JPWO2018151070A1 - Optical anisotropic - Google Patents

Abstract

In a thin film such as an optical anisotropic body and a retardation film obtained by curing a polymerizable liquid crystal composition, an optical anisotropic body having good orientation after a post-process, high transparency, and high retardation holding ratio is provided. The present invention provides a polymerization initiator (I), a polymerizable liquid crystal compound (II) having two or more polymerizable functional groups in one or two or more molecules, and optionally one or two or more types. A polymerizable liquid crystal compound (II) contained in an optically anisotropic layer using a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound (II-1) having one polymerizable functional group, and optionally contained An optical anisotropic body in which the content of the polymerizable liquid crystal compound (II-1) is 0.0001 mass% or more and 3 mass% or less is provided.

Description

  The present invention relates to an optical anisotropic member used for optical compensation and viewing angle compensation of a liquid crystal display, an optical anisotropic member used for an organic EL, etc., or an optical anisotropic member used for an optical element. , Retardation film, retardation patterning film, brightness enhancement film, antireflection film, thermal barrier film, laminate having a protective layer on the optical anisotropic body, and optical anisotropic body, retardation film, phase difference patterning The present invention relates to a liquid crystal display device, an image display device, an optical element, and a printed matter having a film, a brightness enhancement film, an antireflection film, and a heat shielding film.

  The polymerizable liquid crystal composition is useful as a constituent member of an optical anisotropic body, and the optical anisotropic body is applied to various liquid crystal displays as, for example, a polarizing film and a retardation film. The polarizing film and the retardation film are coated with a polymerizable liquid crystal composition on a substrate, dried with a solvent to form a coating film, and then heated or activated in a state where the polymerizable liquid crystal composition is aligned with an alignment film or the like. It is obtained by irradiating energy rays to cure the polymerizable liquid crystal composition. In particular, the polymerizable liquid crystal composition is applied to a retardation film, a retardation patterning film, a brightness enhancement film, an antireflection film, a heat shielding film, various optical elements such as a diffraction grating and a pickup lens, and an anti-counterfeit printed matter. Applications are being studied.

  When the optical anisotropic body is used for a constituent member such as a liquid crystal display device or an image display device, heat resistance is required. Patent Document 1 discloses that by using a liquid crystal compound having four or more rings such as a benzene ring and a cyclohexane ring, a retardation film having excellent heat resistance can be created in the baking treatment after the retardation film is formed. ing. In liquid crystal display devices, image display devices, etc., there are a firing step, a transparent electrode sputtering step, and a re-baking step after the retardation film is formed, and the orientation of the retardation film is good even after the firing step and the sputtering step. It is required to be. However, in Patent Document 1, the orientation may be deteriorated depending on the polymerizable liquid crystal composition. Further, in Patent Document 2, by adding a multi-branched compound such as a dendrimer to the polymerizable liquid crystal composition, the retardation unevenness is small, and the surface shape change of the retardation film is changed even after the firing process after the retardation film is formed. In addition, it is disclosed that a retardation film can be obtained in which cracks are not generated even in the sputtering step of the transparent electrode, which is a subsequent step of the firing step. However, in Patent Document 2, although a retardation film that does not generate cracks can be obtained, the transparency and retardation holding ratio of the retardation film after the firing process and the sputtering process are not disclosed, and there is room for further improvement. there were.

JP 2011-148761 A JP 2010-138283 A

  The problem to be solved by the present invention is to provide an optical anisotropic body that has good orientation and high transparency and retardation retention even after the firing process and sputtering process after the retardation film formation. is there. In addition, another object is to provide a liquid crystal display device, an image display device, an optical element, and a printed matter having a retardation film, a retardation patterning film, a brightness enhancement film, an antireflection film, and a thermal barrier film.

  In order to solve the above-mentioned problems, the present invention has been conducted by paying attention to the amount of residual monomer contained in the optically anisotropic layer, and as a result, has come to provide the present invention.

  That is, the present invention relates to one or more polymerization initiators (I), one or two or more polymerizable liquid crystal compounds (II) having two or more polymerizable functional groups in the molecule, and Optionally comprising an optically anisotropic layer using a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound (II-1) having one or more kinds of one polymerizable functional group, An optically anisotropic body in which the content of the polymerizable liquid crystal compound (II) contained in the rectangular layer and the polymerizable liquid crystal compound (II-1) optionally contained is 0.0001 mass% or more and 3 mass% or less. provide.

  The optical anisotropic body of the present invention is an optical anisotropic body that has good orientation after the firing step and sputtering step, and has high transparency and retardation retention, so it can be used for various optical materials such as optical films. Useful.

It is a figure which shows an example of the liquid crystal display device of this invention. It is a figure which shows an example of the liquid crystal display device of this invention. It is a figure which shows an example of the liquid crystal display device of this invention. It is a figure which shows an example of the liquid crystal display device of this invention. It is a figure which shows an example of the liquid crystal display device of this invention. It is a figure which shows an example of the liquid crystal display device of this invention. It is a figure which shows an example of the liquid crystal display device of this invention. It is a figure which shows an example of the liquid crystal display device of this invention. It is a figure which shows an example of the liquid crystal display device of this invention. It is a figure which shows an example of the liquid crystal display device of this invention. It is a figure which shows an example of the liquid crystal display device of this invention. It is a figure which shows an example of the liquid crystal display device of this invention. It is a figure which shows an example of the liquid crystal display device of this invention.

(1) Polarizing layer (2) Adhesive layer (3) Light transmissive substrate (4) Color filter layer (5) Flattening layer (6) Alignment film for retardation film (7) Polymerizable liquid crystal composition was used. Retardation film 1
(8) Retardation film 2 using polymerizable liquid crystal composition
(9) Transparent electrode layer (10) Alignment film (11) Liquid crystal composition (12) Alignment film (13) Pixel electrode layer (14) Light transmissive substrate (15) Adhesive layer (16) Polarizing layer (17) Back Light

The best mode of the optical anisotropic body according to the present invention will be described below. In the present invention, the “liquid crystal” of the polymerizable liquid crystal composition used for producing the optical anisotropic body is based on the polymerizable liquid crystal composition. It is intended to exhibit liquid crystallinity in a state where the organic solvent is removed after application to the material. In the present invention, the “liquid crystal” of the polymerizable liquid crystal compound means a case where it is intended to show liquid crystal properties with only one type of polymerizable liquid crystal compound used, or a mixture with other liquid crystal compounds. It is intended to exhibit liquid crystal properties. The polymerizable liquid crystal composition can be polymerized (formed into a film) by performing a polymerization treatment by irradiation with light such as ultraviolet rays, heating, or a combination thereof.
(Polymerizable liquid crystal compound)
The polymerizable liquid crystal compound used in the present invention is not particularly limited as long as it is a compound that exhibits liquid crystallinity alone or in a composition with another compound and has at least one polymerizable functional group. Conventional ones can be used.

For example, Handbook of Liquid Crystals (D. Demus, JW Goodby, GW Gray, WW Spies, V. Vill, published by Wiley-VCH, 1998), Quarterly Chemical Review No. 22, Liquid Crystal Chemistry (Edited by Chemical Society of Japan, 1994), or JP-A-7-294735, JP-A-8-3111, JP-A-8-29618, JP-A-11-80090, A rigid site called mesogen in which a plurality of structures such as 1,4-phenylene group and 1,4-cyclohexylene group are connected as described in Kaihei 11-116538, JP-A-11-148079, etc. A rod-like polymerizable liquid crystal compound having a polymerizable functional group such as a vinyl group, an acrylic group, or a (meth) acryl group, or a maleimide as described in JP-A Nos. 2004-2373 and 2004-99446 Examples thereof include a rod-like polymerizable liquid crystal compound having a group. Among these, a rod-like liquid crystal compound having a polymerizable group is preferable because it is easy to produce a liquid crystal temperature range including a low temperature around room temperature.
(Polyfunctional polymerizable liquid crystal compound)
The optical anisotropic body of the present invention is produced using a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound (II) having two or more polymerizable functional groups in the molecule. Specifically, the polymerizable liquid crystal compound (II) having two or more polymerizable functional groups in the molecule is preferably a compound represented by the following general formula (II-A).

  Formula (II-A)

In the general formula (II-A), P ²¹ represents a polymerizable functional group,
In the general formula (II-A), Sp ²¹ represents an alkylene group having 1 to 18 carbon atoms (the hydrogen atom in the alkylene group represents one or more halogen atoms, a CN group, or a polymerizable functional group). One CH ₂ group present in the alkylene group or two or more CH ₂ groups which are not adjacent to each other independently of each other are independently represented by —O—, —COO—, -OCO- or -OCO-O- may be substituted).
In the general formula ^(II-A), X 21 is _{-O -, - S -, -} OCH 2 -, - CH 2 O -, - CO -, - COO -, - OCO -, - CO-S-, -S-CO -, - O- CO-O -, - CO-NH -, - NH-CO -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - CF ₂ S—, —SCF ₂ —, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —COO—CH ₂ CH ₂ —, _{-OCO-CH 2 CH 2 -,} - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH _{2 -OCO -, - CH = CH} -, - N = N -, - CH = N-N = CH -, - CF = CF -, - C≡C- or a single Represents the total, ^(however, P 21 ^{-Sp 21,} and ^Sp 21 ^-X 21 are, -O-O -, - O -NH - -, do not contain S-S- and -O-S- group.)
In the general formula (II-A), q21 represents 0 or 1,
In the general formula (II-A), MG represents a mesogenic group,
In the general formula (II-A), R ²¹ represents the general formula (II-a).

(In the above general formula (II-a), P ²² represents a polymerizable functional group, Sp ²² represents the same as defined in Sp ²¹ , and X ²² represents that defined in X ^21. (However, P ²² -Sp ²² and Sp ²² -X ²² do not include —O—O—, —O—NH—, —S—S— and —O—S— groups.) .), Q22 represents 0 or 1.)
In the above general formula (II-A), the mesogenic group represented by MG has the general formula (II-b)

(In the general formula (II-b), B1, B2 and B3 are each independently 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2, 5-diyl group, 1,3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene-2, 6-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group-, 1,2,3,4 Tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4,4a, 9,10a-o Tahydrophenanthrene-2,7-diyl group, 1,4-naphthylene group, benzo [1,2-b: 4,5-b ′] dithiophene-2,6-diyl group, benzo [1,2-b: 4,5-b ′] diselenophen-2,6-diyl group, [1] benzothieno [3,2-b] thiophene-2,7-diyl group, [1] benzoselenopheno [3,2-b] selenophene 2,7 represents a diyl group, or a fluorene-2,7-diyl group, one or more F as _{substituents, Cl, CF 3, OCF 3} , CN group, an alkyl group having 1 to 8 carbon atoms ( hydrogen atoms in the alkyl group may be substituted with one or more phenyl groups, in each of two or more CH ₂ groups not one CH ₂ group or adjacent present in this group interconversion Independently, -O-, -COO-, -OCO- or -O O—O— may be substituted.), An alkoxy group having 1 to 8 carbon atoms, an alkanoyl group having 1 to 8 carbon atoms, an alkanoyloxy group having 1 to 8 carbon atoms, and 1 to 1 carbon atoms An alkoxycarbonyl group having 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkenyloxy group having 2 to 8 carbon atoms, an alkenoyl group having 2 to 8 carbon atoms, an alkenoyloxy group having 2 to 8 carbon atoms, and / Or general formula (II-c) as a substituent

(In the above formula (II-c), P ²³ represents a polymerizable functional group,
Sp ²³ represents the same as defined in Sp ²¹ above,
X ²³ represents —O—, —COO—, —OCO—, —OCH ₂ —, —CH ₂ O—, —CH ₂ CH ₂ OCO—, —COOCH ₂ CH ₂ —, —OCOCH ₂ CH ₂ —, or A single bond is represented, q23 represents 0 or 1, and q24 represents 0 or 1. (However, P ²³ -Sp ²³ and Sp ²³ -X ²³ do not include —O—O—, —O—NH—, —S—S— and —O—S— groups). You may,
In the general formula (II-b), Z 1 and Z 2 are each independently —COO—, —OCO—, —CH ₂ CH ₂ —, —OCH ₂ —, —CH ₂ O—, —CH═CH—. , —C≡C—, —CH═CHCOO—, —OCOCH═CH—, —CH ₂ CH ₂ COO—, —CH ₂ CH ₂ OCO—, —COOCH ₂ CH ₂ —, —OCOCH ₂ CH ₂ —, — C═N—, —N═C—, —CONH—, —NHCO—, —C (CF ₃ ) ₂ —, an alkyl group having 2 to 10 carbon atoms which may have a halogen atom, or a single bond. However, when Z1 and Z2 represent a single bond, among the above B1, B2 and B3, the substituents which two adjacent ring structures each have may be combined to form a cyclic group, and r1 is Represents 0, 1, 2 or 3, and when there are a plurality of B1 and Z1, It may be one or different. ).

As described above, in the general formula (II-A), Sp ²¹ represents an alkylene group having 1 to 18 carbon atoms, and the hydrogen atom in the alkylene group is substituted with a group having a polymerizable functional group. However, examples of a group preferable as the group having the polymerizable functional group include a group represented by the general formula (II-c).

In the general formula (II-A), general formula (II-a), and general formula (II-c), P ²¹ , P ^22, and P ²³ are each independently represented by the following formula (P-2-1 To a substituent selected from polymerizable groups represented by formula (P-2-20).

  Among these polymerizable functional groups, from the viewpoint of increasing the polymerizability, the formulas (P-2-1), (P-2-2), (P-2-7), (P-2-12), ( P-2-13) is preferable, and formulas (P-2-1), (P-2-2), and (P-2-7) are more preferable.

  In the general formula (II-b), B1, B2 and B3 may each independently have the above-described substituents, 1,4-phenylene group, 1,4-cyclohexylene group, 2,6 -It preferably represents a naphthylene group.

In the general formula (II-A), general formula (II-a), and general formula (II-c), Sp ²¹ , Sp ²² and Sp ²³ are each independently carbon from the viewpoint of enhancing storage stability. it is preferable that an alkylene group of atoms 1-14, each two or more CH ₂ groups not one CH ₂ group or adjacent existing in the alkylene group independently of one another, -O-, It may be replaced by -COO- or -OCO-. Sp ²¹ , Sp ²² and Sp ²³ are each more preferably independently an alkylene group having 1 to 12 carbon atoms, and are not adjacent to one CH ₂ group present in the alkylene group. Two or more CH ₂ groups may be replaced by —O—.

In the general formula (II-A), general formula (II-a), and general formula (II-c), X ²¹ , X ^22, and X ²³ are each independently —O—, —OCH ₂ —, —CH ₂ O—, —CO—, —COO—, —OCO—, —O—CO—O—, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, _{-OCO-CH = CH -, -} COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 - , —OCO—CH ₂ —, —CH ₂ —COO—, —CH ₂ —OCO—, —CH═CH—, —C≡C— or a single bond are preferred, —O—, —COO—, -OCO-, or is more preferably a single bond (provided ^that, P ²¹ -Sp ^{21, Sp 21 X 21, P 22 -Sp 22,} Sp 22 -X 22, P 23 -Sp 23, and ^Sp 23 ^-X 23 are, -O-O -, - O -NH -, - S-S- and -O- S-group is not included.)

In the general formula (II-b), Z1 and Z2 are each independently —COO—, —OCO—, —CH ₂ O—, —CH═CH—, —C≡C—, —CH ₂ CH _{2. COO -, - CH 2 CH 2} OCO -, - COOCH 2 CH 2 -, - OCOCH 2 CH 2 -, - C = N -, - N = C-, or preferably represents a single bond.

In the general formula (II-b), r1 preferably represents 0 or 1.
(Bifunctional polymerizable liquid crystal compound)
The optical anisotropic body of the present invention is produced using a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound (II) having two or more polymerizable functional groups in the molecule. The product preferably contains a bifunctional polymerizable liquid crystal compound having two polymerizable functional groups in the molecule. As the bifunctional polymerizable liquid crystal compound having two polymerizable functional groups in the molecule, a compound represented by the following general formula (II-2) is preferable.

In the general formula (II-2), P ²²¹ , X ²¹¹ , q ²²¹ , X ²²² , q ²²² , and P ²²² are P ²¹ , X ^{21 in the} general formula (II) or the general formula (II-a), respectively. represent the same as the definition of ^{q21, X 22, q22, P} 22,
In general formula (II-2), Sp ²²¹ and Sp ²²² each independently represent an alkylene group having 1 to 18 carbon atoms (the hydrogen atom in the alkylene group is one or more halogen atoms, or CN It may be substituted by a group, two or more of CH ₂ groups, independently of one another each of the present in the radical is not one CH ₂ group or adjacent, -O -, - COO -, - OCO -Or -OCO-O- may be substituted).
In the general formula (II-2), MG ² represents a mesogenic group, and as the mesogenic group, the general formula (II-2-b)

(In the general formula (II-2-b), B11, B21 and B31 are each independently 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran- 2,5-diyl group, 1,3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene- 2,6-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group-, 1,2,3 4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4, 4a, 9, 0a-octahydrophenanthrene-2,7-diyl group, 1,4-naphthylene group, benzo [1,2-b: 4,5-b ′] dithiophene-2,6-diyl group, benzo [1,2- b: 4,5-b ′] diselenophen-2,6-diyl group, [1] benzothieno [3,2-b] thiophene-2,7-diyl group, [1] benzoselenopheno [3,2-b ] Represents a selenophene-2,7-diyl group or a fluorene-2,7-diyl group, and has at least one F, Cl, CF ₃ , OCF ₃ , CN group or an alkyl having 1 to 8 carbon atoms as a substituent. group (the hydrogen atom in the alkyl group may be substituted with one or more phenyl groups, each of two or more CH ₂ groups not one CH ₂ group or adjacent present in this group Independently of each other, -O-, -COO-, -OCO Or may be replaced by -OCO-O-), an alkoxy group having 1 to 8 carbon atoms, an alkanoyl group having 1 to 8 carbon atoms, an alkanoyloxy group having 1 to 8 carbon atoms, or the number of carbon atoms May have an alkoxycarbonyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkenyloxy group having 2 to 8 carbon atoms, and / or an alkenoyl group having 2 to 8 carbon atoms,
In the general formula (II-2-b), Z11 and Z21 are each independently —COO—, —OCO—, —CH ₂ CH ₂ —, —OCH ₂ —, —CH ₂ O—, —CH═. CH—, —C≡C—, —CH═CHCOO—, —OCOCH═CH—, —CH ₂ CH ₂ COO—, —CH ₂ CH ₂ OCO—, —COOCH ₂ CH ₂ —, —OCOCH ₂ CH ₂ — , -C = N -, - N = C -, - CONH -, - NHCO -, - C (CF 3) 2 -, alkyl group or a single bond may C2-10 have a halogen atom R11 represents 0, 1, 2 or 3, and when there are a plurality of B11 and Z11, they may be the same or different, but Z11 and Z21 each represent a single bond B11, B21 and B31, two adjacent ring structures Substituents each having a structure may combine to form a cyclic group. ) Is preferred.

In the general formula (II-2), P ²²¹ and P ²²² are each independently from the viewpoint of enhancing the polymerizability, and the above formulas (P-2-1), (P-2-2), (P- 2-7), (P-2-12), and (P-2-13) are preferable, and Formulas (P-2-1) and (P-2-2) are more preferable.

In the general formula (II-2), Sp ²²¹ and Sp ²²² are preferably each independently an alkylene group having 1 to 14 carbon atoms, from the viewpoint of enhancing storage stability. One CH ₂ group present or two or more non-adjacent CH ₂ groups may each be independently replaced by —O—, —COO— or —OCO—. Sp ²²¹ and Sp ²²² are more preferably each independently an alkylene group having 1 to 12 carbon atoms, and one CH ₂ group present in the alkylene group or two or more not adjacent to each other. The CH ₂ group may be replaced by —O—.

In the general formula (II-2), X ²²¹ and X ²²² each independently represent —O—, —OCH ₂ —, —CH ₂ O—, —CO—, —COO—, —OCO—, — O—CO—O—, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —COO—CH ₂ CH ₂ —, —OCO _{-CH 2 CH 2 -, - CH} 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 - It preferably represents OCO-, -CH = CH-, -C≡C- or a single bond, and more preferably represents -O-, -COO-, -OCO- or a single bond (provided that P ^{221- Sp 221, Sp 221 -X 221,} P 222 -Sp 222,及Sp ²²² -X ²²² may, -O-O -, - O -NH -, - does not contain S-S- and -O-S- group)..

In the above general formula (II-2-b), B11, B21 and B31 each independently may have the above-described substituents such as 1,4-phenylene group, 1,4-cyclohexylene group, 2 , 6-naphthylene group, Z11 and Z21 are each independently —COO—, —OCO—, —CH ₂ CH ₂ —, —OCH ₂ —, —CH ₂ O—, —CH═CH. -, -C≡C-, -C = N-, -N = C-, or a single bond is preferable, and r11 preferably represents 0 or 1.

  Examples of the general formula (II-2) include compounds represented by the following general formulas (II-2-1) to (II-2-4), but are not limited to the following general formulas. is not.

In the general formulas (II-2-1) to (II-2-4), P ²²¹ , Sp ²²¹ , X ²²¹ , q ²²¹ , X ²²² , Sp ²²² , q ²²² , and P ²²² are respectively the above general formulas. Represents the same as the definition of (II-2), and the preferred group also represents the same as the definition of the general formula (II-2);
In the general formulas (II-2-1) to (II-2-4), B111, B112, B113, B21, and B31 are the same as the definitions of B11 to B31 in the general formula (II-2-b). And preferred groups also represent the same definitions as B11 to B31, and may be the same or different,
In the general formulas (II-2-1) to (II-2-4), Z111, Z112, Z113, and Z21 represent the same definitions as Z11 to Z21 in the general formula (II-2-b). Preferred groups also represent the same definitions as Z11 to Z21, and may be the same or different.

  Among the compounds represented by the general formulas (II-2-1) to (II-2-4), the compounds represented by the general formulas (II-2-2) to (II-2-4) It is preferable to use a compound having three or more ring structures because the orientation of the resulting film is good and the curability is good, and the general formula (II-2-2) having three ring structures in the compound is preferable. It is particularly preferable to use the compound represented by 2).

  Examples of the compounds represented by the general formulas (II-2-1) to (II-2-4) include the following general formulas (II-2-1-1) to (II-2-1-25) ) Is exemplified, but not limited thereto.

In the formula, R ^d and R ^e each independently represent a hydrogen atom or a methyl group,
The cyclic group has one or more F, Cl, CF ₃ , OCF ₃ , CN groups, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and 1 to 1 carbon atoms as a substituent. 8 alkanoyl groups, alkanoyloxy groups having 1 to 8 carbon atoms, alkoxycarbonyl groups having 1 to 8 carbon atoms, alkenyl groups having 2 to 8 carbon atoms, alkenyloxy groups having 2 to 8 carbon atoms, carbon atoms It may have an alkenoyl group having 2 to 8 carbon atoms and an alkenoyloxy group having 2 to 8 carbon atoms.

  m1, m2, m3, and m4 each independently represent an integer of 0 to 8, and n1, n2, n3, and n4 each independently represent 0 or 1.

  The compounds represented by the above general formula (II-2-1-1) to general formula (II-2-1-25) are more specifically represented by the following general formula (II-2-2-1) to general formula Although the compound represented by (II-2-2-36) can be illustrated, it is not necessarily limited to these.

  Although 1 type, or 2 or more types can be used for the polymeric liquid crystal compound which has two polymeric functional groups, 1 type-5 types are preferable and 2 types-5 types are more preferable.

General formula (II-2), general formula (II-2-1) to general formula (II-2-4), general formula (II-2-1-1) to general formula (II-2) -1-21), or a polymerizability represented by general formula (II-2-2-1) to general formula (II-2-2-36) having two polymerizable functional groups in the molecule The total content of the liquid crystal compounds is such that the polymerizable liquid crystal compound (II), polymerizable liquid crystal compound (II-1) and The total content of the chiral compound (III) is preferably 20 to 100% by mass, more preferably 25 to 100% by mass, and particularly preferably 30 to 100% by mass. When importance is attached to the curability of the resulting coating film, the lower limit is preferably 40% by mass or more, and more preferably 50% by mass or more.
(Polyfunctional polymerizable liquid crystal compound)
The optical anisotropic body of the present invention is produced using a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound (II) having two or more polymerizable functional groups in the molecule. The product may contain a polyfunctional polymerizable liquid crystal compound having three or more polymerizable functional groups. As the polyfunctional polymerizable liquid crystal compound having three or more polymerizable functional groups, it is preferable to use a compound having three polymerizable functional groups. Among the compounds represented by the general formula (II-A), as a polyfunctional polymerizable liquid crystal compound having 3 or 4 polymerizable functional groups in the molecule, the following general formula (II-3-1) to The compound represented by general formula (II-3-2) can be illustrated.

The general formula (II-3-1) ~ the general formula ^{(II-3-2), P 231} , X 231, q231, X 232, q232, P 232, P 233, X 233, q234, q233, X 234 , Q236, q235, P ²³⁴ , X ²³⁵ , q238, q237, and P ²³⁵ are P ²¹ and X ^{21 in} the above general formula (II), general formula (II-a), and general formula (II-c), respectively. represent the same as the definition of ^{q21, X 22, q22, P} 22, P 23, X 23, q24, q23, X 23, q24, q23, P 23, X 23, q24, q23, P 23,
In General Formula (II-3-1) to General Formula (II-3-2), Sp ²³¹ , Sp ²³² , Sp ²³³ , Sp ²³⁴ and Sp ²³⁵ are each independently an alkylene having 1 to 18 carbon atoms. Represents a group (the hydrogen atom in the alkylene group may be substituted by one or more halogen atoms or CN groups, one CH ₂ group present in the group or two or more non-adjacent ones) And each CH ₂ group may be independently replaced by —O—, —COO—, —OCO— or —OCO—O—.
In the general formula (II-3-2), j3 represents 0 or 1,
In the general formula (II-3-1) to general formula (II-3-2), MG ³ represents a mesogenic group, and the mesogenic group includes the general formula (II-3-b).

(In the general formula (II-3-b), B11, B21 and B31 are each independently 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran- 2,5-diyl group, 1,3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene- 2,6-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group-, 1,2,3 4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4, 4a, 9, 0a-octahydrophenanthrene-2,7-diyl group, 1,4-naphthylene group, benzo [1,2-b: 4,5-b ′] dithiophene-2,6-diyl group, benzo [1,2- b: 4,5-b ′] diselenophen-2,6-diyl group, [1] benzothieno [3,2-b] thiophene-2,7-diyl group, [1] benzoselenopheno [3,2-b ] Represents a selenophene-2,7-diyl group or a fluorene-2,7-diyl group, and has at least one F, Cl, CF ₃ , OCF ₃ , CN group or an alkyl having 1 to 8 carbon atoms as a substituent. group (the hydrogen atom in the alkyl group may be substituted with one or more phenyl groups, each of two or more CH ₂ groups not one CH ₂ group or adjacent present in this group Independently of each other, -O-, -COO-, -OCO Or may be replaced by -OCO-O-), an alkoxy group having 1 to 8 carbon atoms, an alkanoyl group having 1 to 8 carbon atoms, an alkanoyloxy group having 1 to 8 carbon atoms, or the number of carbon atoms An alkoxycarbonyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkenyloxy group having 2 to 8 carbon atoms, and / or an alkenoyl group having 2 to 8 carbon atoms,
In the general formula (II-3-b), the Z11 and Z21 each independently, -COO -, - OCO -, - CH 2 CH 2 -, - OCH 2 -, - CH 2 O -, - CH = CH—, —C≡C—, —CH═CHCOO—, —OCOCH═CH—, —CH ₂ CH ₂ COO—, —CH ₂ CH ₂ OCO—, —COOCH ₂ CH ₂ —, —OCOCH ₂ CH ₂ — , -C = N -, - N = C -, - CONH -, - NHCO -, - C (CF 3) 2 -, alkyl group or a single bond may C2-10 have a halogen atom R11 represents 0, 1, 2, or 3, and when there are a plurality of B11 and Z11, they may be the same or different. In the case where Z11 and Z21 represent a single bond, the substituents of the two adjacent ring structures among B11, B21 and B31 are combined to form a cyclic group. Well,
In the general formula (II-3-1) to general formula (II-3-2), P ²³¹ , P ²³² , P ²³³ , P ²³⁴ , and P ²³⁵ are each independently from the viewpoint of increasing the polymerizability, The above formulas (P-2-1), (P-2-2), (P-2-7), (P-2-12), and (P-2-13) are preferable, and the formula (P-2 -1) and (P-2-2) are more preferable.

In the above general formula (II-3-1) to general formula (II-3-2), Sp ²³¹ , Sp ²³² , Sp ²³³ , Sp ²³⁴ and Sp ²³⁵ are each independently from the viewpoint of enhancing storage stability. , preferably represents an alkylene group having 1 to 14 carbon atoms, and each of the two or more CH ₂ groups not one CH ₂ group or adjacent existing in the alkylene group independently of one another, -O It may be replaced by-, -COO- or -OCO-. Further, Sp ²³¹ , Sp ²³² , Sp ²³³ , Sp ²³⁴ and Sp ²³⁵ each independently preferably represent an alkylene group having 1 to 12 carbon atoms, and one CH ₂ present in the alkylene group. A group or two or more non-adjacent CH ₂ groups may be replaced by —O—.

In the above general formula (II-3-1) to general formula (II-3-2), X ²³¹ , X ²³² , X ²³³ , X ²³⁴ and X ²³⁵ are each independently —O—, —OCH _{2. -, - CH 2 O -,} - CO -, - COO -, - OCO -, - OCO-O -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH _{-, - OCO-CH = CH} -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH _2- , —OCO—CH ₂ —, —CH ₂ —COO—, —CH ₂ —OCO—, —CH═CH—, —C≡C— or a single bond is preferably represented, —O—, —COO -, - OCO-, or more preferably a single bond (provided ^{that, P} 231 -S ^{231, Sp 231 -X 231, P} 232 -Sp 232, Sp 232 -X 232, P 233 -Sp 233, Sp 233 -X 233, P 234 -Sp 234, Sp 234 -X 234, P 235 -Sp 235, And Sp ²³⁵ -X ²³⁵ does not include -O-O-, -O-NH-, -S-S-, and -O-S- groups.

In the general formula (II-3-b), B11, B21 and B31 each independently may have the above-described substituents such as 1,4-phenylene group, 1,4-cyclohexylene group, 2 , 6-naphthylene group, Z11 and Z21 are each independently —COO—, —OCO—, —CH ₂ CH ₂ —, —OCH ₂ —, —CH ₂ O—, —CH═CH. -, -C≡C-, -C = N-, -N = C-, or a single bond is preferable, and r11 preferably represents 0 or 1.

In the general formula (II-3-1), in _{^{MG 3, - (X 233)}} q234 - group having represented by polymerizable groups _{(Sp ²³³⁾ q233} ^-P ₂₃₃ groups are present in the MG ³ Substitution as a substituent of B11, B21 and / or B31.

In the general formula (II-3-2), in the Sp group,-(X ²³⁴ ) _{q 236-} (Sp ²³⁴ ) _{q 235} -P ²³⁴ group and existing-(X ²³⁴ ) _{q 236-} (Sp ²³⁴ ) _{q 235-} The group having a polymerizable group represented by the P ²³⁴ group is substituted with a hydrogen atom in the alkylene group present in the Sp group.

  Examples of the compounds represented by the above general formula (II-3-1) to general formula (II-3-2) include the following general formulas (II-3-3-1) to (II-3-3-10). ), But is not limited to the following general formula.

In formula (II-3-3-1) ~ (II -3-3-10), P 231 ~P 235, Sp 231 ~Sp 235, X 231 ~X 235, q231~q238, MG 3 are, Each represents the same definition as in general formula (II-3-1) to general formula (II-3-2).

  In the general formulas (II-3-3-1) to (II-3-3-10), B111, B112, B113, B21, and B31 are respectively B11 of the general formula (II-3-b), It represents the same thing as the definition of B21 and B31, and the preferable group also represents the same thing as the definition of B11 to B31, and may be the same or different.

  In the general formulas (II-3-3-1) to (II-3-3-10), Z111, Z112, Z113, and Z21 are the same as Z11 and Z21 in the general formula (II-3-b), respectively. It represents the same as the definition, and preferred groups also represent the same as the definitions of Z11 to Z21, and may be the same or different.

  Examples of the compounds represented by the general formulas (II-3-3-1) to (II-3-3-10) include the following formulas (II-3-3-3-1) to (II-3). Although the compound represented by -3-3-3) is illustrated, it is not limited thereto.

In the formula, R ^f , R ^g, and R ^h each independently represent a hydrogen atom or a methyl group, and R ⁱ , R ^j, and R ^k are each independently a hydrogen atom, a halogen atom, or a carbon number of 1 to 6 An alkyl group, an alkoxy group having 1 to 6 carbon atoms, a cyano group, and when these groups are an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, all are unsubstituted, Alternatively, it may be substituted with one or two or more halogen atoms, and the cyclic group has one or more F, Cl, CF ₃ , OCF ₃ , CN groups, C 1-8 carbon atoms as substituents. An alkyl group, an alkoxy group having 1 to 8 carbon atoms, an alkanoyl group having 1 to 8 carbon atoms, an alkanoyloxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, and 2 to 2 carbon atoms. 8 alkenyl groups, carbon atoms Number 2-8 alkenyloxy group, alkenoyl group having 2 to 8 carbon atoms, which may have a alkenoyloxy group having from 2 to 8 carbon atoms.
m4 to m9 each independently represents an integer of 0 to 18, and n4 to n9 each independently represents 0 or 1.

  The polyfunctional polymerizable liquid crystal compound having three or more polymerizable functional groups can be used alone or in combination of two or more.

The optical anisotropic body of the present invention is produced using a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound (II) having two or more polymerizable functional groups in the molecule. In the product, the total content of the polyfunctional polymerizable liquid crystal compound having three or more polymerizable functional groups in the molecule is the polymerizable liquid crystal compound (II), polymerizable liquid crystal compound ( Of the total content of II-1) and chiral compound (III), it is preferably 0 to 80% by mass, more preferably 0 to 60% by mass, and particularly preferably 0 to 40% by mass. . When importance is attached to the rigidity of the obtained film, the lower limit is preferably 10% by mass or more, more preferably 20% by mass or more, and particularly preferably 30% by mass or more, When emphasizing the low curing shrinkage of the resulting film, the upper limit is preferably 50% by mass or less, more preferably 35% by mass or less, and particularly preferably 20% by mass or less.
(Monofunctional polymerizable liquid crystal compound)
The optical anisotropic body of the present invention is produced using a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound (II) having two or more polymerizable functional groups in the molecule. The product may contain a monofunctional polymerizable liquid crystal compound having one polymerizable functional group in the molecule as an optional component. As the monofunctional polymerizable liquid crystal compound having one polymerizable functional group in the molecule, a compound represented by the following general formula (II-1) is preferable.

In the general formula (II-1), P ²¹¹ represents a polymerizable functional group,
In the general formula (II-1), X ²¹¹ represents —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CO—, —COO—, —OCO—, —CO—S—, — S-CO -, - O- CO-O -, - CO-NH -, - NH-CO -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - CF 2 S—, —SCF ₂ —, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —COO—CH ₂ CH ₂ —, — OCO—CH ₂ CH ₂ —, —CH ₂ CH ₂ —COO—, —CH ₂ CH ₂ —OCO—, —COO—CH ₂ —, —OCO—CH ₂ —, —CH ₂ —COO—, —CH ₂ -OCO-, -CH = CH-, -N = N-, -CH = NN-CH-, -CF = CF-, -C≡C- or single bond The stands, ^(however, P 211 ^{-Sp 211,} and ^Sp 211 ^{-X 211} may, -O-O -, - O -NH - -, do not contain S-S- and -O-S- group.)
In general formula (II-1), q211 represents 0 or 1,
In General Formula (II-1), R ²¹¹ represents a hydrogen atom, a halogen atom, a cyano group, one —CH ₂ —, or two or more non-adjacent —CH ₂ — each independently —O—. , -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-,- NH—, —N (CH ₃ ) —, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —CH═CH—, — A linear or branched alkyl group having 1 to 12 carbon atoms and a linear or branched alkenyl group having 1 to 12 carbon atoms, which may be substituted by CF═CF— or —C≡C—, and the alkyl group , One or more hydrogen atoms of the alkenyl group are substituted with a halogen atom or a cyano group If multiple substitutions are made, they may be the same or different,
In the general formula (II-1), Sp ²¹¹ represents an alkylene group having 1 to 18 carbon atoms (the hydrogen atom in the alkylene group may be substituted with one or more halogen atoms or a CN group). In this group, one CH ₂ group or two or more non-adjacent CH ₂ groups are independently of each other by —O—, —COO—, —OCO— or —OCO—O—. May be replaced)
In the general formula (II-1), MG ¹ represents a mesogenic group, and the mesogenic group includes the general formula (II-1-b)

(In the above general formula (II-1-b), B11, B21 and B31 are each independently 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran- 2,5-diyl group, 1,3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene- 2,6-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group-, 1,2,3 4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4, 4a, 9, 0a-octahydrophenanthrene-2,7-diyl group, 1,4-naphthylene group, benzo [1,2-b: 4,5-b ′] dithiophene-2,6-diyl group, benzo [1,2- b: 4,5-b ′] diselenophen-2,6-diyl group, [1] benzothieno [3,2-b] thiophene-2,7-diyl group, [1] benzoselenopheno [3,2-b ] Represents a selenophene-2,7-diyl group or a fluorene-2,7-diyl group, and has at least one F, Cl, CF ₃ , OCF ₃ , CN group or an alkyl having 1 to 8 carbon atoms as a substituent. group (the hydrogen atom in the alkyl group may be substituted with one or more phenyl groups, each of two or more CH ₂ groups not one CH ₂ group or adjacent present in this group Independently of each other, -O-, -COO-, -OCO Or may be replaced by -OCO-O-), an alkoxy group having 1 to 8 carbon atoms, an alkanoyl group having 1 to 8 carbon atoms, an alkanoyloxy group having 1 to 8 carbon atoms, or the number of carbon atoms May have an alkoxycarbonyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkenyloxy group having 2 to 8 carbon atoms, and / or an alkenoyl group having 2 to 8 carbon atoms,
In the general formula (II-1-b), Z11 and Z21 are each independently —COO—, —OCO—, —CH ₂ CH ₂ —, —OCH ₂ —, —CH ₂ O—, —CH═. CH—, —C≡C—, —CH═CHCOO—, —OCOCH═CH—, —CH ₂ CH ₂ COO—, —CH ₂ CH ₂ OCO—, —COOCH ₂ CH ₂ —, —OCOCH ₂ CH ₂ — , -C = N -, - N = C -, - CONH -, - NHCO -, - C (CF 3) 2 -, alkyl group or a single bond may C2-10 have a halogen atom , R11 represents 0, 1, 2, or 3, and when there are a plurality of B11 and Z11, they may be the same or different. In the case where Z11 and Z21 represent a single bond, the substituents of the two adjacent ring structures among B11, B21 and B31 are combined to form a cyclic group. Well,
In the general formula (II-1), ^P211 is the above-described formula (P-2-1), (P-2-2), (P-2-7), (P- 2-12) and (P-2-13) are preferable, and Formulas (P-2-1), (P-2-2), and (P-2-7) are more preferable.

In the general formula (II-1), Sp ²¹¹ preferably represents an alkylene group having 1 to 14 carbon atoms independently from the viewpoint of enhancing storage stability, and 1 present in the alkylene group. Two CH ₂ groups or two or more non-adjacent CH ₂ groups may be each independently replaced by —O—, —COO— or —OCO—. Moreover, it is more preferable that Sp ²¹¹ independently represents an alkylene group having 1 to 12 carbon atoms, and one CH ₂ group present in the alkylene group or two or more CH ₂ not adjacent to each other. The group may be replaced by -O-.

In the general formula (II-1), X ²¹¹ is independently —O—, —OCH ₂ —, —CH ₂ O—, —CO—, —COO—, —OCO—, —O—CO. -O -, - CH = CH- COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 _{CH 2 -, - CH 2 CH} 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO-, -CH = CH-, -C≡C- or a single bond is preferable, and -O-, -COO-, -OCO-, or a single bond is more preferable (provided that P ²¹¹ -Sp ²¹¹ , and ^Sp 211 ^{-X 211} may, -O-O -, - O -NH -, - S-S And it does not contain -O-S- group.).

In the general formula (II-1), R ²¹¹ represents a hydrogen atom, a halogen atom, a cyano group, one —CH ₂ —, or two or more non-adjacent —CH ₂ —, each independently —O -, -CO-, -COO-, -OCO-, -O-CO-O-, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH A linear or branched alkyl group having 1 to 12 carbon atoms or a linear or branched alkenyl group having 1 to 12 carbon atoms, which may be substituted by = CH-, -CH = CH-, or -C≡C- It is preferable that one or two or more hydrogen atoms of the alkyl group or alkenyl group may be substituted with a halogen atom or a cyano group. It may be different. R ²¹¹ is a hydrogen atom, a halogen atom, a cyano group, one —CH ₂ —, or two or more non-adjacent —CH ₂ —, each independently —O—, —CO—, —COO. Represents a linear or branched alkyl group having 1 to 12 carbon atoms or a linear or branched alkenyl group having 1 to 8 carbon atoms, which may be substituted by-, -OCO-, or -C≡C-. More preferably, one or more hydrogen atoms of the alkyl group or alkenyl group may be substituted with a halogen atom or a cyano group, and when a plurality of substituents are substituted, they may be the same or different. Also good.

In the above general formula (II-1-b), B11, B21 and B31 each independently may have the above-described substituents such as 1,4-phenylene group, 1,4-cyclohexylene group, 2 , 6-naphthylene group, Z11 and Z21 are each independently —COO—, —OCO—, —CH ₂ CH ₂ —, —OCH ₂ —, —CH ₂ O—, —CH═CH. -, -C≡C-, -C = N-, -N = C-, or a single bond is preferable, and r11 preferably represents 0 or 1.

  Examples of the general formula (II-1) include compounds represented by the following general formulas (II-1-1) to (II-1-4), but are not limited to the following general formulas. is not.

In the general formulas (II-1-1) to (II-1-4), P ²¹¹ , Sp ²¹¹ , X ²¹¹ , and q ²¹¹ are the same as defined in the general formula (II-1). Represent,
In the general formulas (II-1-1) to (II-1-4), B111, B112, B113, B21, and B31 are the same as the definitions of B11 to B31 in the general formula (II-1-b). And preferred groups also represent the same definitions as B11 to B31, and may be the same or different,
In the general formulas (II-1-1) to (II-1-4), Z111, Z112, Z113, and Z21 represent the same definitions as Z11 to Z21 in the general formula (II-1-b). And preferred groups also represent the same definitions as Z11 to Z21, and may be the same or different,
In the general formulas (II-1-1) to (II-1-4), R ²¹¹ represents a hydrogen atom, a halogen atom, a cyano group, one —CH ₂ —, or two or more non-adjacent — CH ₂ — is independently —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, —CO. —NH—, —NH—CO—, —NH—, —N (CH ₃ ) —, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH A straight-chain or branched alkyl group having 1 to 12 carbon atoms, which may be substituted by ═CH—, —CH═CH—, —CF═CF— or —C≡C—; Represents a chain or branched alkenyl group, and one or more hydrogen atoms of the alkyl group or alkenyl group are a halogen atom, It may be substituted with a cyano group, and when multiple substitutions are made, they may be the same or different.

  Among the general formulas (II-1-1) to (II-1-4), from the viewpoint of orientation after polymerization, the general formulas (II-1-1) to (II-1-2) The compounds represented are preferred.

  The compounds represented by the general formulas (II-1-1) to (II-1-4) are represented by the following formulas (II-1-1-1) to (II-1-1-26). The compounds represented are exemplified, but not limited thereto.

In the formula, R ^c represents a hydrogen atom or a methyl group, m represents an integer of 0 to 18, n represents 0 or 1, and R ²¹¹ represents the above general formulas (II-1-1) to (II- 1-4) represents the same as the definition of 1-4), but R ²¹¹ represents a hydrogen atom, a halogen atom, a cyano group, one —CH ₂ — is —O—, —CO—, —COO—, —OCO—, It preferably represents a linear alkyl group having 1 to 6 carbon atoms or a linear alkenyl group having 1 to 6 carbon atoms, which may be substituted by
The cyclic group has one or more F, Cl, CF ₃ , OCF ₃ , CN groups, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and 1 to 1 carbon atoms as a substituent. 8 alkanoyl groups, alkanoyloxy groups having 1 to 8 carbon atoms, alkoxycarbonyl groups having 1 to 8 carbon atoms, alkenyl groups having 2 to 8 carbon atoms, alkenyloxy groups having 2 to 8 carbon atoms, carbon atoms It may have an alkenoyl group having 2 to 8 carbon atoms and an alkenoyloxy group having 2 to 8 carbon atoms.

  The compounds represented by the above general formula (II-1-1-1) to general formula (II-1-1-26) are more specifically represented by the following general formula (II-1-2-1) to general formula: Although the compound represented by (II-1-2-37) can be illustrated, it is not necessarily limited to these.

The optical anisotropic body of the present invention is produced using a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound (II) having two or more polymerizable functional groups in the molecule. The product may contain a monofunctional polymerizable liquid crystal compound having one polymerizable functional group in the molecule as an optional component, and the above general formula (II-1), general formula (II-1- 1) to General Formula (II-1-4), General Formula (II-1-1-1) to General Formula (II-1-1-26), or General Formula (II-1-2) 1) to the general formula (II-1-2-37), the total content of the monofunctional polymerizable liquid crystal compound having one polymerizable functional group in the molecule is in the polymerizable liquid crystal composition. Of the total content of the polymerizable liquid crystal compound (II), the polymerizable liquid crystal compound (II-1) and the chiral compound (III), 0 Preferably contains 30 mass%, more preferably contains 0 to 20 wt%, particularly preferably contains 0 to 10 mass%. When emphasizing the curability of the resulting coating film, the upper limit is preferably 40% by mass or less, and more preferably 30% by mass or less.
(Chiral compound)
The optical anisotropic body of the present invention is produced using a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound (II) having two or more polymerizable functional groups in the molecule. The product contains a chiral compound (III) which may optionally exhibit liquid crystallinity or may be non-liquid crystalline.

  The chiral compound used in the present invention preferably has one or more polymerizable functional groups. The polymerizable chiral compound preferably has one or more polymerizable functional groups. Examples of such compounds include JP-A-11-193287, JP-A-2001-158788, JP-T 2006-52669, JP-A-2007-269639, JP-A-2007-269640, 2009. -84178 and the like, including a chiral saccharide such as isosorbide, isomannite, glucoside, etc., and a rigid site such as a 1,4-phenylene group and a 1,4-cyclohexylene group, and a vinyl group A polymerizable chiral compound having a polymerizable functional group such as an acryloyl group, a (meth) acryloyl group, or a maleimide group, a polymerizable chiral compound comprising a terpenoid derivative as described in JP-A-8-239666, NATURE VOL35 467-469 pages (November 30, 1995) Published), NATURE VOL 392, pages 476 to 479 (issued on April 2, 1998), or the like, or a polymerizable chiral compound comprising a mesogenic group and a spacer having a chiral moiety, or JP-T-2004-504285. And a polymerizable chiral compound containing a binaphthyl group as described in JP-A-2007-248945. Among them, a chiral compound having a large helical twisting power (HTP) is preferable.

  The compounding amount of the polymerizable chiral compound needs to be appropriately adjusted depending on the helical induction force of the compound, but the polymerization contained in the polymerizable liquid crystal composition used when producing the optical anisotropic body of the present invention. Among the total content of the crystalline liquid crystal compound (II), the polymerizable liquid crystal compound (II-1) and the chiral compound (III), 0 to 25% by mass is preferable, and 0 to 20% by mass is more preferable. The content is preferably 0 to 15% by mass.

  Examples of the general formula of the chiral compound include general formulas (III-1) to (III-4), but are not limited to the following general formula.

In the formula, Sp ^3a and Sp ^3b each independently represent an alkylene group having 0 to 18 carbon atoms, and the alkylene group is a carbon atom having one or more halogen atoms, a CN group, or a polymerizable functional group. It may be substituted by an alkyl group having 1 to 8, two or more of CH ₂ groups, independently of one another each of the present in the radical is not one CH ₂ group or adjacent, each other oxygen atom in the form that does not bind directly _{to, -O -, - S -,} - NH -, - N (CH 3) -, - CO -, - COO -, - OCO -, - OCOO -, - SCO -, - COS- Or may be replaced by -C≡C-
A1, A2, A3, A4, and A5 are each independently 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group, , 3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene-2,6-diyl group, pyridine -2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group-, 1,2,3,4-tetrahydronaphthalene-2,6 -Diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4,4a, 9,10a-octahydro Fe Trento-2,7-diyl group, 1,4-naphthylene group, benzo [1,2-b: 4,5-b ′] dithiophene-2,6-diyl group, benzo [1,2-b: 4, 5-b ′] diselenophen-2,6-diyl group, [1] benzothieno [3,2-b] thiophene-2,7-diyl group, [1] benzoselenopheno [3,2-b] selenophene-2 , 7-diyl group, or fluorene-2,7-diyl group, n, l and k each independently represent 0 or 1, and 0 ≦ n + 1 + k ≦ 3,
Z0, Z1, Z2, Z3, Z4, Z5, and Z6 are each independently —COO—, —OCO—, —CH ₂ CH ₂ —, —OCH ₂ —, —CH ₂ O—, —CH═. CH—, —C≡C—, —CH═CHCOO—, —OCOCH═CH—, —CH ₂ CH ₂ COO—, —CH ₂ CH ₂ OCO—, —COOCH ₂ CH ₂ —, —OCOCH ₂ CH ₂ — , -CONH-, -NHCO-, an alkyl group which may have a halogen atom having 2 to 10 carbon atoms or a single bond;
n5 and m5 each independently represent 0 or 1,
R ^3a and R ^3b represent a hydrogen atom, a halogen atom, a cyano group, or an alkyl group having 1 to 18 carbon atoms, and the alkyl group may be substituted with one or more halogen atoms or CN. two or more CH ₂ groups not one CH ₂ group or adjacent present in the radical are each, independently of one another, in the form of oxygen atoms are not directly bonded to each other, -O -, - S -, - NH—, —N (CH ₃ ) —, —CO—, —COO—, —OCO—, —OCOO—, —SCO—, —COS— or —C≡C— may be substituted,
Alternatively, R ^3a and R ^3b are represented by the general formula (III-a)

(In the formula, P ^3a represents a polymerizable functional group.)
P ^3a preferably represents a substituent selected from a polymerizable group represented by the following formula (P-1) to formula (P-20).

  Among these polymerizable functional groups, from the viewpoint of enhancing the polymerizability and storage stability, the formula (P-1) or the formulas (P-2), (P-7), (P-12), (P-13) ) Is preferable, and formulas (P-1), (P-7), and (P-12) are more preferable.

  Specific examples of the chiral compound include compounds (III-5) to (III-46), but are not limited to the following compounds.

(In the formula, m and n each independently represent an integer of 1 to 18, R and R _{1 to} R ₄ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms. An alkoxy group, a carboxy group, or a cyano group, when these groups are alkyl groups having 1 to 6 carbon atoms, or alkoxy groups having 1 to 6 carbon atoms, all are unsubstituted, or one or two It may be substituted with the above halogen atoms.)
(Combination of multiple types of polymerizable liquid crystal compounds)
The optical anisotropic body of the present invention is produced using a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound (II) having two or more polymerizable functional groups in the molecule. It is preferable to use a mixture of a plurality of the polymerizable liquid crystal compounds in the product. When at least one monofunctional polymerizable liquid crystal compound and at least one bifunctional polymerizable liquid crystal compound and / or polyfunctional polymerizable liquid crystal compound are used in combination, the curability of the resulting film is improved. Preferably, at least one monofunctional polymerizable liquid crystal compound and at least one bifunctional polymerizable liquid crystal compound are more preferably used in combination. Among these, when it is desired to further reduce the amount of residual monomer of the optical anisotropic body of the present invention, the above-mentioned (II-2-2) to (II) having three or more ring structures in the compound as a bifunctional polymerizable liquid crystal compound. It is preferable to obtain a mixture of polymerizable liquid crystal compounds using a compound selected from -2-4).

In the polymerizable liquid crystal composition used for producing the optical anisotropic body of the present invention, a polymerizable liquid crystal compound having one polymerizable functional group in the molecule and two or more polymerizable functional groups in the molecule. The total amount of the polymerizable liquid crystal compound having a content of 60% by mass to 100% by mass of the total amount of the polymerizable liquid crystal compound (II), the polymerizable liquid crystal compound (II-1) and the chiral compound (III). It is particularly preferable that the content be 70% by mass to 100% by mass.
(Polymerizable discotic compound)
The polymerizable liquid crystal composition used when producing the optical anisotropic body of the present invention exhibits liquid crystallinity other than the polymerizable compound represented by the above general formula (II-A) and general formula (II-1). Alternatively, it may contain a polymerizable discotic compound that may be non-liquid crystalline.

  The polymerizable discotic compound used in the present invention preferably has at least one polymerizable functional group. Examples of such compounds include polymerizable compounds described in, for example, JP-A-7-281028, JP-A-7-287120, JP-A-7-333431, and JP-A-8-27284. Is mentioned.

  Although the compounding quantity of a polymerizable discotic compound needs to be suitably adjusted with a compound, it is preferable to contain 0-10 mass% among polymeric compositions.

  Examples of the general formula of the polymerizable discotic compound include general formulas (4-1) to (4-3), but are not limited to the following general formula.

In the formula, Sp ⁴ represents an alkylene group having 0 to 18 carbon atoms, and the alkylene group is substituted with one or more halogen atoms, CN group, or an alkyl group having 1 to 8 carbon atoms having a polymerizable functional group. It may be, independently each two or more CH ₂ groups not one CH ₂ group or adjacent present in this group to each other, in a manner that oxygen atoms are not directly bonded to each other, -O Replaced by —, —S—, —NH—, —N (CH ₃ ) —, —CO—, —COO—, —OCO—, —OCOO—, —SCO—, —COS— or —C≡C—. You may,
A ⁴ represents 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group, 1,3-dioxane-2,5-diyl group, tetrahydro Thiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene-2,6-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5 -Diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group-, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene- 2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4,4a, 9,10a-octahydrophenanthrene-2,7-diyl group, 1,4- Naphthile Benzo [1,2-b: 4,5-b ′] dithiophene-2,6-diyl group, benzo [1,2-b: 4,5-b ′] diselenophen-2,6-diyl group , [1] benzothieno [3,2-b] thiophene-2,7-diyl group, [1] benzoselenopheno [3,2-b] selenophene-2,7-diyl group, or fluorene-2,7- Represents a diyl group,
n5 represents 0 or 1,
Z ^4a is —CO—, —CH ₂ CH ₂ —, —CH ₂ O—, —CH═CH—, —CH═CHCOO—, —CH ₂ CH ₂ COO—, —CH ₂ CH ₂ OCO—, — COCH ₂ CH ₂ — represents an alkyl group which may have a halogen atom having 2 to 10 carbon atoms or a single bond,
Z ^4b is —COO—, —OCO—, —OCH ₂ —, —CH ₂ O—, —CH═CH—, —C≡C—, —CH═CHCOO—, —OCOCH═CH—, —CH ₂ CH _{2 COO -, - CH 2 CH} 2 OCO -, - COOCH 2 CH 2 -, - OCOCH 2 CH 2 -, - CONH -, - NHCO -, - OCOO-, a halogen atom having 2 to 10 carbon atoms Represents a good alkyl group or a single bond,
R ⁴ represents a hydrogen atom, a halogen atom, a cyano group, or an alkyl group having 1 to 18 carbon atoms, and the alkyl group may be substituted with one or more halogen atoms or CN. and two or more CH ₂ groups not one CH ₂ group or adjacent to existing independently of one another each in the form of oxygen atoms are not directly bonded to each other, -O -, - S -, - NH-, _{-N (CH 3) -, -} CO -, - COO -, - OCO -, - OCOO -, - SCO -, - COS- or may be replaced by -C≡C-,
Or R ⁴ represents the general formula (4-a)

(In the formula, P ^4a represents a polymerizable functional group, and Sp ^3a represents the same meaning as Sp ¹ ).
P ^4a preferably represents a substituent selected from a polymerizable group represented by the following formula (P-1) to formula (P-20).

  Among these polymerizable functional groups, from the viewpoint of enhancing the polymerizability and storage stability, the formula (P-1) or the formulas (P-2), (P-7), (P-12), (P-13) ) Is preferable, and formulas (P-1), (P-7), and (P-12) are more preferable.

Specific examples of the polymerizable discotic compound include compounds (4-4) to (4-8), but are not limited to the following compounds.
(Polymerization initiator)
(Photopolymerization initiator)
The polymerizable liquid crystal composition used for producing the optical anisotropic body of the present invention preferably contains a photopolymerization initiator. It is preferable to contain at least one photopolymerization initiator. Specifically, “Irgacure 651”, “Irgacure 184”, “Darocur 1173”, “Irgacure 907”, “Irgacure 127”, “Irgacure 369”, “Irgacure 379”, “Irgacure 819”, “Irgacure 819” manufactured by BASF "Irgacure 2959", "Irgacure 1800", "Irgacure 250", "Irgacure 754", "Irgacure 784", "Irgacure OXE01", "Irgacure OXE02", "Lucirin TPO", "Darocure 1173", "Darocure MBF" and LAMBSON “Esacure 1001M”, “Esacure KIP150”, “Speed Cure BEM”, “Speed Cure BMS”, “Speed Cure MBP”, “Speed Cure PBZ”, “Speed Cure ITX” "Speedcure DETX", "Speedcure EBD", "Speedcure MBB", "Speedcure BP", "Kayacure DMBI" manufactured by Nippon Kayaku Co., Ltd., "TAZ-A" manufactured by Nippon Shibel Hegner (currently DKSH) "Adekaoptomer SP-152", "Adekaoptomer SP-170", "Adekaoptomer N-1414", "Adekaoptomer N-1606", "Adekaoptomer N-1717" manufactured by ADEKA, “Adekaoptomer N-1919”, “Syracure UVI-6990”, “Syracure UVI-6974” and “Syracure UVI-6972” manufactured by UCC, “Adekaoptomer SP-150” manufactured by Asahi Denka Kogyo Co., Ltd. , SP-152, SP-170, SP-172 "or Rhodia's" PHOTOINI " IATOR2074 ", BASF Corp. of" Irgacure 250 ", GE Silicones Co., Ltd. of" UV-9380C ", Midori Chemical Co., Ltd. of the" DTS-102 ", and the like.

The amount of the photopolymerization initiator used was 100 parts by mass with the total content of the polymerizable liquid crystal compound (II), the polymerizable liquid crystal compound (II-1) and the chiral compound (III) contained in the polymerizable liquid crystal composition. In this case, it is preferable to add 0.1 to 7 parts by mass, more preferably 1 to 7 parts by mass, further preferably 2 to 7 parts by mass, and particularly preferably 4 to 7 parts by mass. These can be used alone or in combination of two or more, and a sensitizer or the like may be added. By using the photopolymerization initiator in an amount of 3 to 7 parts by mass, the orientation state in the subsequent steps after the retardation film formation (firing step, transparent electrode sputtering step, further firing step) is good, transparency, An optical anisotropic body having a high phase difference retention can be obtained. If the usage-amount of a photoinitiator is 0.1 mass part or less, sclerosis | hardenability may deteriorate. Moreover, when it exceeds 7 mass parts, the orientation of a phase difference film may deteriorate.
(Thermal polymerization initiator)
In the polymerizable liquid crystal composition used for producing the optical anisotropic body of the present invention, a thermal polymerization initiator may be used in combination with a photopolymerization initiator. Known and commonly used thermal polymerization initiators can be used, such as methyl acetoacetate peroxide, cumene hydroperoxide, benzoyl peroxide, bis (4-t-butylcyclohexyl) peroxydicarbonate, t-butyl. Peroxybenzoate, methyl ethyl ketone peroxide, 1,1-bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane, p-pentahydroperoxide, t-butylhydroperoxide, dicumyl peroxide, isobutyl Peroxide, di (3-methyl-3-methoxybutyl) peroxydicarbonate, organic peroxide such as 1,1-bis (t-butylperoxy) cyclohexane, 2,2′-azobisisobutyronitrile , 2,2′-azobis (2,4 Azonitrile compounds such as dimethylvaleronitrile), azoamidin compounds such as 2,2′-azobis (2-methyl-N-phenylpropion-amidin) dihydrochloride, 2,2′azobis {2-methyl-N- [1, An azoamide compound such as 1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, an alkylazo compound such as 2,2′azobis (2,4,4-trimethylpentane), or the like can be used.

The amount of the thermal polymerization initiator used is 100 parts by mass with the total content of the polymerizable liquid crystal compound (II), the polymerizable liquid crystal compound (II-1) and the chiral compound (III) contained in the polymerizable liquid crystal composition. In this case, it is preferable to add 0.1 to 7 parts by mass, more preferably 0.3 to 7 parts by mass, and particularly preferably 0.5 to 7 parts by mass. These may be used alone or in combination of two or more.
(Curing agent)
The polymerizable liquid crystal composition used when producing the optical anisotropic body of the present invention may be used in combination with a curing agent. Specific examples include aliphatic polyamines such as diethylenetriamine and triethylenetetramine, EH-235R-2 manufactured by ADEKA, and ketimine compounds such as jER cure H3 and H30 manufactured by Mitsubishi Chemical.

The amount of the curing agent used is when the total content of the polymerizable liquid crystal compound (II), the polymerizable liquid crystal compound (II-1) and the chiral compound (III) contained in the polymerizable liquid crystal composition is 100 parts by mass. Is preferably 0.01 to 20 parts by mass, more preferably 0.05 to 15 parts by mass, and particularly preferably 0.1 to 10 parts by mass. These may be used alone or in combination of two or more.
(Organic solvent)
An organic solvent may be added to the polymerizable liquid crystal composition used in producing the optical anisotropic body of the present invention. As the organic solvent used in the polymerizable liquid crystal composition, an organic solvent in which the polymerizable liquid crystal compound exhibits good solubility is preferable, and an organic solvent having a low boiling point that can be dried at a temperature of 100 ° C. or lower is preferable. Specifically, it is preferable to use an organic solvent having a boiling point of 135 ° C. or less, more preferably 125 ° C., and most preferably 115 ° C. By using an organic solvent having a boiling point of 135 ° C. or lower, an optically anisotropic body having a good orientation state and a high retardation holding ratio in subsequent steps after the retardation film formation (firing step, transparent electrode sputtering step, further firing step) Can be obtained. When the boiling point of the organic solvent to be used exceeds 135 ° C., the orientation and retardation retention in the subsequent steps after the retardation film formation (baking step, transparent electrode sputtering step, further baking step) are deteriorated. Examples of the organic solvent used in producing the optical anisotropic body of the present invention include aromatic hydrocarbons such as toluene, ester solvents such as methyl acetate, ethyl acetate, propyl acetate, and butyl acetate, methyl ethyl ketone, and methyl isobutyl. Examples thereof include ketone solvents such as ketone and cyclopentanone, ether solvents such as tetrahydrofuran and 1,2-dimethoxyethane, propylene glycol monomethyl ether acetate, and diethylene glycol monomethyl ether acetate. These can be used alone or in combination of two or more, but any one of ketone solvents, ether solvents, ester solvents and aromatic hydrocarbon solvents It is preferable to use the above from the viewpoint of solution stability. Note that the amount of residual solvent contained in the optically anisotropic layer is measured as follows. Specifically, first, the optical anisotropic body of the present invention is immersed in 1 ml of anisole for 24 hours. An organic solvent other than anisole may be used as long as the organic solvent can obtain sufficient solubility of the polymerizable liquid crystal compound. The anisole solution from which the residual solvent was extracted was analyzed using gas chromatography, and the residual solvent amount (ppm) of the optical anisotropic body was calculated.

  The polymerizable liquid crystal composition used in producing the optical anisotropic body of the present invention can be applied to a substrate when it is made into a solution using an organic solvent. The ratio of the organic solvent used in the polymerizable liquid crystal composition is not particularly limited as long as the applied state is not significantly impaired, but the total amount of the organic solvent contained in the polymerizable liquid crystal composition is 10 to 95% by mass. It is preferably 12 to 90% by mass, more preferably 15 to 85% by mass.

  When the polymerizable liquid crystal composition is dissolved in the organic solvent, it is preferably heated and stirred in order to uniformly dissolve the polymerizable liquid crystal composition. The heating temperature at the time of heating and stirring may be appropriately adjusted in consideration of the solubility of the composition to be used in the organic solvent, but is preferably 15 ° C to 110 ° C, more preferably 15 ° C to 105 ° C from the viewpoint of productivity, 15 to 100 ° C is more preferable, and 20 to 90 ° C is particularly preferable.

  Moreover, when adding an organic solvent, it is preferable to stir and mix with a dispersion stirrer. Specific examples of the dispersion stirrer include a disperser having a stirring blade such as a disper, a propeller, and a turbine blade, a paint shaker, a planetary stirrer, a shaker, a stirrer, a shaker, or a rotary evaporator. In addition, an ultrasonic irradiation apparatus can be used.

The number of rotations of stirring when adding the organic solvent is preferably adjusted as appropriate depending on the stirring device used, but the number of rotations of stirring is preferably 10 rpm to 1000 rpm in order to obtain a uniform polymerizable liquid crystal composition solution, and 50 rpm More preferably, it is set to ˜800 rpm, and particularly preferably 150 rpm to 600 rpm.
(Polymerization inhibitor)
It is preferable to add a polymerization inhibitor to the polymerizable liquid crystal composition used in producing the optical anisotropic body of the present invention. Examples of the polymerization inhibitor include phenol compounds, quinone compounds, amine compounds, thioether compounds, nitroso compounds, and the like.

  Examples of phenolic compounds include p-methoxyphenol, cresol, t-butylcatechol, 3.5-di-t-butyl-4-hydroxytoluene, 2.2'-methylenebis (4-methyl-6-t-butylphenol) 2.2′-methylenebis (4-ethyl-6-tert-butylphenol), 4.4′-thiobis (3-methyl-6-tert-butylphenol), 4-methoxy-1-naphthol, 4,4′- Dialkoxy-2,2′-bi-1-naphthol, and the like.

  As quinone compounds, hydroquinone, methylhydroquinone, tert-butylhydroquinone, p-benzoquinone, methyl-p-benzoquinone, tert-butyl-p-benzoquinone, 2,5-diphenylbenzoquinone, 2-hydroxy-1,4-naphthoquinone 1,4-naphthoquinone, 2,3-dichloro-1,4-naphthoquinone, anthraquinone, diphenoquinone and the like.

  Examples of amine compounds include p-phenylenediamine, 4-aminodiphenylamine, N.I. N'-diphenyl-p-phenylenediamine, Ni-propyl-N'-phenyl-p-phenylenediamine, N- (1.3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, N.I. N′-di-2-naphthyl-p-phenylenediamine, diphenylamine, N-phenyl-β-naphthylamine, 4.4′-dicumyl-diphenylamine, 4.4′-dioctyl-diphenylamine and the like.

  Examples of thioether compounds include phenothiazine and distearyl thiodipropionate.

  Examples of the nitroso compounds include N-nitrosodiphenylamine, N-nitrosophenylnaphthylamine, N-nitrosodinaphthylamine, p-nitrosophenol, nitrosobenzene, p-nitrosodiphenylamine, α-nitroso-β-naphthol, and the like, N, N-dimethyl p-nitrosoaniline, p-nitrosodiphenylamine, p-nitronedimethylamine, p-nitrone-N, N-diethylamine, N-nitrosoethanolamine, N-nitrosodi-n-butylamine, N-nitroso-Nn-butyl- 4-butanolamine, N-nitroso-diisopropanolamine, N-nitroso-N-ethyl-4-butanolamine, 5-nitroso-8-hydroxyquinoline, N-nitrosomorpholine, N-nitroso-N-phenylhydroxylamine Ammonium salt, ditrosobenzene, 2,4.6-tri-tert-butylnitronebenzene, N-nitroso-N-methyl-p-toluenesulfonamide, N-nitroso-N-ethylurethane, N-nitroso-N- n-propyl urethane, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, sodium 1-nitroso-2-naphthol-3,6-sulfonate, sodium 2-nitroso-1-naphthol-4-sulfonate 2-nitroso-5-methylaminophenol hydrochloride, 2-nitroso-5-methylaminophenol hydrochloride and the like.

The addition amount of the polymerization inhibitor used in the polymerizable liquid crystal composition used in producing the optical anisotropic body of the present invention is the polymerizable liquid crystal compound (II) and polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition. When the total content of (II-1) and chiral compound (III) is 100 parts by mass, it is preferably 0.01 to 1.0 part by mass, and 0.05 to 0.5 part by mass. Is more preferable.
(Orientation control agent)
The polymerizable liquid crystal composition used when producing the optical anisotropic body of the present invention is one kind of an alignment control agent that further promotes alignment in order to make the polymerizable liquid crystal compound horizontally or planarly aligned. You may contain above. Alignment control agents that can be contained include alkyl carboxylates, alkyl phosphates, alkyl sulfonates, fluoroalkyl carboxylates, fluoroalkyl phosphates, fluoroalkyl sulfonates, polyoxyethylene derivatives, fluoro Examples include alkylethylene oxide derivatives, polyethylene glycol derivatives, alkylammonium salts, fluoroalkylammonium salts, and the like, and fluorine-containing surfactants are particularly preferable. Specifically, “Megafuck F-251”, “Megafuck F-444”, “Megafuck F-510”, “Megafuck F-552”, “Megafuck F-553”, “Megafuck F-” "554", "Megafuck F-555", "Megafuck F-558", "Megafuck F-560", "Megafuck F-561", "Megafuck F-563", "Megafuck F-565" , “Megafuck F-570”, “Megafuck R-40”, “Megafuck R-41”, “Megafuck R-43”, “Megafuck R-94” (above, manufactured by DIC Corporation), “ Examples include “FTX-218” (manufactured by Neos Co., Ltd.).

  Examples of the orientation control agent that can be used include compounds represented by the following general formulas (5-1) to (5-4), but the structure is not limited thereto.

(In the formula, each R may be the same or different and represents an alkoxy group having 1 to 30 carbon atoms which may be substituted with a fluorine atom. In the formula, m1, m2 and m3 each represent an integer of 1 or more. Represents.)
(Chain transfer agent)
It is also preferable to add a chain transfer agent to the polymerizable liquid crystal composition used when producing the optical anisotropic body of the present invention in order to further improve the adhesion to the substrate when the optical anisotropic body is used. Examples of chain transfer agents include aromatic hydrocarbons, halogenated hydrocarbons such as chloroform, carbon tetrachloride, carbon tetrabromide, and bromotrichloromethane, and thiol compounds such as monothiol, dithiol, trithiol, and tetrathiol. However, aromatic hydrocarbons and thiol compounds are more preferable. Specifically, compounds represented by the following general formulas (8-1) to (8-12) are preferable.

In the formula, R ⁶⁵ represents an alkyl group having 2 to 18 carbon atoms, and the alkyl group may be linear or branched, and one or more methylene groups in the alkyl group are oxygen atoms. And a sulfur atom that is not directly bonded to each other, it may be substituted with an oxygen atom, a sulfur atom, —CO—, —OCO—, —COO—, or —CH═CH—, and R ⁶⁶ is a carbon atom. Represents an alkylene group of 2 to 18, wherein one or more methylene groups in the alkylene group are oxygen atoms, sulfur atoms, -CO-, -OCO- , —COO—, or —CH═CH— may be substituted.

The amount of the chain transfer agent added is the polymerizable liquid crystal compound (II), polymerizable liquid crystal compound (II-1) and chiral compound (in the polymerizable liquid crystal composition used in producing the optical anisotropic body of the present invention). When the total content of III) is 100 parts by mass, it is preferably 0.5 to 10 parts by mass, and more preferably 1.0 to 5.0 parts by mass.
(Other additives)
Furthermore, in order to adjust the physical properties, additives such as polymerizable compounds that do not have liquid crystallinity, thixotropic agents, ultraviolet absorbers, infrared absorbers, antioxidants, surface treatment agents, etc., do not significantly reduce the liquid crystal alignment ability. To the extent that can be added.
(Optical anisotropic)
The optical anisotropic body of the present invention is obtained by applying the polymerizable liquid crystal composition of the present invention on a substrate having an alignment function, and the liquid crystal molecules in the polymerizable liquid crystal composition of the present invention are nematic, smectic, It can be obtained by aligning and polymerizing a chiral nematic phase and a chiral smectic phase. In the optical anisotropic body of the present invention, the later-described retardation film is one of uses of the optical anisotropic body, and is included in the concept of the optical anisotropic body.

  The optically anisotropic body of the present invention is a polymerizable liquid crystal compound (II) having one or more polymerization initiators (I), one or two or more polymerizable functional groups in one or more molecules. And optionally including an optically anisotropic layer using a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound (II-1) having one or two or more one polymerizable functional groups, Content of the polymerizable liquid crystal compound (II) contained in the optically anisotropic layer and the polymerizable liquid crystal compound (II-1) optionally contained is 0.0001 mass% or more and 3 mass% or less. And The content of the unreacted polymerizable liquid crystal compound (II) contained in the optically anisotropic layer and the optionally contained unreacted polymerizable liquid crystal compound (II-1) is less than 0.0001% by mass. The orientation and transparency in the firing step after forming the retardation film, the transparent electrode sputtering step, and the further firing step are deteriorated. Further, when the content of the polymerizable liquid crystal compound (II) contained in the optically anisotropic layer and the unreacted polymerizable liquid crystal compound (II-1) optionally contained exceeds 3% by mass, the retardation film The orientation, heat resistance, and retardation retention in the firing step after formation, the transparent electrode sputtering step, and the further firing step are deteriorated. The content of the polymerizable liquid crystal compound (II) contained in the optically anisotropic layer and the optionally contained polymerizable liquid crystal compound (II-1) is 0.0001% by mass or more and 1% by mass or less. More preferably, it is 0.0001% by mass or more and 0.5% by mass or less. In order to make the content of the polymerizable liquid crystal compound (II) contained in the optically anisotropic layer and the polymerizable liquid crystal compound (II-1) optionally contained in the above range, a polymerizable liquid crystal composition is used. A method of heating the polymerizable liquid crystal composition when polymerizing by UV irradiation is exemplified. Specifically, the temperature during UV irradiation is preferably 50 ° C to 60 ° C, more preferably 50 ° C to 58 ° C, and most preferably 50 ° C to 55 ° C. By setting the temperature during UV irradiation to 50 to 60 ° C., the residual monomer amount of the optical anisotropic body can be adjusted to 0.0001 to 3% by mass, and the baking step after forming the optical anisotropic layer is transparent. An optically anisotropic body having a good orientation state in the electrode sputtering step and further firing step, and high transparency and retardation retention can be obtained. The amount of residual monomer contained in the optically anisotropic layer may be a known method, and an example is a measuring method using high performance liquid chromatography (HPLC). Specifically, the obtained optical anisotropic body of the present invention is immersed in acetone for 24 hours. After immersion, the acetone solution from which the residual monomer has been extracted is concentrated with an evaporator. The solution may be an organic solvent other than acetone as long as sufficient solubility of the polymerizable liquid crystal compound can be obtained. After concentration by an evaporator, the obtained residue is dissolved in 1 ml of tetrahydrofuran (THF). Using high performance liquid chromatography (HPLC), the amount of residual monomer (% by mass) of the optical anisotropic body is calculated.

In the optical anisotropic body of the present invention, the amount of residual solvent contained in the optical anisotropic layer is preferably 2500 ppm or less. If the amount of residual solvent contained in the optically anisotropic layer exceeds 2500 ppm, the orientation and retardation retention ratio may be deteriorated in the firing step after forming the optically anisotropic layer, the transparent electrode sputtering step, and the further firing step. is there. Further, the amount of residual solvent contained in the optically anisotropic layer is more preferably 1500 ppm or less. The amount of the residual solvent contained in the optically anisotropic layer can be adjusted to 2500 ppm or less by using the organic solvent having a boiling point of 135 ° C. or less. In addition, although the well-known method can be used for the amount of residual solvent contained in an optically anisotropic layer, the measuring method using gas chromatography (GC) is mentioned as an example. Measure as follows. First, specifically, the obtained optical anisotropic body of the present invention is immersed in 1 ml of anisole for 24 hours to obtain an anisole solution from which a residual solvent is extracted. The obtained anisole solution is analyzed by gas chromatography (GC), and the residual solvent amount (ppm) is calculated. (Retardation film)
The retardation film of the present invention is produced in the same manner as the optical anisotropic body of the present invention. A liquid crystalline compound uniformly forms a continuous alignment state with respect to the substrate, and a retardation film is obtained. The retardation film using the optical anisotropic body of the present invention is synonymous with the retardation layer and the retardation film.

  Examples of the retardation film obtained by aligning and polymerizing the polymerizable liquid crystal composition of the present invention on a substrate by coating or the like include a positive A plate, a negative C plate, and a biaxial plate.

  Here, the positive A plate has a refractive index in the in-plane slow axis direction of the retardation film nx, a refractive index in the in-plane fast axis direction of the retardation film ny, and a refractive index in the thickness direction of the retardation film. The phase difference film has a relationship of “nx> ny = nz” when nz. In the negative C plate, the refractive index in the in-plane slow axis direction of the retardation film is nx, the refractive index in the in-plane fast axis direction of the retardation film is ny, and the refractive index in the thickness direction of the retardation film is nz. Sometimes the retardation film has a relationship of “nx = ny> nz”. In the biaxial plate, the refractive index in the in-plane slow axis direction of the retardation film is nx, the refractive index in the in-plane fast axis direction of the retardation film is ny, and the refractive index in the thickness direction of the retardation film is nz. The retardation film has a relationship of “nx> ny> nz”.

The retardation film using the optical anisotropic body of the present invention is used for applications such as liquid crystal display devices, displays, optical elements, optical components, colorants, security markings, laser emission members, optical films, and compensation films. Accordingly, it is applied in a form suitable for the application. Moreover, an adhesive, an adhesive layer, an adhesive, an adhesive layer, a protective film, a polarizing film, or the like may be laminated.
(Phase difference patterning film)
The retardation patterning film using the optical anisotropic body of the present invention is obtained by sequentially laminating a substrate, an alignment film, and a polymer of a polymerizable liquid crystal composition in the same manner as the optical anisotropic body of the present invention. In the polymerization step, patterning is performed so as to obtain partially different phase differences. Patterning may be in different directions, such as lattice patterning, circular patterning, polygonal patterning, and the like. The retardation patterning film of the present invention is applied according to the use such as a liquid crystal display device, a display, an optical element, an optical component, a colorant, a security marking, a laser emission member, an optical film, and a compensation film. .

As a method of obtaining a partially different phase difference, an alignment film is provided on a substrate, and when the polymerizable liquid crystal composition of the present invention is applied and dried during alignment treatment, the polymerizable liquid crystal composition is patterned and aligned. To process. Examples of such an alignment treatment include a fine rubbing treatment, a polarized ultraviolet visible light irradiation treatment through a photomask, and a fine shape processing treatment. As the alignment film, known and commonly used ones are used. Such alignment films include polyimide, polysiloxane, polyamide, polyvinyl alcohol, polycarbonate, polystyrene, polyphenylene ether, polyarylate, polyethylene terephthalate, polyether sulfone, epoxy resin, epoxy acrylate resin, acrylic resin, coumarin compound, chalcone. Examples of the compound include compounds, cinnamate compounds, fulgide compounds, anthraquinone compounds, azo compounds, and arylethene compounds. The compound subjected to the alignment treatment by fine rubbing is preferably an alignment treatment or a compound in which crystallization of the material is promoted by adding a heating step after the alignment treatment. Among the compounds that perform alignment treatment other than rubbing, it is preferable to use a photo-alignment material.
(Brightness enhancement film)
The brightness enhancement film using the optical anisotropic body of the present invention is produced in the same manner as the optical anisotropic body of the present invention. By laminating a retardation film and a λ / 4 wavelength plate obtained by curing the polymerizable liquid crystal composition with an adhesive layer or the like, it can be used as the brightness enhancement film of the present invention. By providing the brightness enhancement film of the present invention, in a liquid crystal display device, light from a backlight can be effectively used, brightness can be improved, and luminous efficiency can be increased.
(Antireflection film)
The antireflection film using the optical anisotropic body of the present invention is produced in the same manner as the optical anisotropic body of the present invention. By laminating a retardation film and a λ / 4 wavelength plate obtained by curing a polymerizable liquid crystal composition with an adhesive layer or the like, it can be used as an antireflection film of the present invention. An image display device such as an organic EL has problems such as reflection of external light and reflection of a background. However, the above problem can be prevented by providing the antireflection film of the present invention.
(Thermal barrier film)
The thermal barrier film using the optical anisotropic body of the present invention is produced in the same manner as the optical anisotropic body of the present invention. By laminating a retardation film obtained by curing a polymerizable liquid crystal composition, it can be used as a heat shielding film of the present invention. By providing the thermal barrier film of the present invention, it is possible to prevent transmission of visible light, infrared light, or the like of sunlight.
(Optical anisotropic body manufacturing method)
(Base material)
The base material used for the optical anisotropic body of the present invention is a base material that is usually used for a liquid crystal display device, a display, an optical component or an optical film, and is dried at the time of application after coating of the polymerizable liquid crystal composition of the present invention. If it is the material which has heat resistance which can endure heating, there will be no restriction | limiting in particular. Examples of such a substrate include organic materials such as a glass substrate, a metal substrate, a ceramic substrate, and a plastic substrate. In particular, when the substrate is an organic material, examples thereof include cellulose derivatives, polyolefins, polyesters, polycarbonates, polyacrylates (acrylic resins), polyarylate, polyether sulfone, polyimide, polyphenylene sulfide, polyphenylene ether, nylon, and polystyrene. Among them, plastic base materials such as polyester, polystyrene, polyacrylate, polyolefin, cellulose derivative, polyarylate, and polycarbonate are preferable, base materials such as polyacrylate, polyolefin, and cellulose derivative are more preferable, and COP (cycloolefin polymer) is used as the polyolefin. It is particularly preferable to use TAC (triacetyl cellulose) as the cellulose derivative and PMMA (polymethyl methacrylate) as the polyacrylate. As a shape of a base material, you may have a curved surface other than a flat plate. These base materials may have an electrode layer, an antireflection function, and a reflection function as needed.

In order to improve the applicability and adhesiveness of the polymerizable liquid crystal composition used in producing the optical anisotropic body of the present invention, surface treatment of these substrates may be performed. Examples of the surface treatment include ozone treatment, plasma treatment, corona treatment, silane coupling treatment, and the like. In addition, in order to adjust the light transmittance and reflectance, an organic thin film, an inorganic oxide thin film, a metal thin film, etc. are provided on the substrate surface by a method such as vapor deposition, or in order to add an optical added value. The material may be a pickup lens, a rod lens, an optical disk, a retardation film, a light diffusion film, a color filter, or the like. Among these, a pickup lens, a retardation film, a light diffusion film, and a color filter that have higher added value are preferable.
(Orientation treatment)
In addition, the substrate is usually subjected to an alignment treatment so that the polymerizable liquid crystal composition is aligned when the polymerizable liquid crystal composition used in producing the optical anisotropic body of the present invention is applied and dried. Or an alignment film may be provided. Examples of the alignment treatment include stretching treatment, rubbing treatment, polarized ultraviolet visible light irradiation treatment, ion beam treatment, and the like. When the alignment film is used, a known and conventional alignment film is used. Such alignment films include polyimide, polysiloxane, polyamide, polyvinyl alcohol, polycarbonate, polystyrene, polyphenylene ether, polyarylate, polyethylene terephthalate, polyether sulfone, epoxy resin, epoxy acrylate resin, acrylic resin, coumarin compound, chalcone. Examples of the compound include compounds, cinnamate compounds, fulgide compounds, anthraquinone compounds, azo compounds, and arylethene compounds. The compound subjected to the alignment treatment by rubbing is preferably an alignment treatment or a compound in which crystallization of the material is promoted by inserting a heating step after the alignment treatment. Among the compounds that perform alignment treatment other than rubbing, it is preferable to use a photo-alignment material.
(Application)
Application methods for obtaining the optical anisotropic body of the present invention include applicator method, bar coating method, spin coating method, roll coating method, direct gravure coating method, reverse gravure coating method, flexo coating method, ink jet method, and die coating. Methods, cap coating methods, dip coating methods, slit coating methods, and the like can be performed using known and conventional methods. After applying the polymerizable liquid crystal composition, it is dried as necessary.
(Polymerization method)
Regarding the polymerization operation of the polymerizable liquid crystal composition for obtaining the optical anisotropic body of the present invention, generally, light such as ultraviolet rays is used in a state where the liquid crystal compound in the polymerizable liquid crystal composition is horizontally or planarly aligned with respect to the substrate. It is performed by irradiation or heating. When the polymerization is performed by light irradiation, specifically, it is preferable to irradiate ultraviolet light of 390 nm or less, and most preferable to irradiate light having a wavelength of 250 to 370 nm. However, when the polymerizable liquid crystal composition causes decomposition or the like due to ultraviolet light of 390 nm or less, it may be preferable to perform the polymerization treatment with ultraviolet light of 390 nm or more. This light is preferably diffused light and unpolarized light.

  Examples of the method for polymerizing the polymerizable liquid crystal composition used in the production of the optical anisotropic body of the present invention include a method of irradiating active energy rays and a thermal polymerization method. The method of irradiating active energy rays is preferable because the reaction proceeds, and among them, the method of irradiating light such as ultraviolet rays is preferable because the operation is simple.

A polymerizable liquid crystal composition usually has a liquid crystal phase within a range from a C (solid phase) -N (nematic) transition temperature (hereinafter abbreviated as a C-N transition temperature) to an NI transition temperature in a temperature rising process. Indicates. On the other hand, in the temperature lowering process, a non-equilibrium state is taken thermodynamically, so that the liquid crystal state may be maintained without being solidified even at a temperature below the CN transition temperature. This state is called a supercooled state. In the present invention, the liquid crystal composition in a supercooled state is also included in the state in which the liquid crystal phase is retained. Specifically, it is preferable to irradiate ultraviolet light of 390 nm or less, and most preferable to irradiate light having a wavelength of 250 to 370 nm. However, when the polymerizable composition causes decomposition or the like due to ultraviolet light of 390 nm or less, it may be preferable to perform polymerization treatment with ultraviolet light of 390 nm or more. This light is preferably diffused light and unpolarized light. The ultraviolet irradiation intensity is preferably in the range of 0.05 kW / m ^{2 to} 10 kW / m ² . In particular, the range of 0.2 kW / m ^{2 to 2} kW / m ² is preferable. When the ultraviolet intensity is less than 0.05 kW / m ² , it takes a lot of time to complete the polymerization. On the other hand, when the intensity exceeds ² kW / m ² , the liquid crystal molecules in the polymerizable liquid crystal composition tend to be photodegraded, and the order parameter of the polymerizable liquid crystal changes, and the retardation of the film after polymerization may be distorted. There is sex.

  After only a specific part is polymerized by UV irradiation using a mask, the orientation state of the unpolymerized part is changed by applying an electric field, a magnetic field or temperature, and then the unpolymerized part is polymerized. An optical anisotropic body having a plurality of regions having orientation directions can also be obtained.

  Further, when only a specific portion was polymerized by ultraviolet irradiation using a mask, the alignment was regulated in advance by applying an electric field, magnetic field or temperature to the unpolymerized polymerizable liquid crystal composition, and the state was maintained. An optical anisotropic body having a plurality of regions having different orientation directions can also be obtained by irradiating light from above the mask and polymerizing it.

The optical anisotropic body obtained by polymerizing the polymerizable liquid crystal composition of the present invention can be peeled off from the substrate and used alone as an optical anisotropic body, or it can be used as an optical anisotropic body as it is without peeling from the substrate. You can also In particular, since it is difficult to contaminate other members, it is useful when used as a laminated substrate or by being attached to another substrate.
(Liquid crystal display device)
The liquid crystal display device of the present invention is a display element in which a liquid crystal substance is sealed between light transmissive substrates such as glass. The liquid crystal display device changes the polarization state of the backlight polarized by the polarizing plate placed on the back side of the liquid crystal cell by changing the molecular orientation of the liquid crystal material by electrical control from a display control device (not shown). The image is displayed by controlling the amount of light transmitted through the polarizing plate arranged on the viewing side of the liquid crystal cell. In the liquid crystal display device of this embodiment, rod-shaped liquid crystal molecules having negative dielectric anisotropy are aligned.

  In the liquid crystal display device according to an embodiment of the present invention, it is preferable to use the negative C plate of the retardation film of the present invention in order to widen the viewing angle by compensating the viewing angle dependence of the polarization axis orthogonality. Further, it is preferable to use a positive A plate in combination, and it is more preferable to stack a positive A plate and a negative C plate.

  When laminating a positive A plate and a negative C plate, it is preferable to use a positive A plate as the first retardation film. The positive A plate has an in-plane retardation value in the range of 30 to 500 nm at a wavelength of 550 nm. Are preferred. The Nz coefficient is preferably in the range of 0.9 to 1.1. As a negative C plate, the thickness direction retardation value at a wavelength of 550 nm is preferably in the range of 20 to 400 nm.

The refractive index anisotropy in the thickness direction is represented by a thickness direction retardation value Rth defined by the equation (2). As the thickness direction retardation value Rth, an in-plane retardation value R ₀ , a retardation value R ₅₀ measured by tilting the slow axis as an inclination axis by 50 °, a film thickness d, and an average refractive index n ₀ of the film are used. Thus, nx, ny, and nz can be obtained by numerical calculation from the formula (1) and the following formulas (4) to (7), and these can be substituted into the formula (2). Further, the Nz coefficient can be calculated from Expression (3). The same applies to other descriptions in the present specification.

R ₀ = (nx−ny) × d (1)
Rth = [(nx + ny) / 2−nz] × d (2)
Nz coefficient = (nx−nz) / (nx−ny) (3)
R ₅₀ = (nx−ny ′) × d / cos (φ) (4)
(Nx + ny + nz) / 3 = n ₀ (5)
here,
φ = sin ⁻¹ [sin (50 °) / n ₀ ] (6)
ny ′ = ny × nz / [ny ² × sin ² (φ) + nz ² × cos ² (φ)] ^1/2 (7)
In the commercially available phase difference measuring device, the numerical calculation shown here is automatically performed in the device, and the in-plane retardation value _R0 , the thickness direction retardation value Rth, etc. are automatically displayed. There are many. An example of such a measuring apparatus is RETS-100 (manufactured by Otsuka Chemical Co., Ltd.).

  The retardation film of the present invention is either a liquid crystal display device (out-cell type, FIG. 1) disposed outside the liquid crystal cell or a liquid crystal display device (in-cell type) where the retardation film is disposed inside the liquid crystal cell. It can also be applied to liquid crystal display devices. From the viewpoint of improving productivity by reducing the thickness, weight, and pasting process of the liquid crystal display device, it is better to use an in-cell type retardation film.

  The “in-cell type retardation film” of the present invention includes a retardation film on the inner side sandwiched between a pair of light-transmitting substrates, and is disposed inside the liquid crystal cell. For the retardation film, an optically anisotropic body polymerized with the polymerizable liquid crystal composition aligned is used. The liquid crystal display device shown in FIGS. 2 and 3 is only one example of arrangement, and the position where the retardation film is provided is not limited thereto. For example, a retardation film may be provided at a desired position, such as between the electrode and the alignment film on the back side (FIGS. 10 and 11).

  The liquid crystal display device of the present invention may have a color filter. The color filter includes a black matrix and at least an RGB three-color pixel portion. Any method may be used for forming the color filter layer. The liquid crystal display device of the present invention may have an alignment film for aligning the liquid crystal composition on the surface of the first substrate that contacts the liquid crystal composition on the second substrate. The alignment film material is as described in the alignment treatment of the present invention.

In the liquid crystal display device of the present invention, a conductive metal oxide can be used as a material for the transparent electrode. Examples of the metal oxide include indium oxide (In ₂ O ₃ ), tin oxide (SnO ₂ ), and zinc oxide. (ZnO), indium tin oxide (In ₂ O ₃ —SnO ₂ ), indium zinc oxide (In ₂ O ₃ —ZnO), niobium-doped titanium dioxide (Ti _1-x Nb _x O ₂ ), fluorine-doped tin oxide, graphene Nanoribbons or metal nanowires can be used, but zinc oxide (ZnO), indium tin oxide (In ₂ O ₃ —SnO ₂ ), or indium zinc oxide (In ₂ O ₃ —ZnO) is preferable. For patterning these transparent conductive films, a photo-etching method, a method using a mask, or the like can be used.

  The liquid crystal display device of the invention may have a polarizing layer. The polarizing layer is a member having a function of converting natural light into linearly polarized light. The polarizing layer may be a film having a polarizing function. For example, a film obtained by stretching a polyvinyl alcohol film by adsorbing iodine or a dichroic dye, a film obtained by stretching a polyvinyl alcohol film, and an iodine or dichroic dye. Or the film which made the dichroic dye adsorb | suck, the film which apply | coated the aqueous solution containing a dichroic dye on a board | substrate, and formed the polarizing layer, a wire grid polarizer, etc. are mentioned.

  When using a wire grid polarizer, it is preferable to use a material formed of a conductive material such as Al, Cu, Ag, Cu, Ni, Cr, and Si.

  Moreover, the polarizing layer may further include a film serving as a protective film, if necessary. Examples of the protective film include polyolefin films such as polyethylene, polypropylene and norbornene polymers, polyethylene terephthalate films, polymethacrylic acid ester films, polyacrylic acid ester films, and cellulose ester films.

  In one embodiment of the present invention, an in-cell polarizing layer may be provided in which a polarizing layer is installed in the liquid crystal cell. An example of the liquid crystal display device in this case is shown in FIGS.

The optical member having the polarizing layer described above may be provided with an adhesive layer for bonding with the liquid crystal cell. An adhesive layer can also be provided for bonding with other members other than the liquid crystal cell. The pressure-sensitive adhesive forming the pressure-sensitive adhesive layer is not particularly limited. For example, an acrylic polymer, a silicone-based polymer, a polyester, a polyurethane, a polyamide, a polyether, a fluorine-based or rubber-based polymer is appropriately used as a base polymer. It can be selected and used. The liquid crystal composition of the present invention includes cyanobiphenyl, phenylcyclohexyl, phenylbenzoate, cyclohexylbenzoate, azomethine, azobenzene, pyrimidine, dioxane, cyclohexylcyclohexane, stilbene, tolan, etc. There can be used known ones.
(Image display device)
The image display device of the present invention can be used in various devices for image display. Examples of the image display device include an organic EL display device, a plasma display display device, and the like, and the use, type, and configuration of the image display device are not limited. When configuring the image display device, components such as a diffusion plate, an antireflection film, a protective film, a light diffusion plate, and a backlight can be arranged.
(Optical element)
The optical anisotropic body of the present invention can also be used as an optical element. Examples of the optical element include a diffraction grating and a pickup lens, but there are no limitations on the use, type, and configuration of the optical element.
(Printed matter)
The optical anisotropic body of the present invention can also be used as a printed matter. An example of the printed material is one printed to prevent counterfeiting, but there is no limitation on the use, type, and configuration of the printed material.

Hereinafter, the present invention will be described with reference to Synthesis Examples, Examples, and Comparative Examples, but the present invention is not limited to these examples. Unless otherwise specified, “part” and “%” are based on mass.
(Preparation of polymerizable liquid crystal composition)
Each polymerizable liquid crystal composition of the present invention for a retardation film was prepared as follows.

Compounds represented by the following formulas (A-1) to (A-10), which are polymerizable liquid crystal compounds having two or more polymerizable functional groups in the molecule shown in Tables 1 to 4, 1 Compounds represented by the following formulas (B-1) to (B-3), which are polymerizable liquid crystal compounds having a polymerizable functional group, and formulas (C-1) to (C-4), which are chiral compounds. The following methyl hydroquinone (MEHQ) (D-1), which is a polymerization inhibitor, and compounds (E-1) to (E-3), which are polymerization initiators, with respect to 100 parts by mass of the total amount of the compounds represented by The following Megafac F-554 (F-1), which is an orientation control agent, and the following cyclopentanone (G-1), toluene (G-2), and cyclohexanone (G-3), which are organic solvents, are shown in Table 1. Each polymerizable liquid crystal composition was prepared using the ratio (parts by mass) shown in Table 4.
(Preparation of polymerizable liquid crystal composition (1))
As shown in Table 1, 20.0 parts by mass of the compound represented by the formula (A-1), 40.0 parts by mass of the compound represented by the formula (A-2), and the formula (A-3) For a total of 100 parts by mass of 10.0 parts by mass of the compound, 15.0 parts by mass of the compound represented by the formula (A-4), and 15.0 parts by mass of the compound represented by the formula (A-5), Methylhydroquinone (MEHQ) (D-1) 0.1 part by mass, polymerization initiator (E-1) 4.0 part by mass, a compound represented by Megafac F-554 (F-1) as an alignment controller Using 0.15 parts by mass and 300 parts by mass of the organic solvent cyclopentanone (G-1), using a stirrer having a stirring propeller, stirring speed of 500 rpm, and solution temperature of 60 ° C. After stirring for 1 hour, it is filtered through a 0.2 μm membrane filter to obtain a polymerizable liquid crystal composition (1). .
(Preparation of polymerizable liquid crystal compositions (1) to (23) and comparative polymerizable liquid crystal compositions (24) to (36))
Similar to the preparation of the polymerizable liquid crystal composition (1) of the present invention, the formula (A-1) to the formula (A-10), the formula (B-1) to the formula (B-3), and the formula shown in Table 1 (C-1) to formula (C-4), a polymerization inhibitor (D-1), polymerization initiators (E-1) to (E-3), an alignment controller (F-1), an organic solvent (G -1) to (G-3), except that the respective compounds were changed to the ratios shown in Tables 1 to 4, respectively, under the same conditions as the preparation of the polymerizable liquid crystal composition (1). Liquid crystalline compositions (2) to (23) and comparative polymerizable liquid crystal compositions (24) to (36) were obtained.

  The following table shows specific compositions of the polymerizable liquid crystal compositions (1) to (23) and comparative polymerizable liquid crystal compositions (24) to (36) of the present invention.

MEHQ (D-1)
Irgacure 907 (E-1)
Irgacure OXE02 (E-2)
DTS-102 (E-3)
Mega Fuck F-554 (F-1)
Cyclopentanone (G-1)
Toluene (G-2)
Cyclohexanone (G-3)
Example 1
(Residual monomer amount, residual solvent amount)
<Preparation of optical anisotropic body for residual monomer amount and residual solvent amount evaluation>
A polyimide alignment film material for a horizontal alignment film was applied on a light-transmitting substrate by spin coating, dried at 100 ° C. for 10 minutes, and then baked at 200 ° C. for 60 minutes to obtain a coating film. The obtained coating film was rubbed. The rubbing treatment was performed using a commercially available rubbing apparatus. The prepared polymerizable liquid crystal composition (1) was applied to the substrate obtained through the above steps at 700 rpm / 30 sec using a spin coater at room temperature and dried at 80 ° C. for 2 minutes. Then, after leaving at 25 ° C. for 2 minutes, use a high-pressure mercury lamp to set the irradiation amount to 3000 mJ / cm ² and the irradiation temperature to 50 ° C. in a nitrogen atmosphere. Then, the optical anisotropic body of Example 1 was obtained by irradiating with UV light. The amount of residual monomer and the amount of residual solvent contained in the obtained optically anisotropic layer were evaluated.
(Residual monomer amount)
The obtained optical anisotropic body was immersed in acetone for 24 hours to obtain an acetone solution in which residual monomers were extracted. The obtained acetone solution was concentrated with an evaporator. A solution obtained by dissolving the concentrated residue in 1 ml of tetrahydrofuran (THF) was analyzed by high performance liquid chromatography (HPLC), and the amount of residual monomer (mass%) of the optical anisotropic body was calculated.
(Residual solvent amount)
The obtained optical anisotropic body was immersed in 1 ml of anisole for 24 hours to obtain an anisole solution from which the remaining solvent was extracted. The obtained anisole solution was analyzed by gas chromatography, and the residual solvent amount (ppm) was calculated.
(Orientation, transparency)
<Preparation of optical anisotropic body for evaluation of orientation and transparency>
An optical anisotropic body for evaluation of orientation and transparency was prepared by the same manufacturing method as the optical anisotropic body for evaluating the residual monomer amount and residual solvent amount. The obtained optical anisotropic body was baked (230 ° C. for 30 minutes). After the firing treatment, ITO sputtering is performed on the obtained optical anisotropic body using a sputtering apparatus at 50 ° C. under a pressure of 3.7 × 10 ⁻¹ Pa, an argon flow rate of 90 sccm, and an oxygen gas flow rate of 4.7 sccm for 2 minutes. Halfway, an ITO film having a thickness of 700 mm was formed on the optical anisotropic body. Then, baking processing (150 degreeC for 10 minutes) was performed, and orientation and transparency were evaluated.
<Evaluation of orientation>
○: There are no defects visually, and there are no defects even when observed with a polarizing microscope.
Δ: There are no defects visually, but a non-oriented portion exists in part by observation with a polarizing microscope.
X: Although there is no defect visually, the non-orientation part exists as a whole by observation with a polarizing microscope.
<Evaluation of transparency>
The transparency of the optical anisotropic body obtained in the orientation evaluation test was visually evaluated.
○: Transparent by visual inspection.
(Triangle | delta): The opaque part exists in a part visually.
X: An opaque part exists visually.
(Phase difference retention)
<Preparation of optical anisotropic body for evaluating retardation retention>
The optical anisotropic body of Example 1 was obtained by the same production method as the above-mentioned optical anisotropic bodies for residual monomer amount and residual solvent amount evaluation. The phase difference of the obtained optical anisotropic body was measured.

The obtained optical anisotropic body was baked (230 ° C. for 30 minutes). After the baking treatment, ITO sputtering was performed on the optical anisotropic body at 50 ° C. under a pressure of 3.7 × 10 ⁻¹ Pa, an argon flow rate of 90 sccm, an oxygen gas flow rate of 4.7 sccm for 2 and a half minutes using a sputtering apparatus. A 700 mm ITO film was formed on the optical anisotropic body. Then, the baking process (150 degreeC for 10 minutes) was performed, and the phase difference was measured.
<Evaluation of phase difference retention>
Using RETS-100 (manufactured by Otsuka Chemical Co., Ltd.), the phase difference after the formation of the optical anisotropic body and after the post-process was measured, and the retardation holding ratio (%) was calculated from the following formula.
Retardation retention ratio (%) = [(phase difference after post-process) / (phase difference after formation of optical anisotropic body)] × 100
The results obtained are shown in the table below.

(Examples 2 to 21, Comparative Examples 1 to 12)
Optically anisotropic bodies were prepared using the polymerizable liquid crystal compositions (2) to (21) and (24) to (35), and the orientation, transparency, and retardation retention were measured. The results are shown in the above table as Examples 2 to 21 and Comparative Examples 1 to 12, respectively. The production methods of the optical anisotropic bodies of Examples 2 to 21 and Comparative Examples 1 to 12 are as follows.

As in Example 1, the optically anisotropic body for evaluating the orientation of Example 2 was coated with a polyimide alignment film material for a horizontal alignment film on a light-transmitting substrate by spin coating, and the temperature was 100 ° C. And dried for 10 minutes, followed by baking at 200 ° C. for 60 minutes to obtain a coating film. The obtained coating film was rubbed. The rubbing treatment was performed using a commercially available rubbing apparatus. Each of the prepared polymerizable liquid crystal compositions was applied to the obtained base material at 700 rpm / 30 sec using a spin coater at room temperature, dried at 80 ° C. for 2 minutes, and then allowed to stand at 25 ° C. for 2 minutes. By using a mercury lamp and irradiating with UV light while setting the irradiation amount to 3000 mJ / cm ² in a nitrogen atmosphere and setting the temperature at the time of irradiation to 60 ° C. An optical anisotropic body was obtained. Further, the evaluation of the orientation, transparency, and retardation holding ratio was performed by forming an ITO film on the optical anisotropic body under the same conditions as in Example 1. The optically anisotropic bodies for evaluation of orientation in Examples 3 to 6 have an irradiation temperature of 50 ° C., and the optical anisotropic bodies for evaluation of orientation in Comparative Examples 1 to 4 have an irradiation temperature of 75 ° C. The optical anisotropic bodies for evaluation of orientation in Comparative Examples 5 to 6 were set to 25 ° C. and irradiated with UV light to obtain optical anisotropic bodies of Examples and Comparative Examples. Further, the evaluation of the orientation, transparency, and retardation holding ratio was performed by forming an ITO film on the optical anisotropic body under the same conditions as in Example 1.

The optically anisotropic materials for evaluating the orientation, transparency, and retardation retention rate of Examples 7 and 9 to 17 were prepared by applying a polyimide alignment film material for a horizontal alignment film on a light-transmitting substrate by spin coating. After coating and drying at 100 ° C. for 10 minutes, a coating film was obtained by baking at 200 ° C. for 60 minutes. The obtained coating film was rubbed. The rubbing treatment was performed using a commercially available rubbing apparatus. Each of the prepared polymerizable liquid crystal compositions was applied to the obtained substrate at 400 rpm / 30 sec using a spin coater at room temperature, dried at 80 ° C. for 2 minutes, and then allowed to stand at 25 ° C. for 2 minutes. Using a mercury lamp, in each nitrogen atmosphere, set the irradiation amount to 3000 mJ / cm ² and the irradiation temperature to 50 ° C. and irradiate with UV light. An example optical anisotropic body was obtained. In addition, the evaluation of the orientation, transparency, and retardation retention was performed by forming an ITO film on the optical anisotropic body under the same conditions as in Example 1. The optical anisotropic body for evaluation of orientation in Example 8 has an irradiation temperature of 60 ° C., and the optical anisotropic body for evaluation of alignment in Comparative Examples 7 to 10 has an irradiation temperature of 75 ° C. By setting and irradiating with UV light, optical anisotropic bodies of Examples and Comparative Examples were obtained. In addition, the evaluation of the orientation, transparency, and retardation retention was performed by forming an ITO film on the optical anisotropic body under the same conditions as in Example 1.

The optical anisotropic bodies for evaluating the orientation of Examples 18 to 19 and Comparative Example 11 were prepared by adding a solution containing 3% by weight of cinnamic acid polymer (H) (organic solvent cyclopentanone) on a light-transmitting substrate. It was applied by spin coating, dried at 80 ° C. for 2 minutes, and then allowed to stand at 25 ° C. for 2 minutes. And the photo-alignment film was obtained by irradiating parallel light from the perpendicular direction with respect to a base material (irradiation amount: 100 mJ / cm < ² >).

(The cinnamic acid polymer (H) was prepared as follows. 1 part (10.0 mmol) of the compound (I) represented by the above structural formula was dissolved in 10 parts of ethyl methyl ketone, 0.01 part of azobisisobutyronitrile (AIBN) is added and heated under reflux for 2 days under a nitrogen atmosphere to obtain a solution, the solution is then added dropwise to 60 parts of methanol and the precipitated solid is filtered. The obtained solid was dissolved in 5 parts of THF, dropped into 120 parts of ice-cooled hexane, and the precipitated solid was filtered, and the obtained solid was dissolved in 5 parts of THF and dropped into 120 parts of ice-cooled methanol, and stirred. (The precipitated solid is filtered. The obtained solid is dissolved in THF and then vacuum-dried.)
Each of the prepared polymerizable liquid crystal compositions was applied to the obtained base material at 700 rpm / 30 sec using a spin coater at room temperature, dried at 80 ° C. for 2 minutes, and then allowed to stand at 25 ° C. for 2 minutes. Using a mercury lamp, in each nitrogen atmosphere, set the irradiation amount to 3000 mJ / cm ² and the irradiation temperature to 50 ° C. and irradiate with UV light. The optical anisotropic bodies of Examples and Comparative Examples were obtained. In addition, the evaluation of the orientation, transparency, and retardation retention was performed by forming an ITO film on the optical anisotropic body under the same conditions as in Example 1.

As in Example 18, the optical anisotropic bodies for evaluation of orientation in Examples 20 to 21 were prepared by using a solution containing 3% by weight of cinnamic acid polymer (H) on an optically transparent substrate (organic solvent cyclopenta Non-) is applied by spin coating, dried at 80 ° C. for 2 minutes, and then allowed to stand at 25 ° C. for 2 minutes. A photo-alignment film was obtained by irradiating linearly polarized light with parallel light from the direction perpendicular to the substrate (irradiation amount: 100 mJ / cm ² ).
Each of the prepared polymerizable liquid crystal compositions was applied to the obtained substrate at 400 rpm / 30 sec using a spin coater at room temperature, dried at 80 ° C. for 2 minutes, and then allowed to stand at 25 ° C. for 2 minutes. Using a mercury lamp, in each nitrogen atmosphere, set the irradiation amount to 3000 mJ / cm ² and the irradiation temperature to 50 ° C. and irradiate with UV light. The optical anisotropic bodies of Examples and Comparative Examples were obtained. In addition, the evaluation of the orientation, transparency, and retardation retention was performed by forming an ITO film on the optical anisotropic body under the same conditions as in Example 1. Moreover, the optical anisotropic body of Comparative Example 12 was obtained by setting the optical anisotropic body for evaluating the orientation of Comparative Example 12 so that the temperature during irradiation was 75 ° C. and irradiating with UV light. . In addition, the evaluation of the orientation, transparency, and retardation retention was performed by forming an ITO film on the optical anisotropic body under the same conditions as in Example 1.
(Examples 22 to 23, Comparative Example 13)
(VA mode liquid crystal display device)
Optically anisotropic bodies were prepared using the polymerizable liquid crystal compositions (22) to (23) and (36), and the orientation, transparency and retardation retention were measured. The results are shown in the above table as Examples 22 to 23 and Comparative Example 13, respectively. The production methods of the optical anisotropic bodies of Examples 22 to 23 and Comparative Example 13 are as follows.

The optically anisotropic bodies for evaluating the orientation of Examples 22 to 23 were provided with a color filter layer (4) and a planarizing layer (5) on a light-transmitting substrate (3), and then a cinnamic acid polymer ( A solution containing 3% by weight of H) (organic solvent cyclopentanone) was applied by spin coating, dried at 80 ° C. for 2 minutes, then allowed to stand at 25 ° C. for 2 minutes, and then a high-pressure mercury lamp was used. By irradiating linearly polarized light of visible ultraviolet light having a wavelength of about 313 nm and parallel light from a direction perpendicular to the substrate through a polarizing filter (irradiation amount: 100 mJ / cm ² ), a photo-alignment film (6) Got.

The obtained substrate was coated with the polymerizable liquid crystal composition (18) of Example 18 at 700 rpm / 30 sec using a spin coater at room temperature, dried at 80 ° C. for 2 minutes, and left at 25 ° C. for 2 minutes. Then, using a high-pressure mercury lamp, the first retardation film (7) was obtained by irradiating with UV light by setting the irradiation amount to 3000 mJ / cm ² in a nitrogen atmosphere. . On the retardation film 1, the adjusted polymerizable liquid crystal compositions (22) to (23) shown in the above table were applied at 400 rpm / 30 sec using a spin coater at room temperature, dried at 80 ° C. for 2 minutes, and then After leaving at 25 ° C. for 2 minutes, use a high-pressure mercury lamp to set the irradiation amount to 3000 mJ / cm ² in a nitrogen atmosphere and the irradiation temperature to 50 ° C. Then, UV light was irradiated to obtain a second retardation film (8). Evaluation of orientation, transparency, and retardation retention was performed by depositing an ITO film (9) on the second retardation film (8) under the same conditions as in Example 1. An ITO film (9), which is a transparent electrode layer, was deposited on the second retardation film (8), and then an alignment film (10) was formed. An ITO film (13) as a pixel electrode layer was attached to the light transmissive substrate (14), an alignment film (12) was formed, and then a weak rubbing treatment was performed. A DIC-mode TFT liquid crystal was injected into the liquid crystal layer (11) between the alignment film layers (10) and (12) to produce VA mode liquid crystal display devices of Examples 22 to 23 (FIG. 13).

An optical anisotropic body for evaluating the orientation of Comparative Example 13 was prepared by providing a color filter layer (4) and a planarizing layer (5) on a light-transmitting substrate (3), and then a cinnamic acid polymer (H). A solution containing 3% by weight (organic solvent cyclopentanone) was applied by spin coating, dried at 80 ° C. for 2 minutes, and then allowed to stand at 25 ° C. for 2 minutes. The photo-alignment film (6) is obtained by irradiating linearly polarized light of visible ultraviolet light having a wavelength of about 313 nm and parallel light from above in a direction perpendicular to the substrate (irradiation amount: 100 mJ / cm ² ). It was.

The obtained substrate was coated with the polymerizable liquid crystal composition (18) of Example 18 at 700 rpm / 30 sec using a spin coater at room temperature, dried at 80 ° C. for 2 minutes, and left at 25 ° C. for 2 minutes. Then, using a high-pressure mercury lamp, the first retardation film (7) was obtained by irradiating with UV light by setting the irradiation amount to 3000 mJ / cm ² in a nitrogen atmosphere. . On the phase difference film 1, the adjusted polymerizable liquid crystal composition (36) shown in the above table was applied at room temperature at 400 rpm / 30 sec using a spin coater, dried at 80 ° C. for 2 minutes, and then at 25 ° C. After leaving for 2 minutes, use a high-pressure mercury lamp to set the irradiation amount to 3000 mJ / cm ² in a nitrogen atmosphere and the irradiation temperature to 75 ° C. Irradiation was performed to obtain a second retardation film (8). Evaluation of orientation, transparency, and retardation retention was performed by depositing an ITO film (9) on the second retardation film (8) under the same conditions as in Example 1. An alignment film (10) was formed on the second retardation film (8) after depositing an ITO film (9) as a transparent electrode layer. An ITO film (13) as a pixel electrode layer was attached to the light transmissive substrate (14), an alignment film (12) was formed, and then a weak rubbing treatment was performed. A TFT liquid crystal manufactured by DIC was injected into the liquid crystal layer (11) between the alignment film layers (10) and (12) to produce a VA mode liquid crystal display device of Comparative Example 13 (FIG. 13).
The results obtained are shown in the table below.

  From the above results, the optically anisotropic substance (Examples 1 to 23) having a residual monomer amount of 0.0001 to 3% by mass and a residual solvent amount of 2500 ppm or less has a residual monomer amount of 0.0001 to 3% by mass and a residual solvent amount of 2500 ppm. As compared with optical anisotropic bodies (Comparative Examples 1 to 13) that do not satisfy the following, an optical anisotropic body having good orientation, high transparency, and high retardation retention can be obtained. Among the total content of the polymerizable liquid crystal compound (II), the polymerizable liquid crystal compound (II-1) and the chiral compound (III) contained in the polymerizable liquid crystal composition, two or more polymerizable functional groups in the molecule When the optically anisotropic body (Examples 1 to 23) having a polymerizable liquid crystal compound content of 20 to 100% by mass is used, the temperature during UV irradiation of the polymerizable liquid crystal composition is set to 50 to 60 ° C. Thus, an optical anisotropic body having good orientation after ITO film formation and baking treatment, and high transparency and retardation retention can be formed. From the difference from the comparative example, it is possible to form a highly curable optical anisotropic body by heating at the time of UV irradiation, and the residual monomer contained in the optical anisotropic body is changed in orientation by the baking treatment after the ITO film formation. Therefore, it is considered that good orientation can be obtained. Furthermore, when the optical anisotropic body (Examples 1 to 23) of the present invention is used, an optical anisotropic body having a residual solvent amount of 2500 ppm or less can be formed by using an organic solvent having a boiling point of 135 ° C. or less, It is possible to obtain an optical anisotropic body having good orientation after the ITO film is formed and baked and having a high retardation retention. It is considered that an optical anisotropic body with good orientation and high retardation retention can be obtained because there are few residual solvents that cause orientation inhibition in the baking treatment after ITO film formation. .

Claims (10)

  One or more polymerization initiators (I), one or two or more polymerizable liquid crystal compounds (II) having two or more polymerizable functional groups in the molecule, and optionally one or more Including an optically anisotropic layer using a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound (II-1) having two or more kinds of one polymerizable functional group, and included in the optically anisotropic layer An optically anisotropic body in which the content of the polymerizable liquid crystal compound (II) and the optionally included polymerizable liquid crystal compound (II-1) is 0.0001 mass% or more and 3 mass% or less. The polymerizable liquid crystal compound (II) having two or more polymerizable functional groups in the molecule is represented by the general formula (II-A)

(In the general formula (II-A), P ²¹ represents a polymerizable functional group,
Sp ²¹ represents an alkylene group having 1 to 18 carbon atoms (the hydrogen atom in the alkylene group may be substituted with one or more halogen atoms, a CN group, or a group having a polymerizable functional group, each of the two or more CH ₂ groups not one CH ₂ group or adjacent existing in the alkylene group independently of one another, -O -, - COO -, - OCO- or --OCO-O-by May be replaced).
In the general formula ^(II-A), X 21 is _{-O -, - S -, -} OCH 2 -, - CH 2 O -, - CO -, - COO -, - OCO -, - CO-S-, -S-CO -, - O- CO-O -, - CO-NH -, - NH-CO -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - CF ₂ S—, —SCF ₂ —, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —COO—CH ₂ CH ₂ —, _{-OCO-CH 2 CH 2 -,} - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH _{2 -OCO -, - CH = CH} -, - N = N -, - CH = N-N = CH -, - CF = CF -, - C≡C- or a single Represents the total, ^(however, P 21 ^{-Sp 21,} and ^Sp 21 ^-X 21 are, -O-O -, - O -NH - -, do not contain S-S- and -O-S- group.)
q21 represents 0 or 1,
MG represents a mesogenic group,
R ²¹ represents the general formula (II-a)

(In General Formula (II-a), P ²² represents a polymerizable functional group, Sp ²² represents the same as defined in Sp ²¹ , and X ²² represents the same as defined in X ^21. represent the same thing ^(although, P ^{22 -Sp 22,} and ^Sp 22 ^-X 22 are, -O-O -, - O -NH -, - does not contain S-S- and -O-S- group. ), Q22 represents 0 or 1),
The mesogenic group represented by MG has the general formula (II-b)

(In the general formula (II-b), B1, B2 and B3 are each independently 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5. -Diyl group, 1,3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene-2,6 -Diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group-, 1,2,3,4-tetrahydro Naphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4,4a, 9 , 10a-Octa Drophenanthrene-2,7-diyl group, 1,4-naphthylene group, benzo [1,2-b: 4,5-b ′] dithiophene-2,6-diyl group, benzo [1,2-b: 4 , 5-b ′] diselenophen-2,6-diyl group, [1] benzothieno [3,2-b] thiophene-2,7-diyl group, [1] benzoselenopheno [3,2-b] selenophene- Represents a 2,7-diyl group or a fluorene-2,7-diyl group, and has one or more F, Cl, CF ₃ , OCF ₃ , CN groups, or an alkyl group having 1 to 8 carbon atoms (substituent) hydrogen atoms in the alkyl group may be substituted with one or more phenyl groups, independently of each one CH ₂ group or not adjoining two or more CH ₂ groups existing in the groups to each other -O-, -COO-, -OCO- or -OCO May be substituted by O-), an alkoxy group having 1 to 8 carbon atoms, an alkanoyl group having 1 to 8 carbon atoms, an alkanoyloxy group having 1 to 8 carbon atoms, or an alkyl group having 1 to 8 carbon atoms. An alkoxycarbonyl group, an alkenyl group having 2 to 8 carbon atoms, an alkenyloxy group having 2 to 8 carbon atoms, an alkenoyl group having 2 to 8 carbon atoms, an alkenoyloxy group having 2 to 8 carbon atoms, and / or Formula (II-c)

(In the formula ^{(II-c), P 23} represents a polymerizable functional group,
Sp ²³ represents the same as defined in Sp ²¹ above,
X ²³ represents —O—, —COO—, —OCO—, —OCH ₂ —, —CH ₂ O—, —CH ₂ CH ₂ OCO—, —COOCH ₂ CH ₂ —, —OCOCH ₂ CH ₂ —, or A single bond is represented, q23 represents 0 or 1, and q24 represents 0 or 1. (However, P ²³ -Sp ²³ and Sp ²³ -X ²³ do not include —O—O—, —O—NH—, —S—S— and —O—S— groups). You may,
Z1 and Z2 are each independently —COO—, —OCO—, —CH ₂ CH ₂ —, —OCH ₂ —, —CH ₂ O—, —CH═CH—, —C≡C—, —CH═. CHCOO -, - OCOCH = CH - , - CH 2 CH 2 COO -, - CH 2 CH 2 OCO -, - COOCH 2 CH 2 -, - OCOCH 2 CH 2 -, - C = N -, - N = C- , —CONH—, —NHCO—, —C (CF ₃ ) ₂ —, an alkyl group having 2 to 10 carbon atoms which may have a halogen atom or a single bond, Z1 and Z2 each represent a single bond In the case, among the above B1, B2, and B3, the substituents each having two adjacent ring structures may combine to form a cyclic group, and r1 represents 0, 1, 2, or 3; When there are a plurality of B1 and Z1, each is the same or different Also good. The optical anisotropic body of Claim 1 which is a compound represented by this. The polymerizable liquid crystal compound (II-1) having one polymerizable functional group in the molecule is represented by the general formula (II-1)

(In General Formula (II-1), ^P211 represents a polymerizable functional group,
X ²¹¹ represents —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO. _{-O -, - CO-NH -} , - NH-CO -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —COO—CH ₂ CH ₂ —, —OCO—CH ₂ CH ₂ —, — _{CH 2 CH 2 -COO -, -} CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CH = CH- , -N = N -, - CH = N-N = CH -, - CF = CF -, - C≡C- or a single bond (provided that, ^{P 2 1} -Sp ^211, and ^Sp 211 ^{-X 211} may, -O-O -, - O -NH -, - does not contain S-S- and -O-S- group).
q211 represents 0 or 1,
R ²¹¹ represents a hydrogen atom, a halogen atom, a cyano group, one —CH ₂ — or two or more non-adjacent —CH ₂ —, each independently —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, —CO—NH—, —NH—CO—, —NH—, —N (CH ₃ ). -, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -CH = CH-, -CF = CF- or -C≡C Represents a straight-chain or branched alkyl group having 1 to 12 carbon atoms or a straight-chain or branched alkenyl group having 1 to 12 carbon atoms, which may be substituted by-, one or two of the alkyl group or alkenyl group One or more hydrogen atoms may be substituted with a halogen atom or a cyano group. Each may be the same or different,
Sp ²¹¹ represents an alkylene group having 1 to 18 carbon atoms (the hydrogen atom in the alkylene group may be substituted with one or more halogen atoms or a CN group, and one hydrogen atom present in the group). Or a CH ₂ group or two or more non-adjacent CH ₂ groups may each be independently replaced by —O—, —COO—, —OCO— or —OCO—O—. Represent,
MG ¹ represents a mesogenic group, and the mesogenic group has the general formula (II-1-b)

(In the general formula (II-1-b), B11, B21 and B31 are each independently 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2. , 5-diyl group, 1,3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene-2 , 6-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group-, 1,2,3,4 -Tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4,4a , 9, 10 -Octahydrophenanthrene-2,7-diyl group, 1,4-naphthylene group, benzo [1,2-b: 4,5-b '] dithiophene-2,6-diyl group, benzo [1,2-b : 4,5-b ′] diselenophen-2,6-diyl group, [1] benzothieno [3,2-b] thiophene-2,7-diyl group, [1] benzoselenopheno [3,2-b] Represents a selenophene-2,7-diyl group or a fluorene-2,7-diyl group, and has at least one F, Cl, CF ₃ , OCF ₃ , CN group or an alkyl group having 1 to 8 carbon atoms as a substituent. (hydrogen atom in the alkyl group may be substituted with one or more phenyl groups, each one CH ₂ group or not adjoining two or more CH ₂ groups that are present mutually in this group Independently of —O—, —COO—, —OCO— or -OCO-O- may be substituted.), An alkoxy group having 1 to 8 carbon atoms, an alkanoyl group having 1 to 8 carbon atoms, an alkanoyloxy group having 1 to 8 carbon atoms, and 1 carbon atom May have an alkoxycarbonyl group having 8 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkenyloxy group having 2 to 8 carbon atoms, and / or an alkenoyl group having 2 to 8 carbon atoms,
Z11 and Z21 are each independently —COO—, —OCO—, —CH ₂ CH ₂ —, —OCH ₂ —, —CH ₂ O—, —CH═CH—, —C≡C—, —CH═. CHCOO -, - OCOCH = CH - , - CH 2 CH 2 COO -, - CH 2 CH 2 OCO -, - COOCH 2 CH 2 -, - OCOCH 2 CH 2 -, - C = N -, - N = C- , -CONH-, -NHCO-, -C (CF ₃ ) _2- , an alkyl group having 2 to 10 carbon atoms which may have a halogen atom or a single bond, r11 is 0, 1, 2 or 3 In the case where a plurality of B11 and Z11 are present, they may be the same or different. In the case where Z11 and Z21 represent a single bond, the substituents of the two adjacent ring structures among B11, B21 and B31 are combined to form a cyclic group. Also good. ). The optical anisotropic body of Claim 1 or Claim 2 which is a compound represented by this.   The retardation film using the optical anisotropic body as described in any one of Claims 1-3.   The phase difference patterning film using the optical anisotropic body as described in any one of Claims 1-3.   A brightness enhancement film using the optical anisotropic body according to any one of claims 1 to 3.   The antireflection film using the optical anisotropic body as described in any one of Claims 1-3.   The thermal insulation film using the optically anisotropic body as described in any one of Claims 1-3.   The liquid crystal display device using the optical anisotropic body as described in any one of Claims 1-3.   The optical element which has an optical anisotropic body as described in any one of Claims 1-3.

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