JP2018087152A - Polymerizable liquid crystal compound, retardation film, polarizing plate including the retardation film and optical display - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymerizable liquid crystal compound that has a low liquid crystal phase transition temperature and is used for constituting a retardation film preferably having reverse wavelength dispersion.SOLUTION: The polymerizable liquid crystal compound is represented by formula (a) as given below.SELECTED DRAWING: None

Description

  The present invention relates to a polymerizable liquid crystal compound, a retardation film composed of a polymer in an alignment state of the polymerizable liquid crystal compound, a polarizing plate including the retardation film, and an optical display.

  As an optical film such as a retardation film used in a flat panel display (FPD), for example, a coating liquid obtained by dissolving a polymerizable liquid crystal compound in a solvent is applied to a supporting substrate and then polymerized. There is a coating type optical film. Conventionally, as the polymerizable liquid crystal compound, for example, a nematic liquid crystal compound having a rod-like structure in which 2 to 4 6-membered rings are connected is known. On the other hand, the retardation film is required to be capable of polarization conversion in the entire wavelength region as one of its characteristics, and exhibits reverse wavelength dispersion of [Re (450 nm) / Re (550 nm)] <1. In the wavelength range, it is theoretically known that uniform polarization conversion is possible. A polymerizable compound capable of constituting such a retardation film is disclosed in Patent Document 1, for example.

  Such a coating-type optical film is formed by applying a coating liquid obtained by dissolving a polymerizable liquid crystal compound in a solvent to a support substrate to form a coating film, and then converting the polymerizable liquid crystal compound contained in the coating film into a nematic phase or the like. It can obtain by the method of making it change to a liquid crystal phase state, drying a coating film, and distilling a solvent off (for example, patent document 2).

JP 2011-207765 A Japanese Patent No. 4606195

  In the above method, the polymerizable liquid crystal compound can be transferred to the liquid crystal phase by heating. However, when the liquid crystal phase transition temperature is high as in the liquid crystal compound described in Patent Document 2, problems such as excessive waste of heat energy and deformation of the support substrate on which the liquid crystal compound is applied occur. Production of the film may be difficult.

  Accordingly, an object of the present invention is to provide a polymerizable liquid crystal compound for constituting a retardation film having a low liquid crystal phase transition temperature and preferably having reverse wavelength dispersion. Another object of the present invention is to provide a retardation film composed of a polymer in the alignment state of the polymerizable liquid crystal compound.

［式（ａ）中、
ｍ及びｎは、それぞれ独立に、０〜３の整数を表し、
Ｂ^１、Ｂ^２、Ｄ^１、Ｄ^２、Ｅ^１及びＥ^２は、それぞれ独立に、−ＣＲ^１Ｒ^２−、−ＣＨ_２−ＣＨ_２−、−Ｏ−、−Ｓ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−、−Ｏ−ＣＯ−Ｏ−、−Ｃ（＝Ｓ）−Ｏ−、−Ｏ−Ｃ（＝Ｓ）−、−Ｏ−Ｃ（＝Ｓ）−Ｏ−、−ＣＯ−ＮＲ^１−、−ＮＲ^２−ＣＯ−、−Ｏ−ＣＨ_２−、−ＣＨ_２−Ｏ−、−Ｓ−ＣＨ_２−、−ＣＨ_２−Ｓ−又は単結合を表し、Ｒ^１及びＲ^２は、それぞれ独立に、水素原子、フッ素原子又は炭素数１〜４のアルキル基を表し、
Ａ^１、Ａ^２、Ｇ^１及びＧ^２は、それぞれ独立に、炭素数３〜１６の２価の脂環式炭化水素基又は炭素数６〜２０の２価の芳香族炭化水素基を表し、該脂環式炭化水素基及び該芳香族炭化水素基に含まれる水素原子は、それぞれ独立に、ハロゲン原子、−Ｒ^３、−ＯＲ^４、シアノ基又はニトロ基で置換されていてもよく、該脂環式炭化水素基に含まれる−ＣＨ_２−（メチレン基）は、それぞれ独立に、−Ｏ−、−Ｓ−、−ＮＨ−又は−ＮＲ^５−で置換されていてもよく、該脂環式炭化水素基に含まれる−ＣＨ（−）−（メチン基）は−Ｎ（−）−（窒素原子）で置換されていてもよく、Ｒ^３、Ｒ^４及びＲ^５は、それぞれ独立に、炭素数１〜４のアルキル基を表し、該アルキル基に含まれる水素原子は、フッ素原子で置換されていてもよく、
Ｆ^１及びＦ^２は、それぞれ独立に、炭素数１〜１２のアルカンジイル基を表し、該アルカンジイル基に含まれる水素原子は、それぞれ独立に、−ＯＲ^６又はハロゲン原子で置換されていてもよく、該アルカンジイル基に含まれる−ＣＨ_２−（メチレン基）は、それぞれ独立に、−Ｏ−又は−ＣＯ−で置換されていてもよく、Ｒ^６は、炭素数１〜４のアルキル基を表し、該アルキル基に含まれる水素原子はフッ素原子で置換されていてもよく、
Ｐ^１及びＰ^２は、それぞれ独立に、水素原子又は重合性基を表し、ただしＰ^１及びＰ^２のうち少なくとも１つは重合性基を表し、
Ｊ^１は、水素原子又は炭素数１〜３のアルキル基を表し、
Ｊ^２は、単環構造又は多環構造を有する炭素数３〜２５の炭化水素基を表し、該炭化水素基に含まれる−ＣＨ_２−（メチレン基）は、それぞれ独立に、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＳ−又は−ＮＲ^７−で置換されていてもよく、該炭化水素基に含まれる水素原子は、それぞれ独立に、炭素数１〜６のアルキル基、炭素数３〜６の脂環式炭化水素基又は炭素数６〜１２の芳香族炭化水素基で置換されていてもよく、Ｒ^７は、水素原子又は炭素数１〜６のアルキル基を表す］
で表される重合性液晶化合物。
［２］Ｊ^２は、下記式（ｂ）：

［式（ｂ）中、
Ｋは、−Ｘ^１Ｃ（＝）Ｘ^２−と共に単環構造又は多環構造を構成する、炭素数１〜１１の炭化水素基を表し、該炭化水素基に含まれる−ＣＨ_２−（メチレン基）は、それぞれ独立に、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＳ−又は−ＮＲ^７−で置換されていてもよく、該炭化水素基に含まれる水素原子は、それぞれ独立に、炭素数１〜６のアルキル基、炭素数３〜６の脂環式炭化水素基又は炭素数６〜１２の芳香族炭化水素基で置換されていてもよく、Ｒ^７は、水素原子又は炭素数１〜６のアルキル基を表し、
Ｘ^１及びＸ^２は、それぞれ独立に、−ＣＯ−、−ＣＳ−、−Ｓ−、−Ｏ−又は−ＮＲ^８−を表し、Ｒ^８は、水素原子、炭素数１〜６のアルキル基、炭素数３〜６の脂環式炭化水素基又は炭素数６〜１２の芳香族炭化水素基を表し、
＊は、結合手を表す］
で表される、前記［１］に記載の重合性液晶化合物。
［３］式（ａ）中のＪ^２は、式（ｃ−１）〜式（ｃ−５）：

［式（ｃ−１）〜式（ｃ−５）中、
Ｙ^１１、Ｙ^１２、Ｙ^１３、Ｙ^２１、Ｙ^２２、Ｙ^３１、Ｙ^３２、Ｙ^４１、Ｙ^４２、Ｙ^５１及びＹ^５２は、それぞれ独立に、酸素原子又は硫黄原子を表し、
Ｚ^１１、Ｚ^１２、Ｚ^２１、Ｚ^２２、Ｚ^３１、Ｚ^４１、Ｚ^５１、Ｚ^５２、Ｚ^５３及びＺ^５４は、それぞれ独立に、水素原子、炭素数１〜６のアルキル基、炭素数３〜６の脂環式炭化水素基、又は炭素数６〜１１の芳香族炭化水素基を表し、
＊は、結合手を表す］
のいずれかで表される、前記［１］又は［２］に記載の重合性液晶化合物。
［４］Ｇ^１及びＧ^２はトランス−シクロヘキサン−１，４−ジイル基である、前記［１］〜［３］のいずれかに記載の重合性液晶化合物。
［５］前記［１］〜［４］のいずれかに記載の重合性液晶化合物の配向状態における重合体から構成される位相差フィルム。
［６］前記［５］に記載の位相差フィルムを含む偏光板。
［７］前記［６］に記載の偏光板を含む光学ディスプレイ。 The present invention provides the following preferred embodiments.
[1] The following formula (a):

[In the formula (a),
m and n each independently represents an integer of 0 to 3,
^{B 1, B 2, D 1} , D 2, E 1 and ^{E 2,} each _{^{independently, -CR 1 R 2 -, -}} CH 2 -CH 2 -, - O -, - S -, - CO-O -, -O-CO-, -O-CO-O-, -C (= S) -O-, -O-C (= S)-, -O-C (= S) -O-, -CO Represents —NR ¹ —, —NR ² —CO—, —O—CH ₂ —, —CH ₂ —O—, —S—CH ₂ —, —CH ₂ —S— or a single bond, R ¹ and R ² Each independently represents a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms,
A ¹ , A ² , G ¹ and G ² each independently represent a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, The hydrogen atom contained in the alicyclic hydrocarbon group and the aromatic hydrocarbon group may each independently be substituted with a halogen atom, —R ³ , —OR ⁴ , a cyano group or a nitro group, —CH ₂ — (methylene group) contained in the alicyclic hydrocarbon group may each independently be substituted with —O—, —S—, —NH— or —NR ⁵ —, -CH (-)-(methine group) contained in the formula hydrocarbon group may be substituted with -N (-)-(nitrogen atom), and R ³ , R ⁴ and R ⁵ are each independently Represents an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is substituted with a fluorine atom; Well,
F ¹ and F ² each independently represent an alkanediyl group having 1 to 12 carbon atoms, and each hydrogen atom contained in the alkanediyl group may be independently substituted with —OR ⁶ or a halogen atom. The —CH ₂ — (methylene group) contained in the alkanediyl group may be independently substituted with —O— or —CO—, and R ⁶ is an alkyl group having 1 to 4 carbon atoms. And the hydrogen atom contained in the alkyl group may be substituted with a fluorine atom,
P ¹ and P ² each independently represent a hydrogen atom or a polymerizable group, provided that at least one of P ¹ and P ² represents a polymerizable group;
J ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms,
J ² represents a hydrocarbon group having 3 to 25 carbon atoms having a monocyclic structure or a polycyclic structure, and —CH ₂ — (methylene group) contained in the hydrocarbon group is independently —O—, -S -, - CO -, - CS- , or -NR ⁷ - may be substituted with a hydrogen atom contained in the hydrocarbon group is independently an alkyl group having 1 to 6 carbon atoms, carbon atoms R ⁷ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, which may be substituted with a 3 to 6 alicyclic hydrocarbon group or an aromatic hydrocarbon group having 6 to 12 carbon atoms.
A polymerizable liquid crystal compound represented by:
[2] J ² is represented by the following formula (b):

[In the formula (b),
K ^{is, -X 1 C (=) X} 2 - together constitute a monocyclic structure or a polycyclic structure, a hydrocarbon group of 1 to 11 carbon atoms, -CH ₂ contained in the hydrocarbon group - (methylene Group) may be each independently substituted with —O—, —S—, —CO—, —CS— or —NR ⁷ —, and each hydrogen atom contained in the hydrocarbon group independently represents , An alkyl group having 1 to 6 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms, and R ⁷ is a hydrogen atom or carbon Represents an alkyl group of 1 to 6;
X ¹ and X ² each independently represent —CO—, —CS—, —S—, —O— or —NR ⁸ —, wherein R ⁸ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, Represents an alicyclic hydrocarbon group having 3 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms,
* Represents a bond]
The polymerizable liquid crystal compound according to the above [1], represented by:
[3] J ² in the formula (a) is a formula (c-1) to a formula (c-5):

[In Formula (c-1)-Formula (c-5),
Y ¹¹ , Y ¹² , Y ¹³ , Y ²¹ , Y ²² , Y ³¹ , Y ³² , Y ⁴¹ , Y ⁴² , Y ⁵¹ and Y ⁵² each independently represent an oxygen atom or a sulfur atom,
Z ¹¹ , Z ¹² , Z ²¹ , Z ²² , Z ³¹ , Z ⁴¹ , Z ⁵¹ , Z ⁵² , Z ⁵³ and Z ⁵⁴ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or 3 carbon atoms. Represents an alicyclic hydrocarbon group having 6 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 11 carbon atoms,
* Represents a bond]
The polymerizable liquid crystal compound according to [1] or [2], represented by any one of:
[4] The polymerizable liquid crystal compound according to any one of [1] to [3], wherein G ¹ and G ² are trans-cyclohexane-1,4-diyl groups.
[5] A retardation film composed of a polymer in the alignment state of the polymerizable liquid crystal compound according to any one of [1] to [4].
[6] A polarizing plate comprising the retardation film according to [5].
[7] An optical display including the polarizing plate according to [6].

  According to the present invention, it is possible to provide a polymerizable liquid crystal compound for constituting a retardation film having a low liquid crystal phase transition temperature and preferably having reverse wavelength dispersion. Moreover, according to this invention, the retardation film comprised from the polymer in the orientation state of this polymeric liquid crystal compound can also be provided.

で表される化合物である。 <Polymerizable liquid crystal compound>
The polymerizable liquid crystal compound according to one embodiment of the present invention has the following formula (a):

It is a compound represented by these.

In formula (a), m and n each independently represent an integer of 0 to 3,
^{B 1, B 2, D 1} , D 2, E 1 and ^{E 2,} each _{^{independently, -CR 1 R 2 -, -}} CH 2 -CH 2 -, - O -, - S -, - CO-O -, -O-CO-, -O-CO-O-, -C (= S) -O-, -O-C (= S)-, -O-C (= S) -O-, -CO Represents —NR ¹ —, —NR ² —CO—, —O—CH ₂ —, —CH ₂ —O—, —S—CH ₂ —, —CH ₂ —S— or a single bond, R ¹ and R ² Each independently represents a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms,
A ¹ , A ² , G ¹ and G ² each independently represent a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, The hydrogen atom contained in the alicyclic hydrocarbon group and the aromatic hydrocarbon group may each independently be substituted with a halogen atom, —R ³ , —OR ⁴ , a cyano group or a nitro group, —CH ₂ — (methylene group) contained in the alicyclic hydrocarbon group may each independently be substituted with —O—, —S—, —NH— or —NR ⁵ —, -CH (-)-(methine group) contained in the formula hydrocarbon group may be substituted with -N (-)-(nitrogen atom), and R ³ , R ⁴ and R ⁵ are each independently Represents an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group is substituted with a fluorine atom. It may be,
F ¹ and F ² each independently represent an alkanediyl group having 1 to 12 carbon atoms, and each hydrogen atom contained in the alkanediyl group may be independently substituted with —OR ⁶ or a halogen atom. The —CH ₂ — (methylene group) contained in the alkanediyl group may be independently substituted with —O— or —CO—, and R ⁶ is an alkyl group having 1 to 4 carbon atoms. A hydrogen atom contained in the alkyl group may be substituted with a fluorine atom,
P ¹ and P ² each independently represent a hydrogen atom or a polymerizable group, provided that at least one of P ¹ and P ² represents a polymerizable group;
J ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms,
J ² represents a hydrocarbon group having 3 to 25 carbon atoms having a monocyclic structure or a polycyclic structure, and —CH ₂ — (methylene group) contained in the hydrocarbon group is independently —O—, -S -, - CO -, - CS- , or -NR ⁷ - may be substituted with a hydrogen atom contained in the hydrocarbon group is independently an alkyl group having 1 to 6 carbon atoms, carbon atoms may be substituted with 3-6 alicyclic hydrocarbon group or aromatic hydrocarbon group having 6 to 12 carbon atoms, R ⁷ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

In the formula (a), m and n each independently represent an integer of 0 to 3, preferably an integer of 1 to 2, more preferably 1. Moreover, it is preferable that m and n are mutually the same integer from a viewpoint that it is easy to manufacture the said polymeric liquid crystal compound and can suppress manufacturing cost. Furthermore, when m and n are 2 or 3, a plurality of A ¹ , A ² , B ¹ and B ² may be the same or different from each other. From the viewpoint of easy production of a polymerizable liquid crystal compound industrially, a plurality of A ¹ , A ² , B ¹ and B ² are the same as each other (that is, a plurality of A ¹ are the same). And a plurality of A ² are the same, a plurality of B ¹ are the same, and a plurality of B ² are the same).

Wherein ^{(a), B 1, B} 2, D 1, D 2, E 1 and ^{E 2,} each _{^{independently, -CR 1 R 2 -, -}} CH 2 -CH 2 -, - O -, - S -, -CO-O-, -O-CO-, -O-CO-O-, -C (= S) -O-, -O-C (= S)-, -O-C (= S). —O—, —CO—NR ¹ —, —NR ² —CO—, —O—CH ₂ —, —CH ₂ —O—, —S—CH ₂ —, —CH ₂ —S— or a single bond is represented. . In said formula, R < ¹ > and R < ² > represents a hydrogen atom, a fluorine atom, or a C1-C4 alkyl group each independently.

B ¹ and B ² are each independently —O—, —S—, —O—CO—, —CO—O—, —O from the viewpoint of easy development of the liquid crystal phase of the polymerizable liquid crystal compound. ^{-C (= S) -, -} C (= S) -O -, - CO-NR 1 -, - NR 2 -CO -, - O-CH 2 -, - CH 2 -O -, - S-CH ₂ - or preferably a _-CH 2 -S-, -O -, - and more preferably O-CO- or -CO-O-. From the viewpoint of easily producing the polymerizable liquid crystal compound and suppressing the production cost, it is preferable that B ¹ and B ² are the same. Note that B ¹ and B ² are the same as each other when the structures of B ¹ and B ² when viewed from the center of the phenyl group having a group of —C (= J ² ) J ¹ in the formula (a) are the same. For example, when B ¹ is —O—CO—, B ² that is the same as B ¹ is —CO—O—. The same applies to the relationship between E ¹ and E ² , A ¹ and A ² , G ¹ and G ² , F ¹ and F ^2, and P ¹ and P ² .

D ¹ , D ² , E ¹ and E ² are each independently —O—, —S—, —O—CO—, —CO, from the viewpoint of easy development of the liquid crystal phase of the polymerizable liquid crystal compound. -O -, - O-C ( = S) -, - C (= S) -O -, - CO-NR 1 -, - NR 2 -CO -, - O-CH 2 -, - CH 2 -O —, —S—CH ₂ — or —CH ₂ —S— is preferred, and —O—, —O—CO— or —CO—O— is more preferred. From the viewpoint that the polymerizable liquid crystal compound can be easily produced and the production cost can be suppressed, D ¹ and D ² are preferably the same and / or E ¹ and E ² are the same. It is preferable.

In the formula (a), A ¹ , A ² , G ¹ and G ² are each independently a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms or a divalent aromatic group having 6 to 20 carbon atoms. Represents a hydrocarbon group. Carbon number of the said bivalent alicyclic hydrocarbon group becomes like this. Preferably it is 4-15, More preferably, it is 5-10, More preferably, it is 5-8, Most preferably, it is 5 or 6. Carbon number of the divalent aromatic hydrocarbon group is preferably 6 to 18, more preferably 6 to 16, further preferably 6 to 10, and particularly preferably 5 or 6. The hydrogen atoms contained in the alicyclic hydrocarbon group and the aromatic hydrocarbon group may each independently be substituted with a halogen atom, —R ³ , —OR ⁴ , a cyano group, or a nitro group. Here, R ³ and R ⁴ each independently represent an alkyl group having 1 to 4 carbon atoms, hydrogen atoms contained in the alkyl group may be substituted with a fluorine atom.

  Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Group is preferable, an alkyl group having 1 or 2 carbon atoms is more preferable, and a methyl group is particularly preferable.

Examples of the alkoxy group having 1 to ⁴ carbon atoms in —OR ⁴ include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group. An alkoxy group having 1 to 3 carbon atoms is preferable, an alkoxy group having 1 or 2 carbon atoms is more preferable, and a methoxy group is particularly preferable.

  As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, A fluorine atom, a chlorine atom, or a bromine atom is preferable.

Examples of the divalent alicyclic hydrocarbon group include a cycloalkanediyl group. The —CH ₂ — (methylene group) contained in the alicyclic hydrocarbon group may be independently substituted with —O—, —S—, —NH— or —NR ⁵ —. -CH (-)-(methine group) contained in the cyclic hydrocarbon group may be substituted with -N (-)-(nitrogen atom). Here, R ⁵ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a fluorine atom.

Examples of the divalent alicyclic hydrocarbon group include groups represented by the following formulas (g-1) to (g-4). As the divalent alicyclic hydrocarbon group in which —CH ₂ — (methylene group) contained in the alicyclic hydrocarbon group is replaced with —O—, —S—, —NH— or —NR ⁵ —, Examples include groups represented by the following formula (g-5) to formula (g-8). The divalent alicyclic hydrocarbon group in which —CH (−) — (methine group) contained in the alicyclic hydrocarbon group is replaced with —N (−) — (nitrogen atom) is represented by the following formula (g And groups represented by -9) and formula (g-10). These are preferably 5-membered or 6-membered alicyclic hydrocarbon groups.

  The divalent alicyclic hydrocarbon group is preferably a group represented by the formula (g-1), more preferably a cyclohexane-1,4-diyl group, and trans-cyclohexane- A 1,4-diyl group is particularly preferred.

  Examples of the divalent aromatic hydrocarbon group include groups represented by formula (a-1) to formula (a-8). As the divalent aromatic hydrocarbon group, a 1,4-phenylene group is preferable.

In one embodiment of the present invention, from the viewpoint of production of the polymerizable liquid crystal compound, A ¹ and A ² are preferably each independently a divalent aromatic hydrocarbon group, and 1,4-phenylene More preferably, it is a group. In one embodiment of the present invention, from the viewpoint of production of the polymerizable liquid crystal compound, G ¹ and G ² are preferably each independently a divalent alicyclic hydrocarbon group, More preferably, it is a cyclohexane-1,4-diyl group, and it is particularly preferable that both G ¹ and G ² are trans-cyclohexane-1,4-diyl groups. When both G ¹ and G ² are trans-cyclohexane-1,4-diyl groups, the polymerizable liquid crystal compound exhibits particularly good liquid crystallinity. Also, easy to easily produce the above polymerizable liquid crystal compound, from the viewpoint of capable of suppressing the manufacturing cost, it is preferable that A ¹ and A ² are the same, and / or the G ¹ and G ² equal It is preferable that

In the formula (a), F ¹ and F ² each independently represents an alkanediyl group having 1 to 12 carbon atoms, preferably 2 to 12, more preferably 3 to 12, more preferably 4 to 10, for example 6. Represent. Each hydrogen atom contained in the alkanediyl group may be independently substituted with —OR ⁶ or a halogen atom, and —CH _2- (methylene group) contained in the alkanediyl group is independently It may be substituted with -O- or -CO-. R ⁶ represents an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group may be substituted with a fluorine atom. From the viewpoint that the polymerizable liquid crystal compound can be easily manufactured and the manufacturing cost can be suppressed, F ¹ and F ² are preferably the same as each other.

In formula (a), P ¹ and P ² each independently represent a hydrogen atom or a polymerizable group. However, at least one of P ¹ and P ² is a polymerizable group, and it is preferable that both P ¹ and P ² are polymerizable groups. The polymerizable group is a group containing a group that can participate in a polymerization reaction. The groups that can participate in the polymerization reaction include vinyl group, p- (2-phenylethenyl) phenyl group, acryloyl group, acryloyloxy group, methacryloyl group, methacryloyloxy group, carboxyl group, methylcarbonyl group, hydroxyl group, carbamoyl. Group, an alkylamino group having 1 to 4 carbon atoms, an amino group, a formyl group, -N = C = O, -N = C = S, an oxiranyl group, an oxetanyl group, and the like.

  In terms of suitability for photopolymerization, the polymerizable group is preferably a radical polymerizable group or a cationic polymerizable group. In particular, an acryloyl group, an acryloyloxy group, a methacryloyl group or a methacryloyloxy group is preferable in terms of easy handling and production, and an acryloyl group or an acryloyloxy group is more preferable in terms of high polymerizability.

In formula (a), J ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. J ¹ preferably represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, or an isopropyl group, more preferably a hydrogen atom or a methyl group, from the viewpoint of production of the polymerizable liquid crystal compound.

Wherein (a), J ² represents a hydrocarbon group having 3 to 25 carbon atoms having a single ring structure or a polycyclic structure. Carbon number of this hydrocarbon group becomes like this. Preferably it is 3-20, More preferably, it is 3-16, More preferably, it is 4-14. —CH ₂ — (methylene group) contained in the hydrocarbon group in J ² may be independently substituted with —O—, —S—, —CO—, —CS— or —NR ⁷ —. , R ⁷ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, or an aromatic hydrocarbon group having 6 to 11 carbon atoms. The hydrogen atoms contained in the hydrocarbon group in ^{J 2} is independently an alkyl group having 1 to 6 carbon atoms (preferably 1 to 3 carbon atoms), 3 to 6 carbon atoms (preferably 4-6 carbon atoms ) Or an alicyclic hydrocarbon group or an aromatic hydrocarbon group having 6 to 12 carbon atoms (preferably 6 to 10 carbon atoms, for example 6 carbon atoms).

The single ring structures are those having one ring in the hydrocarbon group represented by J ^2. The polycyclic structure, those having two or more rings in the hydrocarbon group represented by J ^2. In a polycyclic structure, each ring may exist independently of the other rings, and a condensed ring in which a bond of one ring shares a bond with another ring may exist. The condensed ring may be an aliphatic ring, an aromatic ring, a heterocyclic ring, or a ring obtained by combining these rings.

  Examples of the hydrocarbon group having a monocyclic structure or a polycyclic structure include the following (j-1) to (j-16).

で表される。 In a preferred embodiment of the present invention, J ² in formula (a) is represented by the following formula (b):

It is represented by

In formula (b), K ^{is, -X 1 C (=) X} 2 - constituting together mono or poly cyclic structures represent a hydrocarbon group having 1 to 11 carbon atoms, contained in the hydrocarbon group —CH ₂ — (methylene group) may be independently substituted with —O—, —S—, —CO—, —CS— or —NR ⁷ —, and hydrogen contained in the hydrocarbon group Each atom may be independently substituted with an alkyl group having 1 to 6 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms, and R ⁷ Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
X ¹ and X ² each independently represent —CO—, —CS—, —S—, —O— or —NR ⁸ —, wherein R ⁸ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, Represents an alicyclic hydrocarbon group having 3 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms,
* Represents a bond.

When X ¹ and X ² in the formula (b) are each independently —CO—, —CS—, —S—, —O— or —NR ⁸ —, the liquid crystal phase transition temperature, particularly the nematic phase The transition temperature can be lowered. The reason for this is not clear, but it is considered that the formation of π-π stacking between the polymerizable liquid crystal compounds was suppressed. X ¹ and X ² affect the conjugated structure in the phenyl group having a group of —C (═J ² ) J ¹ in formula (a) (for example, π electrons exist in a plane on the benzene ring). It is considered that π-π stacking was suppressed as a result of the steric presence in the side chain of the benzene ring, etc. From the viewpoint of lowering the liquid crystal phase transition temperature of the polymerizable liquid crystal compound according to one embodiment of the present invention, at least one of X ¹ and X ^{2 in} formula (b) may be —CO— or —CS—. More preferably, at least one of X ¹ and X ² in formula (b) is more preferably —CO—.

X ¹ and ^{X 2} are, each independently, -CO -, - CS -, - S -, - O- or -NR ⁸ - ^{J 2} is a group represented by the formula (b) is the number of carbon atoms A group having a heterocyclic skeleton of 3 to 6 or an aromatic ring skeleton composed of two rings having 7 to 9 carbon atoms is preferable. For example, a barbitur ring skeleton, a thiobarbitur ring skeleton, a hydantoin ring skeleton, a thiohydantoin ring skeleton, Groups having a thiazolidinedione ring skeleton, a thiazolidinone ring skeleton, an indandione ring skeleton, a rhodanine ring skeleton, and the like, such as a barbitur ring skeleton, a thiobarbitur ring skeleton, a hydantoin ring skeleton, a thiohydantoin ring skeleton, a thiazolidinedione ring skeleton, A group having a thiazolidinone ring skeleton, an indandione ring skeleton or a rhodanine ring skeleton is more preferable, and a barbitur ring skeleton, a thiobarbitur ring skeleton, a hydan In the ring structure, thiohydantoin ring skeleton, thiazolidinedione ring structure, a group having a indanedione ring skeleton or a rhodanine ring skeleton more preferred. The hydrogen atoms contained in these rings are each independently an alkyl group having 1 to 6 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms. May be substituted.

In a particularly preferred embodiment, J ² in formula (a) is represented by any one of formula (c-1) to formula (c-5).

In Formula (c-1) to Formula (c-5), Y ¹¹ , Y ¹² , Y ¹³ , Y ²¹ , Y ²² , Y ³¹ , Y ³² , Y ⁴¹ , Y ⁴² , Y ^51, and Y ⁵² are respectively Independently represents an oxygen atom or a sulfur atom,
Z ¹¹ , Z ¹² , Z ²¹ , Z ²² , Z ³¹ , Z ⁴¹ , Z ⁵¹ , Z ⁵² , Z ⁵³ and Z ⁵⁴ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or 3 carbon atoms. Represents an alicyclic hydrocarbon group having 6 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 11 carbon atoms,
* Represents a bond.

The carbon number of the alkyl group in Z ¹¹ , Z ¹² , Z ²¹ , Z ²² , Z ³¹ , Z ⁴¹ , Z ⁵¹ , Z ⁵² , Z ⁵³ and Z ⁵⁴ is preferably 1 to 5, more preferably 1 to 4, More preferably 1 to 3, particularly preferably 1 to 2, very preferably 1. The carbon number of the alicyclic hydrocarbon group in Z ¹¹ , Z ¹² , Z ²¹ , Z ²² , Z ³¹ , Z ⁴¹ , Z ⁵¹ , Z ⁵² , Z ⁵³ and Z ⁵⁴ is preferably 4 to 6, more preferably. 4-5. The number of carbon atoms of the aromatic hydrocarbon group in Z ¹¹ , Z ¹² , Z ²¹ , Z ²² , Z ³¹ , Z ⁴¹ , Z ⁵¹ , Z ⁵² , Z ⁵³ and Z ⁵⁴ is preferably 6 to 10, for example 6 (ie Phenyl group).

Examples of J ² in formula (a) include groups described in Tables 1 to 5 below. In Tables 1 to 5, Me represents a methyl group, Et represents an ethyl group, Pr represents a propyl group (particularly normal propyl group), iPr represents an isopropyl group, Bu represents a butyl group, Ph Represents a phenyl group.

  The liquid crystal phase transition temperature of the polymerizable liquid crystal compound according to one embodiment of the present invention is low. In particular, the nematic phase transition temperature of the polymerizable liquid crystal compound is preferably 110 to 155 ° C, more preferably 115 to 150 ° C, and still more preferably 120 to 145 ° C. When the nematic phase transition temperature of the polymerizable liquid crystal compound is within the above range, excessive waste of heat energy can be suppressed, and at the same time, the heat of the supporting substrate on which the coating liquid containing the polymerizable liquid crystal compound is applied. Therefore, the selectivity of the support substrate can be expanded.

As described above, the polymerizable liquid crystal compound according to one embodiment of the present invention has a low liquid crystal phase transition temperature (particularly nematic phase transition temperature). The reason for this is not clear, but it is considered that the formation of π-π stacking between the polymerizable liquid crystal compounds was suppressed due to the chemical structure of the polymerizable liquid crystal compound. In general, a compound having a benzene ring tends to have a stable structure because the compounds overlap with each other because many π electrons are present. Therefore, such a compound tends to increase the liquid crystal phase transition temperature as a result of increasing the energy required for the liquid crystal phase transition. The polymerizable liquid crystal compound according to an embodiment of the present invention has a low liquid crystal phase transition temperature because the formation of π-π stacking particularly in the Ph-CJ ¹ J ² group in the formula (a) is suppressed. Conceivable.

The core portion (Ph-CJ ¹ J ² group) in the polymerizable liquid crystal compound is advantageous in terms of cost because its production process is short. As described above, according to the present invention, the production cost can be suppressed due to the structure of the core portion while suppressing excessive waste of thermal energy, and therefore a retardation film can be produced at a relatively low cost.

  Examples of the polymerizable liquid crystal compound which is one embodiment of the present invention include compounds represented by the following formulae. The cyclohexane ring in the following formula may be either a trans isomer or a cis isomer, but is preferably a trans isomer.

The maximum absorption wavelength (λ _max ) of the polymerizable liquid crystal compound according to one embodiment of the present invention is preferably 300 to 400 nm, more preferably 315 to 385 nm, and still more preferably 320 to 380 nm. When the maximum absorption wavelength (λ _max ) of the polymerizable liquid crystal compound is not less than the above lower limit, a retardation film composed of a polymer in the alignment state of the liquid crystal composition tends to exhibit reverse wavelength dispersion. . When the maximum absorption wavelength (λ _max ) of the liquid crystal composition is not more than the above upper limit, the absorption in the visible light region is suppressed, so that coloring of the film can be suppressed.

<Method for producing polymerizable liquid crystal compound>
The production method of the polymerizable liquid crystal compound according to one embodiment of the present invention is not particularly limited, and is a known organic compound described in Methoden der Organischen Chemie, Organic Reactions, Organic Syntheses, Comprehensive Organic Synthesis, New Experimental Chemistry Course, etc. Synthetic reaction (eg, condensation reaction, esterification reaction, Williamson reaction, Ullmann reaction, Wittig reaction, Schiff base formation reaction, benzylation reaction, Sonogashira reaction, Suzuki-Miyaura reaction, Negishi reaction, Kumada reaction, Kashiyama reaction, Buchwald -Hart wig reaction, Friedel-Craft reaction, Heck reaction, aldol reaction, etc.) can be produced by appropriately combining depending on the structure.

で表される、重合性液晶化合物（ａ−１）は、
・式（ｂ）：

で表されるアルコール化合物（ｂ）と、式（ｃ）：

で表されるカルボン酸化合物（ｃ）とのエステル化反応を行うことにより製造することができる。なお、前記式（ａ−１）、（ｂ）及び（ｃ）Ａ^１、Ａ^２、Ｂ^１、Ｂ^２、Ｅ^１、Ｅ^２、Ｆ^１、Ｆ^２、Ｇ^１、Ｇ^２、Ｐ^１、Ｐ^２、ｍ、ｎ、Ｊ^１及びＪ^２は、上記で規定されたものと同一である。 For example, the following formula (a-1):

The polymerizable liquid crystal compound (a-1) represented by
Formula (b):

An alcohol compound (b) represented by the formula (c):

It can manufacture by performing esterification reaction with the carboxylic acid compound (c) represented by these. The formulas (a-1), (b) and (c) A ¹ , A ² , B ¹ , B ² , E ¹ , E ² , F ¹ , F ² , G ¹ , G ² , P ¹ , P ² , m, n, J ¹ and J ² are the same as defined above.

  Examples of the carboxylic acid compound (c) include compounds represented by the following formulas (R-1) to (R-104).

  N in Formula (R-1) to Formula (R-104) represents an integer of 1 to 12, preferably an integer of 2 to 12, more preferably an integer of 3 to 12, and further preferably 4 to 10, for example 6. . The cyclohexane ring is preferably a trans isomer.

  The esterification reaction between the alcohol compound (b) and the carboxylic acid compound (c) is preferably performed in the presence of a condensing agent. By carrying out the esterification reaction in the presence of a condensing agent, the esterification reaction can be carried out efficiently and quickly.

  Examples of the condensing agent include 1-cyclohexyl-3- (2-morpholinoethyl) carbodiimide met-para-toluenesulfonate, dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide, 1-ethyl- 3- (3-dimethylaminopropyl) carbodiimide hydrochloride (water-soluble carbodiimide: commercially available as WSC), carbodiimide compounds such as bis (2,6-diisopropylphenyl) carbodiimide and bis (trimethylsilyl) carbodiimide, 2-methyl-6- Nitrobenzoic anhydride, 2,2′-carbonylbis-1H-imidazole, 1,1′-oxalyldiimidazole, diphenylphosphoryl azide, 1 (4-nitrobenzenesulfonyl) -1H-1, 4-triazole, 1H-benzotriazol-1-yloxytripyrrolidinophosphonium hexafluorophosphate, 1H-benzotriazol-1-yloxytris (dimethylamino) phosphonium hexafluorophosphate, N, N, N ′, N ′ -Tetramethyl-O- (N-succinimidyl) uronium tetrafluoroborate, N- (1,2,2,2-tetrachloroethoxycarbonyloxy) succinimide, N-carbobenzoxysuccinimide, O- (6-chlorobenzo) Triazol-1-yl) -N, N, N ′, N′-tetramethyluronium tetrafluoroborate, O- (6-chlorobenzotriazol-1-yl) -N, N, N ′, N′-tetra Methyluronium hexafluorophosphate, 2-butyl Mo-1-ethylpyridinium tetrafluoroborate, 2-chloro-1,3-dimethylimidazolinium chloride, 2-chloro-1,3-dimethylimidazolinium hexafluorophosphate, 2-chloro-1-methylpyridinium iodide 2-chloro-1-methylpyridinium para-toluenesulfonate, 2-fluoro-1-methylpyridinium para-toluenesulfonate, trichloroacetic acid pentachlorophenyl ester, and the like.

  The condensing agent is preferably a carbodiimide compound, 2,2′-carbonylbis-1H-imidazole, 1,1′-oxalyldiimidazole, diphenylphosphoryl azide, 1H-benzotriazol-1-yloxytripyrrolidinophosphonium Hexafluorophosphate, 1H-benzotriazol-1-yloxytris (dimethylamino) phosphonium hexafluorophosphate, N, N, N ′, N′-tetramethyl-O— (N-succinimidyl) uronium tetrafluoroborate, N -(1,2,2,2-tetrachloroethoxycarbonyloxy) succinimide, O- (6-chlorobenzotriazol-1-yl) -N, N, N ', N'-tetramethyluronium hexafluorophosphate, 2-chloro-1,3-di Tyrimidazolinium chloride, 2-chloro-1,3-dimethylimidazolinium hexafluorophosphate, 2-chloro-1-methylpyridinium iodide, and 2-chloro-1-methylpyridinium para-toluenesulfonate and mixtures thereof Selected from the group consisting of

  More preferably, the condensing agent is a carbodiimide compound, 2,2′-carbonylbis-1H-imidazole, 1H-benzotriazol-1-yloxytripyrrolidinophosphonium hexafluorophosphate, 1H-benzotriazol-1-yloxytris. (Dimethylamino) phosphonium hexafluorophosphate, N, N, N ′, N′-tetramethyl-O— (N-succinimidyl) uronium tetrafluoroborate, O- (6-chlorobenzotriazol-1-yl) -N , N, N ′, N′-tetramethyluronium hexafluorophosphate, 2-chloro-1,3-dimethylimidazolinium chloride, and 2-chloro-1-methylpyridinium iodide and mixtures thereof Selected and even more preferred From the viewpoint of economy, a carbodiimide compound.

  Among the carbodiimide compounds, dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (water-soluble carbodiimide: Commercially available as WSC), and bis (2,6-diisopropylphenyl) carbodiimide and mixtures thereof.

  The usage-amount of a condensing agent is 2.0-3.0 mol normally with respect to 1 mol of alcohol compounds (b).

  In the esterification reaction, N-hydroxysuccinimide, benzotriazole, paranitrophenol, 3,5-dibutyl-4-hydroxytoluene and the like may be added as an additive and mixed. The amount of the additive used is preferably 0.03 to 1.2 mol with respect to 1 mol of the condensing agent.

  The esterification reaction may be performed in the presence of a catalyst. Examples of the catalyst include N, N-dimethylaminopyridine, N, N-dimethylaniline, dimethylammonium pentafluorobenzenesulfonate, and mixtures thereof. Among these, N, N-dimethylaminopyridine and N, N-dimethylaniline are preferable, and N, N-dimethylaminopyridine is more preferable. The amount of the catalyst used is preferably 0.01 to 0.5 mol with respect to 1 mol of the alcohol compound (b).

  The esterification reaction is usually performed in a solvent. From the viewpoint of reaction yield and productivity, the solvent is preferably a nonpolar organic solvent such as pentane, hexane, heptane, toluene, xylene, benzene, chlorobenzene, chloroform, and dichloromethane, and acetone, dimethyl sulfoxide, N-methyl. Polar organic solvents such as 2-pyrrolidone, N, N-dimethylformamide, and N, N-dimethylacetamide, and more preferably toluene, xylene, benzene, chlorobenzene, chloroform, dichloromethane acetone, N-methyl-2- Pyrrolidone, N, N-dimethylformamide, and N, N-dimethylacetamide. These solvents may be used alone or in combination of two or more.

  The amount of the carboxylic acid compound (c) to be used is preferably 1.5 to 3.0 mol, more preferably 1.8 to 2.8 mol, more preferably 1 mol with respect to 1 mol of the alcohol compound (b). 1.8-2.5 mol.

  The amount of the solvent used is preferably 0.5 to 50 parts by mass, more preferably 1 to 20 parts by mass with respect to 1 part by mass in total of the alcohol compound (b) and the carboxylic acid compound (c). More preferably, it is 2 to 10 parts by mass.

  The temperature of the esterification reaction is preferably −20 to 30 ° C., more preferably −10 to 20 ° C., and further preferably −10 to 10 ° C. from the viewpoint of reaction yield and productivity. In addition, the esterification reaction time is preferably 1 minute to 72 hours, more preferably 1 to 48 hours, and still more preferably 1 to 24 hours, from the viewpoint of reaction yield and productivity. A polymerizable liquid crystal compound can be obtained from the obtained suspension by a method such as filtration or decantation.

According to the above method, the polymerizable liquid crystal compound can be produced with a small number of steps, which is very advantageous from an industrial viewpoint. In particular, since the manufacturing process of the core portion (Ph-CJ ¹ J ² group) in the polymerizable liquid crystal compound is short, it is very advantageous in terms of cost.

<Phase difference film>
The polymerizable liquid crystal compound which is one embodiment of the present invention is used for constituting a retardation film, preferably a retardation film having reverse wavelength dispersion. In one embodiment of the present invention, there is provided a retardation film composed of a polymer in the alignment state of the polymerizable liquid crystal compound (hereinafter also referred to as “retardation film of the present invention”). The orientation state is a state in which molecules are oriented, and the resulting film has a wavelength dispersibility. The retardation film of the present invention preferably satisfies the wavelength dispersion Re (450 nm) / Re (550 nm) of the following formula (α).
0.6 ≦ Re (450 nm) / Re (550 nm) <1.0 (α)
[In the formula (1), Re (λ) represents a front phase difference value with respect to light having a wavelength of λ nm. ]

  The wavelength dispersion Re (450 nm) / Re (550 nm) of the retardation film of the present invention is more preferably 0.63 or more and less than 1.0, and still more preferably 0.65 or more and less than 1.0. It is preferable that the wavelength dispersion Re (450 nm) / Re (550 nm) of the retardation film of the present invention is equal to or more than the lower limit because circular polarization conversion is possible in a short wavelength region near 450 nm. When the wavelength dispersion Re (450 nm) / Re (550 nm) of the retardation film of the present invention is less than the above upper limit value, the obtained retardation film has reverse wavelength dispersion and is uniform in a wide wavelength range. Polarization conversion is possible.

In a preferred embodiment of the present invention, J ² in the formula (a) has a (c-2) structure, and in such a case, a retardation film having particularly high reverse wavelength dispersion is easily obtained. In this case, Re (450 nm) / Re (550 nm) is preferably 0.60 or more and 0.70 or less. When Re (450 nm) / Re (550 nm) is within this range, when the wavelength dispersion of the retardation film is adjusted to a desired value, the addition amount of the polymerizable liquid crystal compound according to one embodiment of the present invention is small. This is advantageous in terms of cost. That is, as described below, the retardation film of the present invention includes other polymerizable liquid crystal compounds (in addition to structural units derived from the polymerizable liquid crystal compound (hereinafter also referred to as “polymerizable liquid crystal compound (A)”)). Hereinafter, it may be composed of a structural unit derived from “polymerizable liquid crystal compound (B)”, but the addition amount of the polymerizable liquid crystal compound (A) can be reduced.

  The retardation film of the present invention is excellent in transparency and can be used in various optical displays. The thickness of the retardation film is preferably 0.1 to 10 μm, and more preferably 0.5 to 3 μm from the viewpoint of reducing photoelasticity.

  When the retardation film of the present invention is used for a λ / 4 plate, the retardation film obtained has a retardation value Re (550 nm) at a wavelength of 550 nm of preferably 113 to 163 nm, more preferably 130 to 150 nm, and particularly preferably. Is about 135 nm to 150 nm.

  In order to use the retardation film of the present invention as an optical film for VA (Vertical Alignment) mode, Re (550 nm) is preferably 40 to 100 nm, more preferably about 60 to 80 nm. The film thickness may be adjusted.

  In another embodiment of the present invention, a polarizing plate including the retardation film (hereinafter, also referred to as “polarizing plate of the present invention”), in particular, an elliptical polarizing plate and a circular polarizing plate are provided. The polarizing plate of the present invention can be obtained by combining the retardation film of the present invention with a polarizing film. In these elliptically polarizing plates and circularly polarizing plates, the retardation film of the present invention is bonded to a polarizing film. In another embodiment of the present invention, a broadband circular polarizing plate in which the retardation film of the present invention is further bonded to the elliptical polarizing plate or the circular polarizing plate as a broadband λ / 4 plate can be provided.

  In one embodiment of the present invention, an optical display including the polarizing plate of the present invention (hereinafter also referred to as “optical display of the present invention”) can be provided. The optical display of the present invention can be used as, for example, a reflective liquid crystal display and an organic electroluminescence (EL) display. The FPD is not particularly limited, and examples thereof include a liquid crystal display (LCD) and an organic EL display.

  The optical display of the present invention includes the polarizing plate of the present invention, for example, a liquid crystal display device including a bonded product in which the polarizing plate of the present invention and a liquid crystal panel are bonded, the polarizing plate of the present invention, and light emission. An organic EL display device including an organic EL panel on which a layer is bonded can be given.

  In the present invention, the retardation film is a film used for converting linearly polarized light into circularly polarized light or elliptically polarized light, or conversely converting circularly polarized light or elliptically polarized light into linearly polarized light. The retardation film of this invention contains the polymer of the said polymeric liquid crystal compound. That is, the retardation film of the present invention includes a polymer composed of structural units derived from one or more of the polymerizable liquid crystal compounds.

  In addition to the structural unit derived from the polymerizable liquid crystal compound (hereinafter also referred to as “polymerizable liquid crystal compound (A)”), the retardation film of the present invention includes other polymerizable liquid crystal compounds (hereinafter referred to as “polymerizable liquid crystal”). In this case, the retardation film is composed of a polymer in the alignment state of these polymerizable liquid crystal compounds. When the retardation film of the present invention contains a structural unit derived from the polymerizable liquid crystal compound (B) in addition to the structural unit derived from the polymerizable liquid crystal compound (A), the wavelength dispersibility and retardation of the retardation film are increased. The optical properties such as the value and the thermophysical properties can be adjusted to desired values, and the polymerizable liquid crystal compound (A) has a high reverse wavelength dispersion (for example, 0.60 ≦ formula (α) ≦ 0.70). ) Is advantageous in terms of cost. Further, as the polymerizable liquid crystal compound (B), “Liquid Crystal Handbook (Edited by Liquid Crystal Handbook Editorial Board, published by Maruzen Co., Ltd. October 30, 2000)”, Chapter 3 Molecular Structure and Liquid Crystallinity, 3.2 Non-Chiral Rod Shape Among the compounds described in “Liquid Crystal Molecule, 3.3 Chiral Rod-shaped Liquid Crystal Molecule”, compounds having a polymerizable group are exemplified. The retardation film of the present invention may include a structural unit derived from one or more liquid crystal compounds (B).

The retardation film of the present invention can be produced, for example, by the following method.
First, to the polymerizable liquid crystal compound (A), if necessary, additives such as the polymerizable liquid crystal compound (B), a polymerization initiator, a polymerization inhibitor, a photosensitizer, an organic solvent and / or a leveling agent. To prepare a mixed solution. In particular, an organic solvent is preferably included because film formation is facilitated during film formation, and a polymerization initiator is preferably included because it has a function of curing the obtained retardation film.

  The viscosity of the mixed solution containing the polymerizable liquid crystal compound is preferably adjusted to, for example, 10 Pa · s or less, and preferably about 0.1 to 7 Pa · s so as to be easily applied. In addition, the viscosity of a mixed solution can be adjusted with content of an organic solvent.

  Moreover, the density | concentration of solid content in the said mixed solution is 5-50 mass%, for example, Preferably it is 5-30 mass%, More preferably, it is 5-15 mass%. The “solid content” here refers to a component obtained by removing the solvent from the mixed solution (liquid crystal composition). When the concentration of the solid content is 5% by mass or more, the retardation film does not become too thin, and a birefringence index necessary for optical compensation of the liquid crystal panel tends to be provided. Moreover, since the viscosity of a mixed solution is low as it is 50 mass% or less, since there exists a tendency for the nonuniformity to arise in the film thickness of retardation film, it is preferable.

As a polymerization initiator, a photoinitiator, a thermal polymerization initiator, etc. are mentioned, for example, It is preferable that it is a photoinitiator.
Examples of the photopolymerization initiator include benzoins, benzophenones, benzyl ketals, α-hydroxyketones, α-aminoketones, iodonium salts, sulfonium salts, and the like, and more specifically, Irgacure 907. IRGACURE 184, IRGACURE 651, IRGACURE 819, IRGACURE 250, IRGACURE 369 (all manufactured by Ciba Japan Co., Ltd.), Seiko All BZ, Seiko All Z, Seiko All BEE (all manufactured by Seiko Chemical Co., Ltd.), Kayacure BP100 (manufactured by Nippon Kayaku Co., Ltd.), Kayacure UVI-6992 (manufactured by Dow), Adeka optomer SP-152 and Adeka optomer SP-170 (all made by ADEKA Co., Ltd.) Can.

  Content of a polymerization initiator is 0.1-30 mass parts with respect to 100 mass parts of polymeric liquid crystal compounds, Preferably it is 0.5-20 mass parts, More preferably, it is 0.5-10. Part by mass. Within the above range, the polymerizable liquid crystal compound can be polymerized without disturbing the orientation of the liquid crystal compound.

  Examples of the polymerization inhibitor include hydroquinones having a substituent such as hydroquinone or alkyl ether, catechols having a substituent such as alkyl ether such as butylcatechol, pyrogallols, 2,2,6,6-tetramethyl-1 -Radical scavengers such as piperidinyloxy radical, thiophenols, β-naphthylamines, β-naphthols and the like.

  By using a polymerization inhibitor, the polymerization of the polymerizable liquid crystal compound can be controlled, and the stability of the obtained retardation film can be improved. The usage-amount of a polymerization inhibitor is 0.05-30 mass parts with respect to 100 mass parts of polymeric liquid crystal compounds, Preferably it is 0.1-10 mass parts. Within the above range, the polymerizable liquid crystal compound can be polymerized without disturbing the orientation of the liquid crystal compound.

  Examples of the photosensitizer include xanthones such as xanthone or thioxanthone, anthracene having a substituent such as anthracene or alkyl ether, phenothiazine, and rubrene.

  By using a photosensitizer, the polymerization of the polymerizable liquid crystal compound can be made highly sensitive. Moreover, as the usage-amount of a photosensitizer, it is 0.1-30 mass parts with respect to 100 mass parts of polymeric liquid crystal compounds, Preferably it is 0.5-10 mass parts. Within the above range, the polymerizable liquid crystal compound can be polymerized without disturbing the orientation of the polymerizable liquid crystal compound.

  The organic solvent is an organic solvent that can dissolve a polymerizable liquid crystal compound and the like, and may be any solvent that is inert to the polymerization reaction. Examples of the organic solvent include alcohol solvents such as methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, methyl cellosolve, butyl cellosolve or propylene glycol monomethyl ether; ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, gamma-butyrolactone. , Ester solvents such as propylene glycol methyl ether acetate or ethyl lactate; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone or methyl isobutyl ketone; non-chlorine aliphatic such as pentane, hexane or heptane Hydrocarbon solvents: Non-chlorinated aromatic hydrocarbon solvents such as toluene, xylene or phenol, acetonitrile, etc. Nitrile solvents; ether solvents such as tetrahydrofuran or dimethoxyethane; and chlorine solvents such as chloroform or chlorobenzene; amide solvents such as N-methylpyrrolidone (NMP) or N, N-dimethylformamide (DMF) . From the viewpoint of easily dissolving the polymerizable liquid crystal compound, ester solvents, ketone solvents, non-chlorine aromatic hydrocarbon solvents, ether solvents, and amide solvents are preferable, ketone solvents and amide solvents are more preferable, An amide solvent is even more preferable. These organic solvents may be used alone or in combination.

  The content of the organic solvent is preferably 100 to 10,000 parts by mass, more preferably 200 to 5000 parts by mass, and still more preferably 500 to 2500 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound. When the content of the organic solvent is not less than the above lower limit, the retardation film does not become too thin, and a birefringence index necessary for optical compensation of the liquid crystal panel tends to be provided. When the content of the organic solvent is not more than the above upper limit value, the viscosity of the mixed solution tends to be low, so that the film thickness of the retardation film tends not to be uneven.

  As a leveling agent, for example, an additive for radiation-curing coating material (BYK-352, BYK-353, BYK-361N, manufactured by BYK Japan), a coating agent (manufactured by Toray Dow Corning Co., Ltd .: SH28PA, DC11PA, ST80PA), Paint additives (manufactured by Shin-Etsu Chemical Co., Ltd .: KP321, KP323, X22-161A, KF6001) and fluorine-based additives (Dainippon Ink Chemical Industries, Ltd .: F-445, F-470, F-479), etc. Can be mentioned.

  By using a leveling agent, the obtained retardation film can be smoothed. Furthermore, in the production process of the retardation film, the fluidity of the mixed solution can be controlled, and the crosslinking density of the retardation film obtained by polymerizing the polymerizable liquid crystal compound can be adjusted. Moreover, the specific numerical value of the usage-amount of a leveling agent is 0.05-30 mass parts with respect to 100 mass parts of polymeric liquid crystal compounds, Preferably it is 0.05-10 mass parts. Within the above range, the polymerizable liquid crystal compound can be polymerized without disturbing the orientation of the polymerizable liquid crystal compound.

  The mixed solution thus obtained is applied to a support substrate or the like. The film thickness can be adjusted to give a desired phase difference by appropriately adjusting the coating amount and concentration of the mixed solution. In the case of a mixed solution in which the amount of the polymerizable liquid crystal compound is constant, the retardation value (retardation value, Re (λ)) of the obtained retardation film is determined as shown in the following formula. In order to obtain λ), the film thickness d may be adjusted.

Re (λ) = d × Δn (λ)
(In the formula, Re (λ) represents a retardation value at a wavelength λnm, d represents a film thickness, and Δn (λ) represents a birefringence at a wavelength λnm.)

  Examples of the application method to the supporting substrate include an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, a CAP coating method, and a die coating method. Moreover, the method of apply | coating using coaters, such as a dip coater, a bar coater, or a spin coater, etc. are mentioned.

  As said support base material, glass, a plastic sheet, a plastic film, or a translucent film can be mentioned, for example. Examples of the translucent film include polyolefin films such as polyethylene, polypropylene and norbornene polymers, polyvinyl alcohol films, polyethylene terephthalate films, polymethacrylate films, polyacrylate films, cellulose ester films, and polyethylene naphthalate films. , Polycarbonate film, polysulfone film, polyethersulfone film, polyetherketone film, polyphenylene sulfide film, or polyphenylene oxide film.

  For example, even a process that requires the strength of the retardation film, such as a bonding process, a transporting process, and a storage process of the retardation film of the present invention, can be easily handled without tearing.

  Moreover, it is preferable to form an alignment film on a support substrate and to apply a mixed solution containing the polymerizable liquid crystal compound on the alignment film. The alignment film has a solvent resistance that does not dissolve in the mixed solution when the mixed solution containing the polymerizable liquid crystal compound is applied, has heat resistance during the removal of the solvent and the heat treatment of the alignment of the liquid crystal, and during rubbing. It is preferable that peeling due to friction or the like does not occur, and the polymer or a composition containing the polymer is preferable.

  Examples of the polymer include polyamides and gelatins having an amide bond in the molecule, polyimides having an imide bond in the molecule and polyamic acid that is a hydrolyzate thereof, polyvinyl alcohol, alkyl-modified polyvinyl alcohol, polyacrylamide, polyoxazole, Mention may be made of polymers such as polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid or polyacrylates. These polymers may be used alone, or two or more kinds thereof may be mixed or copolymerized. These polymers can be easily obtained by polycondensation such as dehydration and deamination, chain polymerization such as radical polymerization, anion polymerization, and cation polymerization, coordination polymerization, and ring-opening polymerization.

  Further, these polymers can be applied after being dissolved in a solvent. The solvent is not particularly limited, but specifically water; alcohol such as methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, methyl cellosolve, butyl cellosolve or propylene glycol monomethyl ether; ethyl acetate, butyl acetate, ethylene glycol Ester solvents such as methyl ether acetate, gamma-butyrolactone, propylene glycol methyl ether acetate or ethyl lactate; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone or methyl isobutyl ketone; pentane, hexane or heptane Non-chlorinated aliphatic hydrocarbon solvents such as: Non-chlorinated aromatic hydrocarbon solvents such as toluene or xylene, acetonitrile, etc. Tolyl solvent; ether solvents such as tetrahydrofuran or dimethoxyethane; chlorinated solvents such as chloroform or chlorobenzene; and the like. These organic solvents may be used alone or in combination.

  In order to form the alignment film, a commercially available alignment film material may be used as it is. Examples of commercially available alignment film materials include Sunever (registered trademark, manufactured by Nissan Chemical Industries, Ltd.) or Optmer (registered trademark, manufactured by JSR Corporation).

  If such an alignment film is used, it is not necessary to control the refractive index by stretching, so that in-plane variation in birefringence is reduced. Therefore, there is an effect that it is possible to provide a large retardation film that can cope with an increase in the size of a flat panel display (FPD) on a supporting substrate.

  As a method for forming an alignment film on the support substrate, for example, a commercially available alignment film material or a compound serving as an alignment film material is applied as a solution on the support substrate, and then annealed. An alignment film can be formed on the support substrate.

  The thickness of the alignment film thus obtained is, for example, 10 nm to 10000 nm, preferably 10 nm to 1000 nm. If it is the said range, a polymeric liquid crystal compound etc. can be aligned at a desired angle on this alignment film.

  These alignment films can be rubbed or polarized UV irradiation as required. By forming the alignment film, the polymerizable liquid crystal compound and the like can be aligned in a desired direction.

  As a method for rubbing the alignment film, for example, a method in which a rubbing cloth is wound and a rotating rubbing roll is placed on a stage and brought into contact with the alignment film being conveyed can be used.

  As described above, in the step of preparing the unpolymerized film, the unpolymerized film (liquid crystal layer) may be laminated on the alignment film laminated on any support substrate. In this case, the production cost can be reduced as compared with a method of manufacturing a liquid crystal cell and injecting a mixed solution into the liquid crystal cell. Furthermore, it is possible to produce a film using a roll film.

  The solvent may be dried while the polymerization proceeds, but it is preferable from the viewpoint of film formability that most of the solvent is dried before the polymerization.

  Examples of the solvent drying method include natural drying, ventilation drying, and reduced pressure drying. The specific heating temperature is preferably 10 to 120 ° C, more preferably 25 to 80 ° C. In addition, the heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes. As long as the heating temperature and the heating time are within the above ranges, a supporting substrate that does not necessarily have sufficient heat resistance can be used as the supporting substrate.

  Next, the unpolymerized film (liquid crystal layer) obtained above is polymerized and cured. Thus, a film in which the orientation of the polymerizable liquid crystal compound is fixed, that is, a film containing a polymer of the polymerizable liquid crystal compound that is one embodiment of the present invention (hereinafter also referred to as “polymerized film”) is obtained. As a result, it is possible to produce a polymerized film having a small refractive index change in the plane direction of the film and a large refractive index change in the normal direction of the film.

  The method for polymerizing the unpolymerized film (liquid crystal layer) is determined according to the type of the polymerizable liquid crystal compound. If the polymerizable group contained in the polymerizable liquid crystal compound is photopolymerizable, the unpolymerized film (liquid crystal layer) can be polymerized by photopolymerization, and if the polymerizable group is thermally polymerizable, the unpolymerized film (liquid crystal layer) can be polymerized. In the present invention, it is particularly preferable to polymerize an unpolymerized film (liquid crystal layer) by photopolymerization. According to photopolymerization, an unpolymerized film (liquid crystal layer) can be polymerized at a low temperature, so that the heat resistance selection range of the supporting substrate is widened. In addition, it is easy to manufacture industrially. Photopolymerization is also preferred from the viewpoint of film formability. Photopolymerization is performed by irradiating an unpolymerized film (liquid crystal layer) with visible light, ultraviolet light, or laser light. From the viewpoint of handleability, the irradiation with ultraviolet light, which is particularly preferable, may be performed while heating to a temperature at which the polymerizable liquid crystal compound takes a liquid crystal phase. At this time, the patterned optical film can be obtained by patterning the polymerized film by masking or the like.

  Furthermore, the retardation film of the present invention is a thin film as compared with a stretched film that gives a retardation by stretching a polymer.

  In the manufacturing method of the retardation film of this invention, the process of peeling a support base material may be further included. By setting it as such a structure, the laminated body obtained becomes a film which consists of an oriented film and retardation film. Moreover, in addition to the process of peeling the said support base material, the process of peeling an alignment film may be further included. By setting it as such a structure, a phase difference film can be obtained.

  Hereinafter, the present invention will be described in more detail with reference to examples. Unless otherwise specified, “%” and “part” in the examples mean mass% and part by mass.

(Synthesis Example 1)
Compound (C) was synthesized according to the following scheme.

A 10 mL Schlenk flask equipped with a Dimroth condenser was placed in a nitrogen atmosphere, and 0.55-g of 2,5-dihydroxybenzaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 1,3-dimethyl-2-thiohydantoin (Japanese 0.52 g (manufactured by Kojun Pharmaceutical Co., Ltd.), 0.28 g of ammonium acetate (manufactured by Kanto Chemical Co., Ltd.), and 2 g of acetonitrile (manufactured by Wako Pure Chemical Industries, Ltd.) were added and mixed at 80 ° C. while mixing. Reacted for hours. Then, it cooled to room temperature and isolate | separated the depositing solid by performing filtration. The obtained solid was washed 3 times with 10 g of acetonitrile and then dried under reduced pressure at 40 ° C., to obtain 0.60 g of compound (A). The yield of compound (A) was 63% based on 2,5-dihydroxybenzaldehyde.
In addition, the result of having performed the ¹ H-NMR analysis of the obtained compound (A) is as follows.
¹ H-NMR (DMSO-d ₆ ): δ (ppm) 3.22 (s, 3H), 3.54 (s, 3H), 6.67 to 6.74 (m, 2H), 6.92 ( s, 1H), 7.81 (d, 1H), 8.83 (br, 1H), 9.48 (br, 1H).

A 20 mL four-necked flask equipped with a Dimroth condenser and a thermometer was placed in a nitrogen atmosphere, and 0.50 g of compound (A) and compound (B) synthesized with reference to patent literature (Japanese Patent Laid-Open No. 2010-31223) were prepared in the flask. 1.74 g, 0.0046 g of dimethylaminopyridine (hereinafter abbreviated as DMAP, manufactured by Wako Pure Chemical Industries, Ltd.), 0.029 g of dibutylhydroxytoluene (hereinafter abbreviated as BHT, manufactured by Wako Pure Chemical Industries, Ltd.), And 8 g of chloroform (manufactured by Kanto Chemical Co., Inc.) were added, and 0.60 g of diisopropylcarbodiimide (hereinafter abbreviated as IPC, manufactured by Wako Pure Chemical Industries, Ltd.) was added with a dropping funnel while mixing, and the reaction was continued at 0 ° C. overnight. I let you. Then, the insoluble component was removed by performing filtration. The obtained chloroform solution was dropped into 2-propanol having a weight three times the weight of chloroform contained in the chloroform solution. Subsequently, the precipitated solid was taken out by filtration. Next, the obtained solid was washed 3 times with 10 g of 2-propanol (manufactured by Wako Pure Chemical Industries, Ltd.), and then dried under reduced pressure at 30 ° C., whereby 0.69 g of compound (C) was obtained. Obtained. The yield of compound (C) was 34% based on compound (A).
In addition, the result of having performed the ¹ H-NMR analysis of the obtained compound (C) is as follows.
¹ H-NMR (CDCl ₃ ): δ (ppm) 1.41-1.82 (m, 24H), 2.27-2.30 (m, 8H), 2.57-2.60 (m, 4H) ), 3.35 (s, 3H), 3.57 (s, 3H), 3.94 (t, 4H), 4.17 (t, 4H), 5.82 (dd, 2H), 6.12 (Dd, 2H), 6.36 to 6.44 (m, 3H), 6.85 to 6.89 (m, 4H), 6.95 to 6.99 (m, 4H), 7.09 to 7 .17 (m, 2H), 8.07 (d, 1H).

About the obtained compound (C), maximum absorption wavelength ((lambda) _max ) was measured using spectrophotometer UV-3150 (made by Shimadzu Corporation). As a result, λ _max was 375 nm.

(Synthesis Example 2)
Compound (E) was synthesized according to the following scheme.

  A 10 mL Schlenk flask equipped with a Dimroth condenser was placed in a nitrogen atmosphere, and 2.50 g of 2,5-dihydroxybenzaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 1,3-dimethylbarbituric acid (Tokyo Chemical Industry) 2.83 g (manufactured by Co., Ltd.), 1.40 g of ammonium acetate (manufactured by Kanto Chemical Co., Ltd.), and 10 g of water were added and reacted at 25 ° C. for 1 hour while mixing. Thereafter, the precipitated solid was separated by filtration. The obtained solid was washed 3 times with 10 g of water, and then dried under reduced pressure at 40 ° C. to obtain 3.30 g of compound (D). The yield of compound (D) was 66% based on 2,5-dihydroxybenzaldehyde.

In addition, the result of having performed the ¹ H-NMR analysis of the obtained compound (D) is as follows.
¹ H-NMR (DMSO-d ₆ ): δ (ppm) 3.18 (s, 3H), 3.20 (s, 3H), 6.74 to 6.88 (m, 2H), 7.64 ( d, 1H), 8.65 (s, 1H), 8.98 (br, 1H), 10.1 (s, 1H).

  The inside of a 20 mL four-necked flask equipped with a Dimroth condenser and a thermometer was placed in a nitrogen atmosphere. Into the flask, 2.00 g of compound (D), 6.67 g of the above compound (B), 0.018 g of DMAP, 0.11 g of BHT And 30 g of chloroform (manufactured by Kanto Chemical Co., Inc.) were added, and 2.28 g of IPC was added with a dropping funnel while mixing, and allowed to react at 0 ° C. overnight. Then, the insoluble component was removed by performing filtration. The obtained chloroform solution was dropped into 2-propanol having a weight three times the weight of chloroform contained in the chloroform solution. Subsequently, the precipitated solid was taken out by filtration. Next, the obtained solid was washed three times with 20 g of 2-propanol (manufactured by Wako Pure Chemical Industries, Ltd.) and then dried under reduced pressure at 30 ° C., whereby 0.84 g of compound (E) was obtained. Obtained. The yield of compound (E) was 11% based on compound (D).

In addition, the result of having performed the ¹ H-NMR analysis of the obtained compound (E) is as follows.
¹ H-NMR (CDCl ₃ ): δ (ppm) 1.20 to 1.82 (m, 24H), 2.27 to 2.29 (m, 8H), 2.58 to 2.61 (m, 4H) ), 3.36 (s, 3H), 3.42 (s, 3H), 3.94 (t, 4H), 4.17 (t, 4H), 5.82 (dd, 2H), 6.12 (Dd, 2H), 6.40 (dd, 2H), 6.85 to 6.90 (m, 4H), 6.94 to 6.99 (m, 4H), 7.21 (d, 1H), 7.27 (dd, 1H), 7.90 (d, 1H), 8.49 (s, 1H)

About the obtained compound (E), maximum absorption wavelength ((lambda) _max ) was measured using spectrophotometer UV-3150 (made by Shimadzu Corporation). As a result, λ _max was 326 nm.

(Synthesis Example 3)
Compound (G) was synthesized according to the following scheme.

  A 10 mL Schlenk flask equipped with a Dimroth condenser was placed in a nitrogen atmosphere, and 2.00 g of 1,5-dihydroxybenzaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 1,3-indandione (Tokyo Chemical Industry Co., Ltd.) 2.12 g, 1.12 g of ammonium acetate (manufactured by Kanto Chemical Co., Ltd.) and 10 g of water were added and reacted at 25 ° C. for 1 hour with mixing. Thereafter, the precipitated solid was separated by filtration. The obtained solid was washed with 10 g of water three times, and then dried under reduced pressure at 40 ° C., to obtain 2.30 g of compound (F). The yield of compound (F) was 60% based on 2,5-dihydroxybenzaldehyde.

In addition, the result of having performed the ¹ H-NMR analysis of the obtained compound (F) is as follows.
¹ H-NMR (DMSO-d ₆ ): δ (ppm) 6.83 (d, 1H), 6.94 (dd, 1H), 7.91 to 7.97 (m, 4H), 8.28 ( s, 1H), 8.39 (d, 1H), 9.12 (s, 1H), 10.22 (s, 1H).

  A 20 mL four-necked flask equipped with a Dimroth condenser and a thermometer was placed in a nitrogen atmosphere, and 0.80 g of the compound (F), 2.77 g of the compound (B), 0.007 g of DMAP, and 0.033 g of BHT were added to the flask. And 4 g of chloroform (manufactured by Kanto Chemical Co., Inc.) were added. Then, the insoluble component was removed by performing filtration. The obtained chloroform solution was dropped into 2-propanol having a weight three times the weight of chloroform contained in the chloroform solution. Subsequently, the precipitated solid was taken out by filtration. Next, the obtained solid was washed 3 times with 10 g of 2-propanol (manufactured by Wako Pure Chemical Industries, Ltd.), and then dried under reduced pressure at 30 ° C., whereby 1.54 g of compound (G) was obtained. Obtained. The yield of compound (G) was 48% based on compound (F).

In addition, the result of having performed the ¹ H-NMR analysis of the obtained compound (G) is as follows.
¹ H-NMR (CDCl ₃ ): δ (ppm) 1.45 to 1.82 (m, 24H), 2.31 to 2.37 (m, 8H), 2.57 to 2.81 (m, 4H) ), 3.94 (t, 4H), 4.18 (t, 4H), 5.83 (dd, 2H), 6.13 (dd, 2H), 6.40 (dd, 2H), 6.86 To 7.01 (m, 8H), 7.20 (d, 1H), 7.33 (dd, 1H), 7.83 to 7.87 (m, 2H), 7.98 to 8.05 (m 3H), 8.20 (d, 1H).

With respect to the obtained compound (G), the maximum absorption wavelength (λ _max ) was measured using a spectrophotometer UV-3150 (manufactured by Shimadzu Corporation). As a result, λ _max was 338 nm.

(Example 1: Measurement of nematic phase transition temperature)
100 mg of the compound (C) obtained by the method described in Synthesis Example 1 was weighed into a vial tube, and further 2 g of chloroform was added and dissolved. The obtained solution was applied to a glass substrate with a PVA alignment film subjected to rubbing treatment and dried. This base was placed on a cooling / heating device (“LNP94-2” manufactured by Japan High-Tech) and heated from room temperature to 180 ° C., and then cooled to room temperature. The state at the time of temperature change was observed with a polarizing microscope (LEXT, manufactured by Olympus Corporation), and the temperature at which the nematic phase was obtained was measured to obtain the nematic phase transition temperature. The results obtained are shown in Table 6.

(Examples 2 and 3: Measurement of nematic phase transition temperature)
The nematic phase transition temperatures of the compounds (E) and (G) obtained by the methods described in Synthesis Examples 2 and 3 were measured in the same manner as in Example 1. The results obtained are shown in Table 6.

(Comparative Examples 1 and 2)
Nematic phase transition temperatures of the following compounds (H) and (I) described in Japanese Patent No. 4606195 were measured in the same manner as in Example 1. The results obtained are shown in Table 6.

Compound (H):

Compound (I):

Example 4
Using the compound (C), a retardation film was produced as follows. First, a photoalignment film forming composition (1) and a retardation film forming composition (1) were prepared as follows.

・溶剤（９５部）：シクロペンタノン <Preparation of composition (1) for forming photo-alignment film>
The following components (photo-alignable material and solvent) were mixed, and the resulting mixture was stirred at 80 ° C. for 1 hour to obtain a photo-alignment film-forming composition (1). In addition, the following photo-alignment materials were synthesize | combined by the direction described in Unexamined-Japanese-Patent No. 2013-33248.
-Photo-alignment material (5 parts):

Solvent (95 parts): cyclopentanone

<Preparation of retardation film forming composition (1)>
A composition for forming a retardation film (1) was obtained by mixing the following compounds at the ratios shown in Table 7 below.

<Manufacture of retardation film (1)>
Cycloolefin polymer film (COP) (ZF-14, manufactured by Nippon Zeon Co., Ltd.) using a corona treatment device (AGF-B10, manufactured by Kasuga Denki Co., Ltd.) under conditions of an output of 0.3 kW and a processing speed of 3 m / min. Processed once. The composition for forming a photo-alignment film (1) is applied to the corona-treated surface using a bar coater, dried at 80 ° C. for 1 minute, and polarized UV irradiation apparatus (SPOT CURE SP-7; USHIO INC.) The alignment film was obtained by performing polarized UV exposure with an integrated light quantity of 100 mJ / cm ² using a product manufactured by company. It was 100 nm when the film thickness of the obtained alignment film was measured with the laser microscope (LEXT, Olympus Corporation make). Subsequently, the retardation film forming composition (1) was applied onto the alignment film using a bar coater, dried at 140 ° C. for 2 minutes, and then a high-pressure mercury lamp (Unicure VB-15201BY-A, USHIO INC.) The phase difference film (1) was produced by irradiating with ultraviolet rays (wavelength: 365 nm, integrated light quantity at a wavelength of 365 nm: 750 mJ / cm ² ) using a company).

<Measurement of optical properties>
The front phase difference value of the retardation film (1) was measured using a measuring machine (KOBRA-WR, manufactured by Oji Scientific Instruments). The front retardation value of the optical film (1) was measured at wavelengths of 450 nm, 550 nm, and 650 nm, respectively, and [Re (450 nm) / Re (550 nm)] (hereinafter referred to as α) was calculated. The results are shown in Table 8.

(Examples 5 and 6)
Retardation films (2) and (3) were produced in the same manner as in Example 4 except that the compound (E) or (G) was used in place of the compound (C), and α was measured. The results are shown in Table 8.

From the above results, the polymerizable liquid crystal compound according to the present invention has a low nematic phase transition temperature, and at the same time, the retardation film composed of the polymer in the alignment state of the polymerizable liquid crystal compound has reverse wavelength dispersion. it is obvious. In particular, it can be seen that the compound (C) in which J ² in the formula (a) has a (c-2) structure has very high reverse wavelength dispersion.

Claims (7)

The following formula (a):

[In the formula (a),
m and n each independently represents an integer of 0 to 3,
^{B 1, B 2, D 1} , D 2, E 1 and ^{E 2,} each _{^{independently, -CR 1 R 2 -, -}} CH 2 -CH 2 -, - O -, - S -, - CO-O -, -O-CO-, -O-CO-O-, -C (= S) -O-, -O-C (= S)-, -O-C (= S) -O-, -CO Represents —NR ¹ —, —NR ² —CO—, —O—CH ₂ —, —CH ₂ —O—, —S—CH ₂ —, —CH ₂ —S— or a single bond, R ¹ and R ² Each independently represents a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms,
A ¹ , A ² , G ¹ and G ² each independently represent a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, The hydrogen atom contained in the alicyclic hydrocarbon group and the aromatic hydrocarbon group may each independently be substituted with a halogen atom, —R ³ , —OR ⁴ , a cyano group or a nitro group, —CH ₂ — contained in the alicyclic hydrocarbon group may each independently be substituted with —O—, —S—, —NH— or —NR ⁵ —, and the alicyclic hydrocarbon group -CH (-)-contained in may be substituted with -N (-)-, R ³ , R ⁴ and R ⁵ each independently represents an alkyl group having 1 to 4 carbon atoms, The hydrogen atom contained in the alkyl group may be substituted with a fluorine atom,
F ¹ and F ² each independently represent an alkanediyl group having 1 to 12 carbon atoms, and each hydrogen atom contained in the alkanediyl group may be independently substituted with —OR ⁶ or a halogen atom. Well, —CH ₂ — contained in the alkanediyl group may be independently substituted with —O— or —CO—, and R ⁶ represents an alkyl group having 1 to 4 carbon atoms, The hydrogen atom contained in the alkyl group may be substituted with a fluorine atom,
P ¹ and P ² each independently represent a hydrogen atom or a polymerizable group, provided that at least one of P ¹ and P ² represents a polymerizable group;
J ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms,
J ² represents a C 3-25 hydrocarbon group having a monocyclic structure or a polycyclic structure, and —CH ₂ — contained in the hydrocarbon group independently represents —O—, —S—, The hydrogen atom contained in the hydrocarbon group may be independently substituted with —CO—, —CS— or —NR ⁷ —, and each independently represents an alkyl group having 1 to 6 carbon atoms or 3 to 6 carbon atoms. It may be substituted with an alicyclic hydrocarbon group or an aromatic hydrocarbon group having 6 to 12 carbon atoms, and R ⁷ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms]
A polymerizable liquid crystal compound represented by: J ² represents the following formula (b):

[In the formula (b),
K ^{is, -X 1 C (=) X} 2 - constituting together mono or poly cyclic structures represent a hydrocarbon group having 1 to 11 carbon atoms, -CH ₂ contained in the hydrocarbon group - is Each independently may be substituted with —O—, —S—, —CO—, —CS— or —NR ⁷ —, and each hydrogen atom contained in the hydrocarbon group independently has 1 carbon atom. May be substituted with an alkyl group having 6 to 6 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms, and R ⁷ is a hydrogen atom or 1 to 6 carbon atoms. Represents an alkyl group of
X ¹ and X ² each independently represent —CO—, —CS—, —S—, —O— or —NR ⁸ —, wherein R ⁸ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, Represents an alicyclic hydrocarbon group having 3 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms,
* Represents a bond]
The polymerizable liquid crystal compound according to claim 1 represented by: J ² in the formula (a) is a formula (c-1) to a formula (c-5):

[In Formula (c-1)-Formula (c-5),
Y ¹¹ , Y ¹² , Y ¹³ , Y ²¹ , Y ²² , Y ³¹ , Y ³² , Y ⁴¹ , Y ⁴² , Y ⁵¹ and Y ⁵² each independently represent an oxygen atom or a sulfur atom,
Z ¹¹ , Z ¹² , Z ²¹ , Z ²² , Z ³¹ , Z ⁴¹ , Z ⁵¹ , Z ⁵² , Z ⁵³ and Z ⁵⁴ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or 3 carbon atoms. Represents an alicyclic hydrocarbon group having 6 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 11 carbon atoms,
* Represents a bond]
The polymerizable liquid crystal compound according to claim 1 or 2 represented by any one of the following: The polymerizable liquid crystal compound according to claim ^1, wherein G ¹ and G ² are trans-cyclohexane-1,4-diyl groups.   The retardation film comprised from the polymer in the orientation state of the polymeric liquid crystal compound in any one of Claims 1-4.   A polarizing plate comprising the retardation film according to claim 5.   An optical display comprising the polarizing plate according to claim 6.