent, has a small optical anisotropy, and a small wavelength dispersion. Here, that the support is transparent means that the light transmittance is 80% or more. Specifically, the small chromatic dispersion means that the ratio of Re400 / Re700 is preferably less than 1.2. Specifically, the small optical anisotropy means that in-plane retardation (Re) is preferably 20 nm or less, and more preferably 10 nm or less. The transparent support preferably has a roll-like or rectangular sheet-like shape, and the optically anisotropic layer can be laminated using the roll-like transparent support and then cut into a required size. preferable. Examples of the polymer include cellulose acylate, polycarbonate, polysulfone, polyethersulfone, polyacrylate and polymethacrylate. Cellulose acylate is preferred, cellulose acetate is more preferred, and triacetyl cellulose is most preferred. About manufacturing a cellulose acylate film using a non-chlorinated solvent, it is described in detail in JIII Journal of Technical Disclosure No. 2001-1745, and the cellulose acylate film described therein is also preferably used in the present invention. it can.

  The polymer film for the support is preferably formed by a solvent cast method. The thickness of the transparent support is preferably 20 to 500 μm, and more preferably 30 to 200 μm. In order to improve the adhesion between the transparent support and the layer (adhesive layer, alignment film or optically anisotropic layer) provided on the transparent support, surface treatment (eg, glow discharge treatment, corona discharge treatment, ultraviolet light ( UV) treatment, flame treatment, saponification treatment). An adhesive layer (undercoat layer) may be provided on the transparent support.

  The retardation plate of the present invention is used for various applications. It can be used as a polarizing plate by being laminated with an optical compensation sheet of a liquid crystal display device, a linearly polarizing film or a transparent protective film.

  The liquid crystal display device usually includes a liquid crystal cell and a polarizing plate. The polarizing plate has a protective film and a polarizing film, and is usually obtained by dyeing a polarizing film made of a polyvinyl alcohol film with iodine, stretching, and laminating both surfaces with a protective film. In the transmissive liquid crystal display device, the polarizing plate is attached to both sides of the liquid crystal cell, and one or more optical compensation sheets may be disposed. In a reflective liquid crystal display device, a reflector, a liquid crystal cell, one or more optical compensation sheets, and a polarizing plate are usually arranged in this order. The liquid crystal cell includes a liquid crystal molecule, two substrates for encapsulating the liquid crystal molecule, and an electrode layer for applying a voltage to the liquid crystal molecule. The liquid crystal cell performs ON / OFF display depending on the alignment state of liquid crystal molecules, and can be applied to both transmission and reflection types. TN (Twisted Nematic), IPS (In-Plane Switching), OCB (Optically Compensatory Bend). ), VA (Vertical Aligned), ECB (Electrically Controlled Birefringence), and STN (Super Twisted Nematic).

  Optical compensation sheets are used in various liquid crystal display devices in order to eliminate image coloring and expand the viewing angle. As the optical compensation sheet, a stretched birefringent polymer film has been conventionally used. In addition, instead of an optical compensation sheet made of a stretched birefringent polymer film, it has been proposed to use an optical compensation sheet having an optically anisotropic layer formed from low-molecular or high-molecular liquid crystalline molecules on a transparent support. ing. Since liquid crystal molecules have various alignment forms, optical properties that cannot be obtained with conventional stretched birefringent polymer films can be realized by using liquid crystal molecules.

[Polarizer]
The retardation plate of the present invention is preferably used for an actual liquid crystal display element after a linear polarizing film or a transparent protective film is bonded to form a polarizing plate. The polarizing film and the transparent protective film will be described below.

(1) Linearly polarizing film Examples of linearly polarizing films include iodine-based polarizing films, dye-based polarizing films using dichroic dyes, and polyene-based polarizing films. The iodine polarizing film and the dye polarizing film are generally produced using a polyvinyl alcohol film. The transmission axis of the polarizing film corresponds to a direction perpendicular to the stretching direction of the film. When the discotic liquid crystalline compound is used for the optically anisotropic layer, the transmission axis of the polarizing film is arranged so as to be substantially parallel to the surface of the discotic liquid crystalline molecule on the alignment film side. . When a rod-like liquid crystal compound is used, the transmission axis of the polarizing film is arranged so as to be substantially parallel to the major axis direction (slow axis) of the rod-like liquid crystal molecule. Usually, it is preferably bonded to the support side of the retardation plate, but may be bonded to the optically anisotropic layer side if necessary.

(2) Transparent protective film A transparent protective film may be bonded to the optically anisotropic layer side of the retardation plate. As the transparent protective film, a transparent polymer film is preferable. That the protective film is transparent means that the light transmittance is 80% or more. As the transparent protective film, generally a cellulose ester film, preferably a triacetyl cellulose film is used. The cellulose ester film is preferably formed by a solvent cast method. The thickness of the transparent protective film is preferably 20 to 500 μm, and more preferably 50 to 200 μm.

  The present invention will be described more specifically with reference to the following examples. The materials, reagents, ratios, operations and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

[Example 1]
1. Production of Retardation Plate of the Present Invention (1) Formation of Alignment Film An optically isotropic triacetyl cellulose film having a thickness of 100 μm was used as a transparent support. The alignment film polymer (Exemplary Compound AL-2) of the present invention was diluted to 4% by mass in a water / methanol mixture, triethylamine was added as a neutralizing agent, and an alignment film coating solution was prepared. This coating solution was applied to one side of the transparent support, the coating layer was heated at 120 ° C. for 2 minutes, dried, and the surface was rubbed to form an alignment film having a thickness of 1 μm. The following rod-like liquid crystal (V-1) was dissolved in methyl ethyl ketone and applied to this alignment film, and the orientation was confirmed at the liquid crystal temperature. As a result, it was found that the molecular long axis direction was aligned in the direction perpendicular to the rubbing direction. It was.

(2) Formation of optically anisotropic layer On the rubbing treatment surface of the alignment film, a coating solution having the following composition was applied using a bar coater.

――――――――――――――――――――――――――――――――――――
Optically anisotropic layer coating solution ――――――――――――――――――――――――――――――――――――
Liquid crystalline compound of the present invention (D-109) 100 parts by mass photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy Japan, Inc.) 3.0 parts by mass sensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) 1 0 parts by weight surfactant (KK-1) 0.4 parts by weight methyl ethyl ketone 270 parts by weight ――――――――――――――――――――――――――――― ―――――――

(KK-1)

The coating layer was heated at 100 ° C. for 2 minutes to align the discotic liquid crystalline molecules. The liquid crystal molecules were polymerized by irradiating with 600 mJ / cm ² of ultraviolet rays at that temperature, and the alignment state was fixed. Thus, an optically anisotropic layer was formed, and a retardation plate was produced.

[Example 2]
(1) Formation of alignment film An optically isotropic triacetylcellulose film having a thickness of 100 μm was used as a transparent support. The polymer for alignment film of the present invention (acrylic acid copolymer (PA732) described in JP-A No. 2002-98836) is diluted to 4% by mass in a water / methanol mixed solution, triethylamine is added as a neutralizing agent, An alignment film coating solution was prepared. This coating solution was applied to one side of the transparent support, the coating layer was heated at 120 ° C. for 2 minutes, dried, and the surface was rubbed to form an alignment film having a thickness of 1 μm. The rod-like liquid crystal (V-1) was dissolved in methyl ethyl ketone and applied to this alignment film, and the orientation was confirmed at the liquid crystal temperature. As a result, it was found that the molecular long axis direction was aligned in the direction perpendicular to the rubbing direction. It was.

Acrylic acid copolymer (PA732)

(2) Formation of optically anisotropic layer On the rubbing-treated surface of the alignment film, the coating liquid used in Example 1 was applied, and a retardation plate was produced in the same manner as in Example.

[Comparative Example 1]
An optically isotropic triacetyl cellulose film having a thickness of 100 μm was used as a transparent support. PVA-203 (manufactured by Kuraray Co., Ltd.) was diluted to 4% by mass in a water / methanol mixture to prepare an alignment film coating solution. This coating solution was applied to one side of the transparent support, the coating layer was heated at 110 ° C. for 2 minutes, dried, and the surface was rubbed to form an alignment film having a thickness of 1 μm. The rod-like liquid crystal (V-1) was dissolved in methyl ethyl ketone and applied to this alignment film, and the orientation was confirmed at the liquid crystal temperature. As a result, it was found that the molecular major axis direction was aligned parallel to the rubbing direction. It was.

[Evaluation of optical compensation sheet]
The ultrathin section of the cross section of the retardation plate obtained in Examples 1 and 2 was prepared using a microtome, and the slice was observed with a polarizing microscope, so that the retardation plate obtained in Examples 1 and 2 was used. It was confirmed that the optically anisotropic layer was hybrid-oriented.
Next, when the retardation plates obtained in Examples 1 and 2 and Comparative Example 1 were observed with a polarizing microscope, the retardation plates obtained in Examples 1 and 2 showed almost no alignment defect. It was confirmed that the film was uniformly oriented. On the other hand, it was confirmed that the retardation plate obtained in Comparative Example 1 had streak-like defects in the direction parallel to the rubbing direction.

Claims (4)

A retardation plate having an alignment film and an optically anisotropic layer formed of at least one layer of a compound represented by the following general formula (DI) on a transparent support, the alignment film comprising: A retardation film characterized by having a characteristic that a major axis direction of a rod-like liquid crystal can be oriented in a direction substantially orthogonal to a rubbing direction when the rod-like liquid crystal is oriented.
General formula (DI)

In formula (DI), Y ₁₁ , Y ₁₂ and Y ₁₃ each independently represent a methine or nitrogen atom. L ₁ , L ₂ and L ₃ each independently represents a single bond or a divalent linking group. To H _1, H _2, H ₃ each independently represent the following general formula (DI-A) or the following general formula (DI-B).
General formula (DI-A)

[YA ₁ and YA ₂ each independently represents a methine group or a nitrogen atom. XA represents an oxygen atom, a sulfur atom, methylene or imino. * Represents a position where L _{1 to} L ₃ are bonded, and ** represents a position where R _{1 to} R ₃ are bonded. ]
General formula (DI-B)

[YB ₁ and YB ₂ each independently represent a methine group or a nitrogen atom. XB represents an oxygen atom, a sulfur atom, methylene, or imino. * Represents a position where L _{1 to} L ₃ are bonded, and ** represents a position where R _{1 to} R ₃ are bonded. ]
In general formula (DI), R < ₁ >, R < ₂ >, R < ₃ > represents the following general formula (DI-R) each independently.
Formula (DI-R): * - (- L 21 - divalent cyclic group) _n1 -L ₂₂ -L ₂₃ -Q1
[* Represents a position bonded to a 5-membered ring in the general formula (DI). L ₂₁ represents a single bond or a divalent linking group, and the divalent cyclic group represents a divalent linking group having at least one cyclic structure. n1 represents an integer of 0 to 4. L ₂₂ is * —O—, * —O—CO—, * —CO—O—, * —O—CO—O—, * —S—, * —N (R) H—, * —SO ₂ —. , * —CH ₂ —, * —CH═CH—, * —C≡C— (wherein, * represents a position bonded to a benzene ring in formula (DI-R)), In the formula (DI-R), L ₂₃ represents —O—, —S—, —C (═O) —, —SO ₂ —, —NH—, —CH ₂ —, —CH═CH—, —C≡. C— represents a divalent linking group selected from the group consisting of these and combinations thereof. When the above group is a group containing a hydrogen atom, the hydrogen atom may be replaced with a substituent. Q ₁ each independently represents a polymerizable group or a hydrogen atom. ] A retardation plate having an alignment film and at least one optically anisotropic layer formed of the compound represented by the general formula (DI) according to claim 1 on a transparent support. The alignment film is an acrylic acid copolymer or a methacrylic acid copolymer containing a repeating unit represented by the following general formula (I) and a repeating unit represented by the following general formula (II) or (III): A characteristic retardation plate.

In general formulas (I) to (III):
R ₁ and R ₂ are each independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms; M is a proton, an alkali metal ion or an ammonium ion; L0 is —O— , -CO -, - NH -, - SO 2 -, an alkylene group, an alkenylene group, a divalent linking group selected from the group consisting of arylene groups and combinations thereof; R ₀ is the number of carbon atoms is 10 to 100 is a hydrocarbon group or a fluorine atom-substituted hydrocarbon group having 1 to 100 carbon atoms; Cy is an aliphatic ring group, an aromatic group or a heterocyclic group; m is 10 to 99 mol% Yes; and n is from 1 to 90 mol%. A retardation plate having an alignment film and an optically anisotropic layer formed of at least one compound represented by the general formula (DI) according to claim 1 on a transparent support, The alignment film is an alignment film including a polymer having at least one structural unit represented by any one of the following general formula (I-TH), general formula (II-TH), and general formula (III-TH). A retardation plate characterized by being.
General formula (I-TH)

(Wherein R ¹ represents a hydrogen atom, a methyl group, a halogen atom or a cyano group, P ¹ represents an oxygen atom, —CO— or —NR ¹² —, and R ¹² represents a hydrogen atom or a substituted or unsubstituted carbon. Represents an alkyl group having 1 to 6 atoms, and L1 is a substituted or unsubstituted alkylene group, divalent cycloaliphatic group, divalent aromatic group, divalent heterocyclic group and combinations thereof. A divalent linking group selected from the group consisting of X ¹ represents a hydrogen bonding group, and n 1 represents an integer of 1 to 3.)
General formula (II-TH)

(In the formula, R ² represents a hydrogen atom, a methyl group, a halogen atom or a cyano group, L ²¹ represents a substituted or unsubstituted divalent aromatic group or divalent heterocyclic group, and P ²¹ represents a single atom. Represents a bond or a divalent linking group selected from the group consisting of —O—, —NR ²¹ —, —CO—, —S—, —SO—, —SO ₂ — and combinations thereof, and R ²¹ represents hydrogen. Represents an atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and L ²² represents a substituted or unsubstituted alkylene group, divalent cycloaliphatic group, divalent aromatic group, divalent group A divalent linking group selected from the group consisting of a heterocyclic group and a combination thereof is represented, X ² represents a hydrogen bonding group, and n2 is an integer of 0 to ^3. )
General formula (III-TH)

(In the formula, L ³¹ represents a substituted or unsubstituted divalent aromatic group or divalent heterocyclic group, and P ³¹ represents a single bond, —O—, —NR ³¹ —, —CO—, — Represents a divalent linking group selected from the group consisting of S—, —SO—, —SO ₂ — and combinations thereof, and R ³¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. L ³² represents a substituted or unsubstituted divalent linkage selected from the group consisting of an alkylene group, a divalent cycloaliphatic group, a divalent aromatic group, a divalent heterocyclic group, and combinations thereof. Represents a group, X ³ represents a hydrogen bonding group, and n3 is an integer of 0 to ^3. )   4. The retardation plate according to claim 1, wherein the optically anisotropic layer is formed from a liquid crystal compound having a hybrid alignment.