TW201829749A - Polymerizable liquid crystal compound, retardation film, polarizing plate and optical display including the retardation film - Google Patents

Abstract

The objective of the present invention is to provide a polymerizable liquid crystal compound having a low liquid crystal phase transition temperature and preferably for constituting a retardation film having reverse wavelength dispersibility. The polymerizable liquid crystal compound of the present invention is represented by the following formula (a):.

Description

 Polymerizable liquid crystal compound, retardation film, and polarizing plate and optical display including the same  

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

An optical film such as a retardation film used in a flat panel display (FPD), for example, a coating liquid obtained by dissolving a coating liquid obtained by dissolving a polymerizable liquid crystal compound in a solvent on a support substrate, and then polymerizing the coating film. membrane. The polymerizable liquid crystal compound which has been conventionally known is, for example, a nematic liquid crystal compound having a rod-like structure in which two to four 6-membered rings are connected. On the other hand, in the case of a retardation film, one of its characteristics requires polarization conversion in the full-wavelength region, and the wavelength of the reverse wavelength dispersion exhibiting [Re(450 nm) / Re (550 nm)] <1 In the domain, theoretically, it is known that the same polarization conversion can be performed. The polymerizable compound which can constitute such a retardation film is described, for example, in Patent Document 1.

The coating type optical film can be applied to a support substrate by a coating liquid obtained by dissolving a polymerizable liquid crystal compound in a solvent to form a coating film, and then the polymerizable liquid crystal compound contained in the coating film is nematic. It is obtained by a method in which the liquid crystal phase is transferred, and the coating film is dried and the solvent is distilled off (for example, Patent Document 2).

 [Previous Technical Literature]    [Patent Literature]  

[Patent Document 1] Japanese Laid-Open Patent Publication No. 2011-207765

[Patent Document 2] Japanese Patent No. 4606195

In the above method, the transfer of the polymerizable liquid crystal compound to the liquid crystal phase state can be carried out by heating. However, when the liquid crystal phase-like temperature of the liquid crystal compound is higher than that of the liquid crystal compound described in the above Patent Document 2, there is a possibility that waste of excess heat energy or deformation of the support substrate coated with the liquid crystal compound may occur, and the retardation film may be produced. It has become difficult.

Accordingly, an object of the present invention is to provide a polymerizable liquid crystal compound which has a low liquid crystal phase transition temperature and is suitable for forming a retardation film having reverse wavelength dispersion. Meanwhile, an object of the present invention is to provide a retardation film which can be composed of a polymer in an oriented state of the polymerizable liquid crystal compound.

The present invention provides the following preferred embodiments.

[1] A polymerizable liquid crystal compound represented by the following formula (a): [In the formula (a), m and n each independently represent an integer of 0 to 3, and B ¹ , B ² , D ¹ , D ² , E ¹ and E ² each independently represent -CR ¹ R ² -, -CH ₂ -CH ₂ -, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S) -, -OC(=S)-O-, -CO-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 represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms, and A ¹ , A ² , G ¹ and G ² each independently represent a carbon number of 3 to a divalent alicyclic hydrocarbon group of 16 or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, wherein the alicyclic hydrocarbon group and the hydrogen atom contained in the aromatic hydrocarbon group may independently be a halogen atom, -R ³ , -OR ⁴ , a cyano group or a nitro group, the -CH ₂ -(methylene group) contained in the alicyclic hydrocarbon group may be independently substituted by -O-, -S-, -NH- or -NR ⁵ -, which The -CH(-)-(methine group) contained in the alicyclic hydrocarbon group may be substituted with -N(-)-(nitrogen atom), and R ³ , R ⁴ and R ⁵ each independently represent an alkane having 1 to 4 carbon atoms. a hydrogen atom contained in the alkyl group may be substituted with a fluorine atom, and F ¹ and F ² each independently represent an alkanediyl group having 1 to 12 carbon atoms. The hydrogen atom contained in the group may be independently substituted with -OR ⁶ or a halogen atom, and the -CH ₂ -(methylene group) contained in the alkanediyl group may be independently substituted with -O- or -CO-, respectively. 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, and P ¹ and P ² each independently represent a hydrogen atom or a polymerizable group, but at least P ¹ and P ² One represents a polymerizable group, J ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and J ² represents a hydrocarbon group having 3 to 25 carbon atoms having a monocyclic structure or a polycyclic structure, and -CH ₂ contained in the hydrocarbon group -(methylene) may be independently substituted with -O-, -S-, -CO-, -CS- or -NR ⁷ -, and the hydrogen atom contained in the hydrocarbon group may independently be 1 to 6 carbon atoms The alkyl group, the alicyclic hydrocarbon group having 3 to 6 carbon atoms or the 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.

[2] The polymerizable liquid crystal compound according to the above [1], wherein J ² is represented by the following formula (b): [In the formula (b), K represents a hydrocarbon group having 1 to 11 carbon atoms together with -X ¹ C(=)X ² -, which has a monocyclic structure or a polycyclic structure, and -CH ₂ - contained in the hydrocarbon group (sub. The group may be independently substituted with -O-, -S-, -CO-, -CS- or -NR ⁷ -, and the hydrogen atom contained in the hydrocarbon group may independently be 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; R ⁷ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and X ¹ and X ² each independently represent -CO-, -CS-, -S-, -O- or -NR ⁸ -, R ⁸ 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 having 6 to 12 carbon atoms A hydrocarbon group, * represents a bond].

[3] The polymerizable liquid crystal compound according to the above [1] or [2] wherein the J ² system in the formula (a) is represented by any one of the formulae (c-1) to (c-5): [In the formulae (c-1) to (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 each independently The ground represents an oxygen atom or a sulfur atom, and Z ¹¹ , Z ¹² , Z ²¹ , Z ²² , Z ³¹ , Z ⁴¹ , Z ⁵¹ , Z ⁵² , Z ⁵³ and Z ⁵⁴ each independently represent a hydrogen atom and a carbon number of 1 to 6. An alkyl group, an alicyclic hydrocarbon group having 3 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 11 carbon atoms, * represents a bonding bond].

[4] The above [1] to [3] The polymerizable liquid crystal compound of any one, wherein G ¹ and G ² trans - cyclohexane-1,4-diyl.

[5] A retardation film which is composed of a polymer in an oriented state of the polymerizable liquid crystal compound according to any one of the above [1] to [4].

[6] A polarizing plate comprising the retardation film according to the above [5].

[7] An optical display comprising the polarizing plate according to the above [6].

According to the present invention, there is provided a polymerizable liquid crystal compound which has a low liquid crystal phase transition temperature and is suitable for forming a retardation film having reverse wavelength dispersion. Meanwhile, according to the present invention, it is possible to provide a retardation film which is composed of a polymer in an oriented state of the polymerizable liquid crystal compound.

 <Polymeric liquid crystal compound>  

The polymerizable liquid crystal compound according to one embodiment of the present invention is a compound represented by the following formula (a).

In the 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 represent -CR ¹ R ² -, -CH ₂ -CH ₂ -, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)- , -OC(=S)-O-, -CO-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 represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms; and A ¹ , A ² , G ¹ and G ² each independently represent a carbon number of 3 to 16 a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and the alicyclic hydrocarbon group and the hydrogen atom contained in the aromatic hydrocarbon group may independently be a halogen atom, -R ³ , - Substituting OR ⁴ , cyano or nitro, the -CH ₂ -(methylene) contained in the alicyclic hydrocarbon group may be independently substituted with -O-, -S-, -NH- or -NR ⁵ -, -CH(-)-(methine group) contained in the alicyclic hydrocarbon group may be substituted with -N(-)-(nitrogen atom); R ³ , R ⁴ and R ⁵ each independently represent a carbon number of 1 to 4. alkyl group, a hydrogen atom with fluorine atoms contained in the alkyl substituent; F. ¹ and F ² each independently represent a carbon number of 1 to 12 alkanediyl group, this Diyl hydrogen atom may be contained in order to independently substituted with a halogen atom or -OR ^6, -CH ₂ the two alkyl groups contained in the - (methylene) can be independently substituted by -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; and P ¹ and P ² each independently represent a hydrogen atom or a polymerizable group, but in P ¹ and P ² At least one represents a polymerizable group; J ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and J ² represents a hydrocarbon group having 3 to 25 carbon atoms having a monocyclic structure or a polycyclic structure, and - contained in the hydrocarbon group CH ₂ -(methylene) may be independently substituted with -O-, -S-, -CO-, -CS- or -NR ⁷ -, and the hydrogen atoms contained in the hydrocarbon group may independently be carbon number 1 The alkyl group to 6 is substituted with 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.

In the formula (a), m and n each independently represent an integer of 0 to 3, and preferably an integer of 1 to 2, more preferably 1. At the same time, it is easy to produce the above polymerizable liquid crystal compound, and it is possible to suppress the production cost, and m and n are preferably the same integers.

Further, 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. In the case of industrially producing a polymerizable liquid crystal compound, there are a plurality of A ¹ , A ² , B ¹ and B ² systems which are respectively identical to each other (that is, there are several identical A ¹ , and there are several identical A ² It is preferable that there are several identical B ¹ and there are several identical B ² ).

In the formula (a), B ¹ , B ² , D ¹ , D ² , E ¹ and E ² each independently represent -CR ¹ R ² -, -CH ₂ -CH ₂ -, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO -NR ¹ -, -NR ² -CO-, -O-CH ₂ -, -CH ₂ -O-, -S-CH ₂ -, -CH ₂ -S- or a single bond. In the above formula, R ¹ and R ² each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms.

B ¹ and B ² are easy to express the liquid crystal phase of the above polymerizable liquid crystal compound, and are independently -O-, -S-, -O-CO-, -CO-O-, -OC (=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. In order to facilitate the production of the above polymerizable liquid crystal compound and to suppress the production cost, it is preferred that B ¹ and B ² are the same as each other. Further, B ¹ and B ² are the same as each other, and the structures of B ¹ and B ² are the same when the phenyl group having a group of -C(=J ² )J ^{1 in} the formula (a) is centered. meaning, for example, B ¹ is -O-CO-, the B ¹ and B ² are identical to each other -CO-O-. Hereinafter, the relationship among 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 is also the same.

In the liquid crystal phase which is easy to express the above polymerizable liquid crystal compound, D ¹ , D ² , E ¹ and E ² are respectively -O-, -S-, -O-CO-, -CO-O-, -OC(=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. In the case where the above polymerizable liquid crystal compound is 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 preferably the same.

In the formula (a), 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 carbon number of the above-mentioned divalent alicyclic hydrocarbon group is preferably from 4 to 15, more preferably from 5 to 10, still more preferably from 5 to 8, particularly preferably from 5 to 6. The carbon number of the above-mentioned divalent aromatic hydrocarbon group is preferably from 6 to 18, more preferably from 6 to 16, more preferably from 6 to 10, particularly preferably from 5 to 6. The alicyclic hydrocarbon group and the hydrogen atom contained in the aromatic hydrocarbon group may be independently 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, and a hydrogen atom contained in the alkyl group may be substituted with a fluorine atom.

The alkyl group having 1 to 4 carbon atoms may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a second butyl group or a third butyl group, and has a carbon number of 1 to 3 The alkyl group is preferred, and the alkyl group having 1 or 2 carbon atoms is more preferred, especially methyl.

The alkoxy group having 1 to 4 carbon atoms in -OR ⁴ may, for example, be a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group or a second butoxy group. The third butoxy group or the like is preferably an alkoxy group having 1 to 3 carbon atoms, more preferably an alkoxy group having 1 or 2 carbon atoms, particularly preferably a methoxy group.

The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and preferably a fluorine atom, a chlorine atom or a bromine atom.

The above-mentioned divalent alicyclic hydrocarbon group may, for example, be a cycloalkanediyl group. -CH ₂ -(methylene) contained in the alicyclic hydrocarbon group may be independently substituted with -O-, -S-, -NH- or -NR ⁵ -, which is contained in the alicyclic hydrocarbon group. CH(-)-(methine) 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 a hydrogen atom contained in the alkyl group may be substituted with a fluorine atom.

The divalent alicyclic hydrocarbon group is a group represented by the following formula (g-1) to formula (g-4). The divalent alicyclic hydrocarbon group in which -CH ₂ -(methylene) contained in the alicyclic hydrocarbon group is substituted with -O-, -S-, -NH- or -NR ⁵ - may be exemplified by the following formula ( G-5) to the group represented by the formula (g-8). The divalent alicyclic hydrocarbon group in which -CH(-)-(methine group) contained in the alicyclic hydrocarbon group is substituted with -N(-)-(nitrogen atom) is exemplified by the following formula (g-9) And the base represented by the formula (g-10). These groups are preferably a 5-membered or 6-membered alicyclic hydrocarbon group.

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

The divalent aromatic hydrocarbon group may, for example, be a group represented by the formula (a-1) to the formula (a-8). The divalent aromatic hydrocarbon group is preferably a 1,4-phenylene group.

In one embodiment of the present invention, in the production of the polymerizable liquid crystal compound, A ¹ and A ² are preferably independently a divalent aromatic hydrocarbon group, and more preferably 1,4-phenylene. good. Meanwhile, in one embodiment of the present invention, in the production of the polymerizable liquid crystal compound, G ¹ and G ² are preferably independently a divalent alicyclic hydrocarbon group, and are trans-cyclohexane. The alkane-1,4-diyl group is more preferred, 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 a trans-cyclohexane-1,4-diyl group, the above polymerizable liquid crystal compound exhibits particularly excellent liquid crystallinity. At the same time, it is preferable that the above-mentioned superposed liquid crystal compound can be produced and the production cost can be suppressed, and it is preferable that A ¹ and A ^{2 are the} same, and/or G ¹ and G ^{2 are the} same.

In the formula (a), F ¹ and F ² each independently represent an alkanediyl group having 1 to 12 carbon atoms, preferably 2 to 12 carbon atoms, more preferably 3 to 12 carbon atoms, particularly carbon number 4; More preferably, it is 10, for example, a carbon number 6 alkanediyl group. The hydrogen atom contained in the alkanediyl group may be independently substituted with -OR ⁶ or a halogen atom, and the -CH ₂ -(methylene group) contained in the alkanediyl group may independently be -O- or - CO-substitution. 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. In order to easily produce the above polymerizable liquid crystal compound and to suppress the production cost, it is preferred that F ¹ and F ² are the same as each other.

In the 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 both of P ¹ and P ² are preferably a polymerizable group. The polymerizable group means a group containing a group which can participate in the polymerization reaction. Examples of the group which can participate in the polymerization reaction include a vinyl group, a p-(2-phenylvinyl)phenyl group, an acryloyl group, an acryloxy group, a methacryl group, a methacryloxy group, a carboxyl group, and the like. Methylcarbonyl, hydroxy, aminomethanyl, alkylamino group having 1 to 4 carbon atoms, amine group, formazan group, -N=C=O, -N=C=S, epoxyethyl group, ring Oxypropyl group and the like.

In terms of photopolymerization, the polymerizable group is preferably a radical polymerizable group or a cationic polymerizable group. In particular, in terms of ease of handling or production, it is preferably an acrylonitrile group, an acryloxy group, a methacryl oxime group or a methacryloxy group, and in the case of high polymerizability, it is an acryl oxime group or an acrylonitrile group. The oxy group is better.

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

In the formula (a), J ² represents a hydrocarbon group having a monocyclic structure or a polycyclic structure and having a carbon number of 3 to 25. The carbon number of the hydrocarbon group is preferably from 3 to 20, more preferably from 3 to 16, more preferably from 4 to 14. -CH ₂ -(methylene) contained in the hydrocarbon group in J ² may be independently substituted with -O-, -S-, -CO-, -CS- or -NR ⁷ -, and 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. Meanwhile, the hydrogen atom contained in the hydrocarbon group in J ² may independently be an alkyl group having 1 to 6 carbon atoms (preferably having 1 to 3 carbon atoms) and a carbon number of 3 to 6 (having a carbon number of 4 to 6). An alicyclic hydrocarbon group or an aromatic hydrocarbon group having 6 to 12 carbon atoms (preferably having a carbon number of 6 to 10, for example, a carbon number of 6).

The monocyclic structure is one having one ring in the hydrocarbon group represented by J ² . The polycyclic structure is a group having two or more hydrocarbon groups represented by J ² . In the polycyclic structure, each ring may exist independently from the other ring, or a condensed ring in which a bond of a ring and a bond of another ring are shared. The condensed ring may be an aliphatic ring or an aromatic ring, and may be a hetero ring or a ring in which the rings are combined.

The hydrocarbon group having a monocyclic structure or a polycyclic structure may, for example, be the following (j-1) to (j-16).

In a preferred embodiment of the present invention, J ² in the formula (a) is represented by the following formula (b).

In the formula (b), K represents a hydrocarbon group having 1 to 11 carbon atoms together with -X ¹ C(=)X ² -, which has a monocyclic structure or a polycyclic structure, and -CH ₂ - (methylene group) contained in the hydrocarbon group ) may be independently substituted with -O-, -S-, -CO-, -CS- or -NR ⁷ -, and the hydrogen atom contained in the hydrocarbon group may independently be an alkyl group having 1 to 6 carbon atoms, carbon 3 to 6 of an alicyclic hydrocarbon group or a carbon number 6 to 12 aromatic hydrocarbon group, R ⁷ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and X ¹ and X ² each independently represent -CO-, - CS-, -S-, -O- or -NR ⁸ -, R ⁸ 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 group having 6 to 12 carbon atoms Hydrocarbyl, * represents a bond.

Since X ¹ and X ² in the formula (b) are independently -CO-, -CS-, -S-, -O- or -NR ⁸ -, the liquid crystal phase transition temperature can be lowered, and in particular, the orientation can be lowered. Column phase transfer temperature. Although the reason is not known, it is believed that the formation of π-π stacking between the polymerizable liquid crystal compounds is suppressed. It is believed that X ¹ and X ² are affected by the conjugated structure in the phenyl group having a group of -C(=J ² )J ^{1 in} the formula (a) (for example, π electrons are not planarly present on the benzene ring, but As a result of the steric presence of the side chain of the benzene ring or the like, the π-π stacking is suppressed. In order to lower the liquid crystal phase transition temperature of the polymerizable liquid crystal compound according to the embodiment of the present invention, it is preferred that at least one of X ¹ and X ² in the formula (b) is -CO- or -CS-. Further, it is more preferable that at least one of X ¹ and X ² in the formula (b) is -CO-.

X ¹ and X ² are each independently represents -CO -, - CS -, - S -, - represented by the formula (b) J of the group ^2, having a carbon-based number from 3 to 6 - O- or -NR ⁸ The heterocyclic skeleton or the group of the aromatic ring skeleton formed by the two rings having 7 to 9 carbon atoms is preferably, for example, a barbituric ring skeleton, a thiobarbitur ring skeleton, and B. Hydantoin ring skeleton, thioacetamidine ring skeleton, thiazolidinedione ring skeleton, thiazolidinone ring skeleton, indanedionone ring skeleton, rhodamine (rhodanine) the base of the ring skeleton, etc., and has a barbiturate ring skeleton, a thiobarbitur ring skeleton, a carbendazim ring skeleton, a thioacetamidine ring skeleton, a thiazolidinedione ring skeleton, a thiazole The base of the alkanone ring skeleton, the decanedione skeleton or the rhodamine ring skeleton is preferred, and has a barbiturate ring skeleton, a thiobarbitur ring skeleton, a carbendazim ring skeleton, and a thioacetamidine group. The ring skeleton, the thiazolidinedione ring skeleton, the decanedione ring skeleton or the rhodamine ring skeleton is more preferred. Further, the hydrogen atoms contained in the rings 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.

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

In the formulae (c-1) to (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 each independently Representing an oxygen atom or a sulfur atom, and Z ¹¹ , Z ¹² , Z ²¹ , Z ²² , Z ³¹ , Z ⁴¹ , Z ⁵¹ , Z ⁵² , Z ⁵³ and Z ⁵⁴ each independently represent a hydrogen atom and an alkyl group having 1 to 6 carbon atoms. The group is an alicyclic hydrocarbon group having 3 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 11 carbon atoms, and * 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 from 1 to 5 and from 1 to 4 More preferably, it is better from 1 to 3, and preferably from 1 to 2, especially 1 is the best. 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, and is 4 Better to 5. The carbon number 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).

J ² in the formula (a) includes, for example, the groups described in the following Tables 1 to 5. Further, in Tables 1 to 5, Me represents a methyl group, Et represents an ethyl group, Pr represents a propyl group (especially n-propyl group), iPr represents an isopropyl group, Bu represents a butyl group, and Ph represents a phenyl group.

The polymerizable liquid crystal compound according to an embodiment of the present invention has a low liquid crystal phase transition temperature. In particular, the nematic phase transition temperature of the above polymerizable liquid crystal compound is preferably from 110 to 155 ° C, more preferably from 115 to 150 ° C, still more preferably from 120 to 145 ° C. When the nematic phase transition temperature of the polymerizable liquid crystal compound is within the above range, excessive waste of thermal energy can be prevented, and the coating liquid containing the polymerizable liquid crystal compound can be applied to prevent the support substrate from being deformed by heat. Expand the selectivity of the support substrate.

As described above, the polymerizable liquid crystal compound according to the embodiment of the present invention has a low liquid crystal phase transition temperature (especially a nematic phase transition temperature). Although the reason is not known, it is considered to be due to the chemical structure of the polymerizable liquid crystal compound, and the formation of π-π stacking between the polymerizable liquid crystal compounds is suppressed. A compound having a benzene ring usually has a stable structure because it has a large number of π electrons and overlaps the compounds. Therefore, this compound requires a higher energy in the liquid crystal phase transfer, and it is easy to increase the liquid crystal phase transition temperature. In the polymerizable liquid crystal compound according to the embodiment of the present invention, it is considered that the formation of π-π in the Ph-CJ ¹ J ² group in the formula (a) is suppressed to cause a lower liquid crystal phase transition temperature.

The core portion (Ph-CJ ¹ J ² group) in the above polymerizable liquid crystal compound is also advantageous in cost because of its short process. As described above, according to the present invention, since it is possible to prevent the excessive waste of thermal energy, the manufacturing cost can be suppressed due to the structure of the core portion, so that a relatively inexpensive retardation film can be produced.

The polymerizable liquid crystal compound of one embodiment of the present invention may, for example, be a compound represented by the following formula. The cyclohexane ring in the following formula, although it may be either trans or cis, is preferably in the trans form.

The maximum absorption wavelength (λ _max ) of the polymerizable liquid crystal compound according to an embodiment of the present invention is preferably 300 to 400 nm, more preferably 315 to 385 nm, and still more preferably 320 to 380. When the maximum absorption wavelength (λ _max ) of the polymerizable liquid crystal compound is at least the above lower limit value, the retardation film composed of the polymer in the aligned state of the liquid crystal composition tends to exhibit reverse wavelength dispersibility. When the maximum absorption wavelength (λ _max ) of the liquid crystal composition is equal to or less than the above upper limit value, absorption in the visible light region can be suppressed, so that coloring of the film can be prevented.

 <Method for Producing Polymerizable Liquid Crystal Compound>  

The method for producing the polymerizable liquid crystal compound according to the embodiment of the present invention is not particularly limited, and can be known by the methods described in Methoden der Organischen Chemie, Organic Reactions, Organic Syntheses, Comprehensive Organic Synthesis, New Experimental Chemistry, and the like. Organic synthesis reactions (eg condensation reaction, esterification reaction, Williamson reaction, Ullman reaction, Wittig reaction, Schiff base formation reaction, benzoylation reaction, taro reaction, Suzuki-Miyaura reaction, root bank reaction, Kumada reaction, Lushan reaction, Buchwald -Heartwig reaction, Friedel Crafts reaction, Heck reaction, Aldol reaction, etc.) are produced in accordance with a suitable combination of their structures.

For example, the following formula (a-1): The polymerizable liquid crystal compound (a-1) represented by the formula (b) can be carried out by: The represented alcohol compound (b) and formula (c): It is produced by the esterification reaction of the carboxylic acid compound (c) shown. Further, the above 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 those specified above.

The carboxylic acid compound (c) is, for example, a compound represented by the following formula (R-1) to formula (R-104).

n in the formula (R-1) to the formula (R-104) represents an integer of 1 to 12, and is preferably an integer of 2 to 12, more preferably an integer of 3 to 12, and an integer of 4 to 10. Even better, such as 6. At the same time, the cyclohexane ring is preferably in the trans form.

The esterification reaction of the alcohol compound (b) with the carboxylic acid compound (c) is preferably carried out in the presence of a condensing agent. The esterification reaction can be carried out efficiently and rapidly by carrying out the esterification reaction in the presence of a condensing agent.

The condensing agent may, for example, be 1-cyclohexyl-3-(2-N-morpholinylethyl)carbodiimidemethyl-p-toluenesulfonate, dicyclohexylcarbodiimide or diisopropylcarbamate. Imine, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride Salt (water-soluble carbodiimide: commercially available as WSC), bis(2,6-diisopropylphenyl)carbodiimide and bis(trimethyldecyl)carbodiimide Compound, 2-methyl-6-nitrobenzoic acid, 2,2'-carbonyl bis-1H-imidazole, 1,1'-oxalyldiimidazole, diphenyl azide, 1 (4-nitrogen Benzenesulfonyl)-1H-1,2,4-triazole, 1H-benzotriazol-1-yloxytripyrrolidinylphosphonium hexafluorophosphate, 1H-benzotriazole-1- Alkoxytris(dimethylamino)phosphonium hexafluorophosphate, N,N,N',N'-tetramethyl-O-(N-succinimide)urea tetrafluoroborate, N-(1,2,2,2-tetrachloroethoxycarbonyloxy) succinimide, N-carbon benzoyloxysuccinimide, O-(6-chlorobenzotriazole-1 -yl)-N,N,N',N'-tetramethyluronium tetrafluoroborate, O-(6-chlorobenzotriazol-1-yl)-N,N,N',N'- Tetramethyluronium hexafluorophosphate Acid salt, 2-bromo-1-ethylpyridinium tetrafluoroborate, 2-chloro-1,3-dimethylimidazolium chloride, 2-chloro-1,3-dimethylimidazolium Fluorophosphate, 2-chloro-1-methylpyridinium iodide, 2-chloro-1-methylpyridinium p-toluenesulfonate, 2-fluoro-1-methylpyridinium p-toluenesulfonate And pentachlorophenyl trichloroacetate and the like.

The condensing agent is preferably selected from the group consisting of carbodiimide compounds, 2,2'-carbonylbis-1H-imidazole, 1,1'-oxalyldiimidazole, diphenyl azide, 1H-benzotriazole- 1-yloxytripyrrolidinylphosphonium hexafluorophosphate, 1H-benzotriazol-1-yloxytris(dimethylamino)phosphonium hexafluorophosphate, N,N,N', N'-tetramethyl-O-(N-succinimide)urea ruthenium tetrafluoroborate, N-(1,2,2,2-tetrachloroethoxycarbonyloxy) succinimide, O-(6-chlorobenzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate, 2-chloro-1,3-dimethylimidazolinium Chloride, 2-chloro-1,3-dimethylimidazolium hexafluorophosphate, 2-chloro-1-methylpyridinium iodide and 2-fluoro-1-methylpyridinium p-toluenesulfonic acid Salt, and the group formed by the mixture of these.

More preferably, the condensing agent is selected from the group consisting of carbodiimide compounds, 2,2'-carbonylbis-1H-imidazole, 1H-benzotriazol-1-yloxytripyrrolidinylphosphonium hexafluorophosphate, 1H- Benzotriazol-1-yloxytris(dimethylamino)phosphonium hexafluorophosphate, N,N,N',N'-tetramethyl-O-(N-ammonium imino) Urea 鎓 tetrafluoroborate, O-(6-chlorobenzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate, 2-chloro-1,3 - dimethylimidazolium chloride and 2-chloro-1-methylpyridinium iodide, and a mixture of such mixtures, in terms of economy, carbodiimide compounds are further good.

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-diisopropylbenzene) Carbodiimide, and mixtures of these are preferred.

The condensing agent is usually used in an amount of from 2.0 to 3.0 mol based on 1 mol of the alcohol compound (b).

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

The esterification reaction can be carried out in the presence of a catalyst. Examples of the catalyst include N,N-dimethylaminopyridine, N,N-dimethylaniline, and dimethylammonium pentafluorobenzenesulfonate, and mixtures thereof. Among them, N,N-dimethylaminopyridine and N,N-dimethylaniline are preferred, and N,N-dimethylaminopyridine is more preferred. 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 carried out in a solvent. In terms of reaction yield or productivity, the solvent is preferably a nonpolar organic solvent such as pentane, hexane, heptane, toluene, xylene, benzene, chlorobenzene, chloroform or dichloromethane, and acetone, a polar organic solvent such as methyl hydrazine, N-methyl-2-pyrrolidone, N,N-dimethylformamide or N,N-dimethylacetamide, more preferably toluene or xylene Benzene, chlorobenzene, chloroform, dichloromethane, acetone, N-methyl-2-pyrrolidone, N,N-dimethylformamide and N,N-dimethylacetamide. These solvents may be used singly or in combination of several kinds.

The carboxylic acid compound (c) is preferably used in an amount of from 1.5 to 3.0 mol, more preferably from 1.8 to 2.8 mol, and from 1.8 to 2.5 mol, relative to 1 mol of the alcohol compound (b). Better.

The solvent is used in an amount of preferably 0.5 to 50 parts by mass, more preferably 1 to 20 parts by mass, and preferably 2 to 10 parts by mass based on 1 part by mass of the total of the alcohol compound (b) and the carboxylic acid compound (c). The quality is better.

The temperature of the esterification reaction is preferably from -20 to 30 ° C in terms of reaction yield or productivity, more preferably from -10 to 20 ° C, still more preferably from -10 to 10 ° C.

Meanwhile, the time of the esterification reaction is preferably from 1 minute to 72 hours in terms of reaction yield or productivity, and more preferably from 1 to 48 hours, still more preferably from 1 to 24 hours.

The polymerizable liquid crystal compound can be obtained from the obtained suspension by a method such as filtration or decantation.

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

 <Relativity film>  

The polymerizable liquid crystal compound according to an embodiment of the present invention can be preferably used to form a retardation film and to form a retardation film having reverse wavelength dispersibility. According to an embodiment of the present invention, there is provided a retardation film (hereinafter also referred to as "the retardation film of the present invention") which is composed of a polymer in an oriented state of the polymerizable liquid crystal compound. Further, the orientation state refers to a state in which the molecules are oriented, and the obtained film has a state in which the wavelength is dispersed. The retardation film of the present invention is preferably a wavelength dispersion degree Re (450 nm) / Re (550 nm) satisfying the following formula (α).

0.6 ≦ Re (450 nm) / Re (550 nm) < 1.0 (α) [In the formula (1), Re (λ) is a front phase difference value indicating light with respect to the wavelength λ nm. ]

The retardation film Re (450 nm) / Re (550 nm) of the retardation film of the present invention is preferably 0.63 or more and less than 1.0, and more preferably 0.65 or more and less than 1.0. The retardation film of the retardation film of the present invention preferably has Re (450 nm) / Re (550 nm) or more as the above lower limit value, and can be circularly polarized in a short wavelength region around 450 nm. If the wavelength dispersion degree Re (450 nm) / Re (550 nm) of the retardation film of the present invention does not reach the above upper limit value, the obtained retardation film has reverse wavelength dispersion property and can be uniform in a wide wavelength range. Polarized conversion.

Further, in a preferred embodiment of the present invention, J ² in the formula (a) is a structure (c-2), and in this case, a retardation film having particularly high reverse wavelength dispersibility is easily obtained. At this time, 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 in this range, when the wavelength dispersibility of the retardation film is adjusted to a desired value, it is necessary to add a small amount of the polymerizable liquid crystal compound of one embodiment of the present invention in a small amount. It is advantageous in terms of cost. In other words, the retardation film of the present invention may be composed of a polymerizable liquid crystal compound derived from another polymerizable liquid crystal compound (hereinafter referred to as "polymerizable liquid crystal compound (A)"). Also referred to as a structural unit structure of the "polymerizable liquid crystal compound (B)"), the amount of the polymerizable liquid crystal compound (A) to be added can be reduced.

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

When the retardation film of the present invention is used in a λ/4 plate, the phase difference Re (550 nm) in the wavelength of 550 nm of the obtained retardation film is preferably 113 to 163 nm, and more preferably 130 to 150 nm. More preferably 135 to 150 nm.

When the retardation film of the present invention is used as the VA (vertical alignment) mode optical film, the film thickness of the retardation film is adjusted so that Re (550 nm) is preferably 40 to 100 nm, and is 60 to 80 nm. Better left and right.

According to another embodiment of the present invention, a polarizing plate (hereinafter also referred to as "the polarizing plate of the present invention") including the retardation film, in particular, an elliptically polarizing plate and a circularly polarizing plate are also provided. The polarizing plate of the present invention can be obtained by combining the retardation film of the present invention and a polarizing film. In the elliptically polarizing plate and the circularly polarizing plate, the retardation film of the present invention is bonded to the polarizing film. Meanwhile, in another embodiment of the present invention, a wide-area circular polarizing plate can be provided, which further laminates the retardation film of the present invention into a wide-area λ/4 plate and is attached to the elliptically polarizing plate or the circularly polarizing plate. .

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

The optical display of the present invention includes the polarizing plate of the present invention, and examples thereof include a liquid crystal display device including a laminate in which a polarizing plate of the present invention and a liquid crystal panel are bonded together, or a polarizing plate and a light-emitting device of the present invention. An organic EL display device of an organic EL panel in which layers are laminated.

Further, in the present invention, the retardation film is a film which is used to convert linearly polarized light into circularly polarized light or elliptically polarized light, or conversely converts circularly polarized light or elliptically polarized light into linearly polarized light. The retardation film of the present invention is a polymer containing the polymerizable liquid crystal compound. In other words, the retardation film of the present invention contains a polymer composed of a structural unit derived from one or two or more kinds of the polymerizable liquid crystal compounds.

In addition to the structural unit derived from the above polymerizable liquid crystal compound (hereinafter also referred to as "polymerizable liquid crystal compound (A)"), the retardation film of the present invention may be derived from another polymerizable liquid crystal compound (hereinafter also referred to as "polymerizability". In the structure of the liquid crystal compound (B)"), the retardation film can be composed of a polymer in a state in which the polymerizable liquid crystal compound is in a state of being aligned.

In addition to the structural unit derived from the polymerizable liquid crystal compound (A), the retardation film of the present invention can adjust the wavelength dispersion and retardation value of the retardation film by containing the structural unit derived from the polymerizable liquid crystal compound (B). The optical properties and the thermal properties are equal to the desired values, and the polymerizable liquid crystal compound (A) is also advantageous in cost when it has a high reverse wavelength dispersibility (for example, 0.60 ( (α) ≦ 0.70). In addition, the polymerizable liquid crystal compound (B) is exemplified by the "Liquid Crystal Handbook (Edited by the Liquid Crystal Manual Editorial Board, Maruzen Co., Ltd., issued on October 30, 2000), Chapter 3, Molecular Structure and Liquid Crystallinity, 3.2 Non-chiral ( A compound having a polymerizable group among the compounds described in "nochiral" rod-like liquid crystal molecules and 3.3 chiral rod-like liquid crystal molecules. The retardation film of the present invention may contain 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, in the above polymerizable liquid crystal compound (A), additives such as the above polymerizable liquid crystal compound (B), a polymerization initiator, a polymerization inhibitor, a photosensitizer, an organic solvent, and/or a leveling agent are added as needed. The mixed solution was prepared. In particular, it is preferable to contain an organic solvent so that film formation is easy at the time of film formation, and it is preferable to contain a polymerization initiator, so that the obtained retardation film has a hardening function.

The viscosity of the mixed solution containing the above polymerizable liquid crystal compound is adjusted to, for example, 10 Pa ‧ or less, and is preferably applied at a level of about 0.1 to 7 Pa ‧ s. Further, the viscosity of the mixed solution can be adjusted by the content of the organic solvent.

Meanwhile, the concentration of the solid content in the above mixed solution is, for example, 5 to 50% by mass, preferably 5 to 30% by mass, more preferably 5 to 15% by mass. In addition, the term "solid content" as used herein means a component obtained by removing a solvent from a mixed solution (liquid crystal composition). When the concentration of the solid content is 5% by mass or more, the retardation film is prevented from becoming too thin, and the desired birefringence can be imparted to the optical compensation of the liquid crystal panel. At the same time, when the content is 50% by mass or less, the viscosity of the mixed solution is low, and the film thickness of the retardation film is less likely to cause unevenness, which is preferable.

The polymerization initiator may, for example, be a photopolymerization initiator, a thermal polymerization initiator or the like, and is preferably a photopolymerization initiator.

Examples of the photopolymerization initiator include, for example, benzoin, benzophenone, benzotrione, α-hydroxyketone, α-aminoketone, iodonium or sulfonium salt, and the like. In other words, Irgacure 907, Irgacure 184, Irgacure 651, Irgacure 819, Irgacure 250, Irgacure 369 (all of which are manufactured by Ciba Japan Co., Ltd.), Seikuol BZ, Seikuol Z, and Seikuol BEE (above, all are Seiko chemistry) (share) system, Kayacure BP100 (manufactured by Nippon Kayaku Co., Ltd.), Kayacure UVI-6992 (manufactured by Dow Co., Ltd.), and Adekaoptmer SP-152 and Adekaoptmer SP-170 (all of which are manufactured by ADEKA Co., Ltd.) .

The content of the polymerization initiator is, for example, 0.1 to 30 parts by mass, and preferably 0.5 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the polymerizable liquid crystal compound. The polymerizable liquid crystal compound can be polymerized without interfering with the orientation of the liquid crystal compound as long as it is within the above range.

Examples of the polymerization inhibitor include, for example, hydroquinones having a substituent such as hydroquinone or an alkyl ether; catechols having a substituent such as an alkyl ether such as butylcatechol; and pyrogallol; A radical scavenger such as 2,6,6-tetramethyl-1-piperidinyloxy radical, a thiophenol, a β-naphthylamine or a β-naphthol.

By using a polymerization inhibitor, polymerization of the polymerizable liquid crystal compound can be controlled, and the stability of the obtained retardation film can be improved. The polymerization inhibitor is used in an amount of, for example, 0.05 to 30 parts by mass, based on 100 parts by mass of the polymerizable liquid crystal compound, and preferably 0.1 to 10 parts by mass. The polymerizable liquid crystal compound can be polymerized without interfering with the orientation of the liquid crystal compound as long as it is within the above range.

The photosensitizer may, for example, be a xanthone such as xanthone or thioxanthone, an anthraquinone or an anthracene having a substituent such as an alkyl ether, phenothiazine or red fluorene.

By using a photosensitizer, the polymerizable liquid crystal compound can be polymerized with high sensitivity.

Meanwhile, the photosensitizer is used in an amount of, for example, 0.1 to 30 parts by mass, and preferably 0.5 to 10 parts by mass, per 100 parts by mass of the polymerizable liquid crystal compound. When it is within the above range, the polymerizable liquid crystal compound can be polymerized without interfering with the orientation of the polymerizable liquid crystal compound.

The organic solvent can dissolve an organic solvent such as a polymerizable liquid crystal compound, and may be any solvent that is inactivated in the polymerization reaction. The organic solvent may, for example, be an alcohol solvent such as methanol, ethanol, ethylene glycol, isopropanol, propylene glycol, methyl cellosolve, butyl cellosolve or propylene glycol monomethyl ether; ethyl acetate, butyl acetate, ethylene glycol An ester solvent such as alcohol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate or ethyl lactate; acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone or a ketone solvent such as methyl isobutyl ketone; a non-chlorinated aliphatic hydrocarbon solvent such as pentane, hexane or heptane; a non-chlorinated aromatic hydrocarbon solvent such as toluene, xylene or phenol; a nitrile solvent such as acetonitrile; tetrahydrofuran or An ether solvent such as dimethoxyethane; a chlorine solvent such as chloroform or chlorobenzene; a guanamine solvent such as N-methylpyrrolidone (NMP) or N,N-dimethylformamide (DMF); Wait. In order to dissolve the polymerizable liquid crystal compound, it is preferably an ester solvent, a ketone solvent, a non-chlorinated aromatic hydrocarbon solvent, an ether solvent or a guanamine solvent, and a ketone solvent and a guanamine solvent. More preferably, the guanamine solvent is more preferred. These organic solvents may be used singly or in combination of several kinds.

The content of the organic solvent is preferably from 100 to 10,000 parts by mass, more preferably from 200 to 5,000 parts by mass, still more preferably from 500 to 2,500 parts by mass, per 100 parts by mass of the polymerizable liquid crystal compound. When the content of the organic solvent is at least the above lower limit value, the retardation film is prevented from becoming too thin, and the desired birefringence can be imparted to the optical compensation of the liquid crystal panel. When the content of the organic solvent is at most the above upper limit value, the viscosity of the mixed solution is low, and the film thickness of the retardation film is less likely to be uneven.

The leveling agent may, for example, be an additive for radiation hardening paint (made by BYK Japan: BYK-352, BYK-353, BYK-361N), and a coating additive (made by Toray Dow Corning): SH28PA, DC11PA, ST80PA), coating additives (Shin-Etsu Chemical Co., Ltd.: KP321, KP323, X22-161A, KF6001) and fluorine-based additives (Daily Ink Chemical Industry Co., Ltd.: F-445, F-470, F-479 )Wait.

The obtained retardation film can be smoothed by using a leveling agent. Further, in the process of the retardation film, the fluidity of the mixed solution can be controlled, or the crosslinking density of the retardation film obtained by polymerizing the polymerizable liquid crystal compound can be adjusted. Meanwhile, the specific value of the amount of the leveling agent used is, for example, 0.05 to 30 parts by mass, and preferably 0.05 to 10 parts by mass, per 100 parts by mass of the polymerizable liquid crystal compound. When it is within the above range, the polymerizable liquid crystal compound can be polymerized without interfering with the orientation of the polymerizable liquid crystal compound.

The thus obtained mixed solution is applied onto a support substrate or the like. Further, by appropriately adjusting the coating amount or concentration of the mixed solution, the film thickness can be adjusted to give a desired phase difference. When the amount of the polymerizable liquid crystal compound is a constant mixed solution, the phase difference (retardation value) and Re(λ) of the obtained retardation film can be adjusted according to the following formula, so that the film thickness can be adjusted. d, to obtain the desired Re (λ).

Re(λ)=d×Δn(λ) (wherein, Re(λ) represents the phase difference value in the wavelength λnm, d represents the film thickness, and Δn(λ) represents the birefringence in the wavelength λnm.)

The coating method of the support substrate may, for example, be a pinch coating method, a direct gravure coating method, a reverse gravure coating method, a CAP coating method, or a die coating method. Meanwhile, a method of coating using a coater such as a dip coater, a bar coater, or a spin coater can be mentioned.

Examples of the support substrate include glass, a plastic sheet, a plastic film, or a light-transmitting film. Further, examples of the light-transmitting film include a polyolefin film such as polyethylene, polypropylene, and a norbornene-based polymer, a polyvinyl alcohol film, a polyethylene terephthalate film, and a polymethacrylate film. Polyacrylate film, cellulose ester film, polyethylene naphthalate film, polycarbonate film, polyfluorene film, polyether ruthenium film, polyether ketone film, polyphenylene sulfide film or polyphenylene oxide film .

In the step of, for example, the step of attaching the retardation film of the present invention, the conveyance step, the storage step, and the like, which requires the strength of the retardation film, it can be easily handled without damage by the use of the support substrate.

Meanwhile, it is preferred to apply a mixed solution containing the above polymerizable liquid crystal compound to the alignment film after forming the alignment film on the support substrate. When the mixed solution containing the above-mentioned polymerizable liquid crystal compound or the like is applied, the alignment film has heat resistance in the case of solvent resistance insoluble in the mixed solution, removal of the solvent, or orientation of the liquid crystal, and heat resistance during wiping, and no friction during wiping. It is preferable to cause peeling or the like, and it is preferably composed of a polymer or a composition containing a polymer.

The polymer may, for example, be a polyamine or a gelatin having a guanamine bond in the molecule, a polyimine having a quinone bond in the molecule, and a polyamine of a hydrolyzate thereof, a polyvinyl alcohol, an alkyl group. Polymers such as polyvinyl alcohol, polypropylene decylamine, polyoxazole, polyethylenimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid or polyacrylate. These polymers may be used singly or in combination of two or more kinds thereof. These polymers can be easily obtained by condensation polymerization such as dehydration or deamination, chain polymerization such as radical polymerization, anionic polymerization or cationic polymerization, coordination polymerization or ring-opening polymerization.

At the same time, these polymers can be coated by dissolving in a solvent. The solvent is not particularly limited, and specific examples thereof include water; alcohol such as methanol, ethanol, ethylene glycol, isopropanol, propylene glycol, methyl cellosolve, butyl cellosolve or propylene glycol monomethyl ether; ethyl acetate; An ester solvent such as butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate or ethyl lactate; acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, a ketone solvent such as methyl amyl ketone or methyl isobutyl ketone; a non-chlorinated aliphatic hydrocarbon solvent such as pentane, hexane or heptane; a non-chlorinated aromatic hydrocarbon solvent such as toluene or xylene; and a nitrile such as acetonitrile. Solvent; ether solvent such as tetrahydrofuran or dimethoxyethane; chlorine solvent such as chloroform or chlorobenzene; These organic solvents may be used singly or in combination of several kinds.

Meanwhile, in order to form an oriented film, a commercially available oriented film material can also be used as it is. The commercially available alignment film material may, for example, be Sun Ever (registered trademark, manufactured by Nissan Chemical Industries Co., Ltd.) or Optomer (registered trademark, manufactured by JSR Co., Ltd.).

When such an alignment film is used, since the refractive index is controlled without stretching, the in-plane scattering of birefringence can be made small. Therefore, it is also possible to efficiently provide a large retardation film corresponding to a large-sized flat panel display device (FPD) on the support substrate.

a method of forming an alignment film on the support substrate, for example, by coating a commercially available alignment film material or a compound as an alignment film material on the support substrate, and then annealing, thereby supporting the support An oriented film is formed on the substrate.

The thickness of the alignment film thus obtained is, for example, 10 nm to 10,000 nm, and preferably 10 nm to 1,000 nm. As long as it is in the above range, the polymerizable liquid crystal compound or the like can be oriented at a desired angle on the alignment film.

At the same time, such oriented films may be wiped or polarized UV irradiated as needed. By forming the alignment film, the polymerizable liquid crystal compound or the like can be oriented in a desired direction.

The method of wiping the orientation film may be, for example, a method in which a rubbing roller that is rotated by wrapping the wiping cloth is brought into contact with an orientation film that is placed on a stage to be transported.

As described above, in the step of preparing the unpolymerized film, an unpolymerized film (liquid crystal layer) may be laminated on the alignment film which has been laminated on any of the support substrates. At this time, the production cost can be reduced as compared with the method of fabricating the liquid crystal cell and injecting the mixed solution into the liquid crystal cell. And a film in the roll film can be produced.

Although it is possible to simultaneously carry out drying of the solvent at the time of carrying out the polymerization, in terms of film formability, it is preferred that the solvent be close to dry before polymerization.

Examples of the method for drying the solvent include natural drying, air drying, and drying under reduced pressure. Specifically, the heating temperature is preferably from 10 to 120 ° C, more preferably from 25 to 80 ° C. At the same time, the heating time is preferably from 10 seconds to 60 minutes, and more preferably from 30 seconds to 30 minutes. As long as the heating temperature and the heating time are within the above range, a supporting substrate which is not sufficiently heat-resistant can be used as the supporting substrate.

Next, the unpolymerized film (liquid crystal layer) obtained above was polymerized and cured. By this, a film in which the polymerizable liquid crystal compound is oriented and fixed, that is, a film containing a polymerizable liquid crystal compound according to an embodiment of the present invention (hereinafter also referred to as "polymer film") can be obtained. Therefore, a polymer film can be produced in which the refractive index change in the plane direction of the film is small, and the refractive index change in the normal direction of the film is large.

The method of polymerizing the unpolymerized film (liquid crystal layer) is determined by the type of the polymerizable liquid crystal compound. When the polymerizable group contained in the polymerizable liquid crystal compound is photopolymerizable, the unpolymerized film (liquid crystal layer) can be polymerized by thermal polymerization as long as the polymerizable group is thermally polymerizable. In the present invention, in particular, it is preferred to polymerize an unpolymerized film (liquid crystal layer) by photopolymerization. According to photopolymerization, since the unpolymerized film (liquid crystal layer) can be polymerized at a low temperature, the range of heat resistance of the support substrate can be widened. At the same time, it is also easy to industrialize. At the same time, in terms of film formability, photopolymerization is also preferred. Photopolymerization can be carried out by irradiating visible light, ultraviolet light or laser light (laser light) on an unpolymerized film (liquid crystal layer). In terms of handleability, ultraviolet light is particularly preferable, and the light irradiation system can be performed while heating to a temperature at which the polymerizable liquid crystal compound becomes a liquid crystal phase. At this time, the polymer film can be drawn with a photomask or the like to obtain a patterned optical film.

Further, the retardation film of the present invention is a film as compared with a stretched film which gives a phase difference when the polymer is extended.

In the method for producing a retardation film of the present invention, the step of peeling off the support substrate may be further included. According to the laminated body obtained as described above, a film composed of an oriented film and a retardation film can be formed. Meanwhile, in addition to the step of peeling off the above support substrate, a step of peeling off the oriented film may be further included. With such a configuration, a retardation film can be obtained.

 [Examples]  

Hereinafter, the present invention will be described in more detail by way of examples. Unless otherwise stated, the terms "%" and "parts" in the examples refer to the mass% and mass parts.

 (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 2,5-dihydroxybenzaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the flask at 0.50 g, 1,3-dimethyl-2- In the case of thiohydantoin (manufactured by Wako Pure Chemical Industries, Ltd.), 0.52 g, ammonium acetate (manufactured by Kanto Chemical Co., Ltd.), 0.28 g, and acetonitrile (manufactured by Wako Pure Chemical Industries, Ltd.), 2 g, while mixing It was allowed to react at 80 ° C for 1 hour. Then, it was cooled to room temperature, and filtered, and the precipitated solid was separated. The obtained solid was washed three 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 the compound (A) was 63% based on 2,5-dihydroxybenzaldehyde.

Further, the results of ¹ H-NMR analysis of the obtained compound (A) are 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 a compound (A) was added to the flask, and 1.74 g of a compound (B) synthesized by the patent document (JP-A-2010-31223) was used. Dimethylaminopyridine (hereinafter referred to as DMAP, manufactured by Wako Pure Chemical Industries, Ltd.), 0.0046 g, dibutylhydroxytoluene (hereinafter, abbreviated as BHT, manufactured by Wako Pure Chemical Industries, Ltd.), 0.029 g, and chloroform (Kanto 8 g of a chemical (manufactured by the company), and 0.60 g of diisopropylcarbodiimide (hereinafter referred to as IPC and Wako Pure Chemical Industries, Ltd.) was added to the dropping funnel, and the reaction was carried out at 0 ° C. late. Then, the insoluble components are removed by filtration. The obtained chloroform solution was dropped into 2-propanol in an amount of 3 times by weight based on the weight of the chloroform contained in the chloroform solution. Next, the precipitated solid was taken out by filtration. Next, the obtained solid was washed three times with 10 g of 2-propanol (manufactured by Wako Pure Chemical Industries, Ltd.), and then dried under reduced pressure at 30 ° C to obtain 0.69 g of a compound (C). The yield of the compound (C) was 34% based on the compound (A).

Further, the results of ¹ H-NMR analysis of the obtained compound (C) are as follows.

¹ H-NMR (CDCl ₃ ): δ (ppm) 1.41 to 1.82 (m, 24H), 2.27 to 2.30 (m, 8H), 2.57 to 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), 6.95~6.99 (m, 4H), 7.09~7.17 (m, 2H), 8.07 (d, 1H).

The maximum absorption wavelength (λ _max ) of the obtained compound (C) was measured by a spectrophotometer UV-3150 (manufactured by Shimadzu Corporation). The result is λ _max of 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 2,5-dihydroxybenzaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the flask to 2.50 g of 1,3-dimethylbarbital. 2.83 g of barbituric acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.40 g of ammonium acetate (manufactured by Kanto Chemical Co., Ltd.), and 10 g of water were allowed to react at 25 ° C for 1 hour while mixing. Then, the precipitated solid was separated by filtration. The obtained solid was washed three 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 the compound (D) was 66% based on 2,5-dihydroxybenzaldehyde.

Further, the results of ¹ H-NMR analysis of the obtained compound (D) are 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), 10.01 (s, 1H).

A 20 mL four-necked flask equipped with a Dimroth condenser and a thermometer was placed in a nitrogen atmosphere, and 2.10 g of the compound (D), 6.67 g of the above compound (B), 0.018 g of DMAP, 0.11 g of BHT, and chloroform (Kantong Chemical) were added to the flask. 30 g of the product (manufactured by the company) was added to 2.28 g of IPC in a dropping funnel while mixing, and allowed to react at 0 ° C overnight. Then, the insoluble components are removed by filtration. The obtained chloroform solution was dropped into 2-propanol in an amount of 3 times by weight based on the weight of the chloroform contained in the chloroform solution. Next, 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 to obtain 0.84 g of a compound (E). The yield of the compound (E) was 11% based on the compound (D).

Further, the results of ¹ H-NMR analysis of the obtained compound (E) are 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~ 6.99 (m, 4H), 7.21 (d, 1H), 7.27 (dd, 1H), 7.90 (d, 1H), 8.49 (s, 1H)

The maximum absorption wavelength (λ _max ) of the obtained compound (E) was measured by a spectrophotometer UV-3150 (manufactured by Shimadzu Corporation). The result is λ _max of 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 2,5-dihydroxybenzaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the flask to 2.00 g of 1,3-decanedione (indan). Dione) (manufactured by Tokyo Chemical Industry Co., Ltd.) 2.12 g, ammonium acetate (manufactured by Kanto Chemical Co., Ltd.), 1.12 g, and 10 g of water were reacted at 25 ° C for 1 hour while mixing. Then, the precipitated solid was separated by filtration. The obtained solid was washed three times with 10 g of water, and then dried under reduced pressure at 40 ° C to obtain 2.30 g of Compound (F). The yield of the compound (F) was 60% based on 2,5-dihydroxybenzaldehyde.

Further, the results of ¹ H-NMR analysis of the obtained compound (F) are 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 above compound (B), 0.007 g of DMAP, 0.033 g of BHT, and chloroform (Kantong Chemical) were added to the flask. 4 g of the product (manufactured by the company) was added to an IPC of 0.87 g in a dropping funnel while mixing, and allowed to react at 0 ° C overnight. Then, the insoluble components are removed by filtration. The obtained chloroform solution was dropped into 2-propanol in an amount of 3 times by weight based on the weight of the chloroform contained in the chloroform solution. Next, the precipitated solid was taken out by filtration. Next, the obtained solid was washed three times with 10 g of 2-propanol (manufactured by Wako Pure Chemical Industries, Ltd.), and then dried under reduced pressure at 30 ° C to obtain 1.54 g of a compound (G). The yield of the compound (G) was 48% based on the compound (F).

Further, the results of ¹ H-NMR analysis of the obtained compound (G) are as follows.

¹ H-NMR (CDCl ₃ ): δ (ppm) 1.45~1.82 (m, 24H), 2.31~2.37 (m, 8H), 2.57~2.81 (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~ 7.87 (m, 2H), 7.98 to 8.05 (m, 3H), 8.20 (d, 1H).

The maximum absorption wavelength (λ _max ) of the obtained compound (G) was measured by a spectrophotometer UV-3150 (manufactured by Shimadzu Corporation). The result is λ _max of 338 nm.

 (Example 1: Measurement of nematic phase transition temperature)  

100 mg (mg) of the compound (C) obtained by the method described in Synthesis Example 1 was weighed in a vial tube, and dissolved by adding 2 g of chloroform. The obtained solution was applied onto a glass substrate with a PVA-attached film coated with a wiping treatment, and dried. This substrate was placed in a cooling and heating device ("LNP94-2" manufactured by Japan Hitech Co., Ltd.), and the temperature was raised 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 Co., Ltd.), and the temperature at which the nematic phase was formed was measured to obtain a 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)  

The nematic phase transition temperature of the following compounds (H) and (I) described in Japanese Patent No. 4606195 was measured in the same manner as in Example 1. The results obtained are shown in Table 6.

 (Example 4)  

Using the above compound (C), a retardation film was produced as follows. First, a composition (1) for forming a photo-alignment film and a composition (1) for forming a retardation film are prepared as follows.

 <Preparation of Composition (1) for Forming Light Oriented Film>  

The following components (photo-alignment material and solvent) were mixed, and the obtained mixture was stirred at 80 ° C for 1 hour to obtain a composition (1) for forming a photo-alignment film. Further, the following photo-alignment material is synthesized by the direction described in JP-A-2013-33248.

‧Light directional materials (5 copies):

‧Solvent (95 parts): cyclopentanone

 <Preparation of Composition (1) for Forming Phase Difference Film>  

The following compounds were mixed at a ratio described in the following Table 7 to obtain a composition (1) for forming a retardation film.

‧ Polymerization initiator: 2-benzyl-dimethylamino-1-(4-morpholinylphenyl)butan-1-one (Irgacure 369; manufactured by BASF, Japan)

‧Leveling agent: polyacrylate compound (BYK-361N; made by BYK, Japan)

‧Solvent: N-methylpyrrolidone (NMP; manufactured by Kanto Chemical Co., Ltd.)

‧Inhibitor: BHT (Wako Pure Chemical Industries Co., Ltd.)

 <Manufacture of retardation film (1)>  

A cycloolefin polymer film (COP) (ZF-14, manufactured by Japan Zeon Co., Ltd.) was produced by a corona treatment apparatus (AGF-B10, manufactured by Kasuga Electric Co., Ltd.) under the conditions of an output of 0.3 kW and a treatment rate of 3 m/min. ) Processed once. The composition for forming a photo-alignment film (1) was coated on the surface subjected to corona treatment by a bar coater, and dried at 80 ° C for 1 minute, using a polarized UV irradiation device (SPOT CURE SP-7; Ushio motor (Stock)), polarized UV exposure was carried out at a cumulative light amount of 100 mJ/cm ² to obtain an oriented film. When the film thickness of the obtained alignment film was measured by a laser microscope (LEXT, manufactured by Olympus Co., Ltd.), it was 100 nm. Next, the composition for forming a retardation film (1) was applied onto the oriented film by a bar coater, and after drying at 140 ° C for 2 minutes, by using a high-pressure mercury lamp (Unicure VB-15201BY-A, Ushio motor ( (manufactured by the company)) irradiated with ultraviolet light (wavelength: 365 nm, cumulative light in a wavelength of 365 nm: 750 mJ/cm ² ) to prepare a retardation film (1)

 <Measurement of optical characteristics>  

The front retardation value of the retardation film (1) was measured by a measuring machine (KOBRA-WR, manufactured by Oji Scientific Instruments Co., Ltd.). The front surface difference value of the optical film (1) at wavelengths of 450 nm, 550 nm, and 650 nm was measured, and [Re (450 nm) / Re (550 nm)] (hereinafter, α) was calculated. The results are shown in Table 8.

 (Examples 5 and 6)  

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

From the above results, it is understood that the polymerizable liquid crystal compound of the present invention has a retardation film having a low phase transition temperature and a retardation film composed of a polymer in an oriented state of the polymerizable liquid crystal compound, and has a reverse wavelength dispersibility. In particular, it is understood that the compound (C) in which J ² in the formula (a) is a structure of (c-2) has a very high reverse wavelength dispersibility.

Claims (7)

A polymerizable liquid crystal compound represented by the following formula (a): In the formula (a), m and n each independently represent an integer of 0 to 3, and B ¹ , B ² , D ¹ , D ² , E ¹ and E ² each independently represent -CR ¹ R ² -, -CH ₂ -CH ₂ -, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)- , -OC(=S)-O-, -CO-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 represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms, and A ¹ , A ² , G ¹ and G ² each independently represent a carbon number of 3 to 16. a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and the alicyclic hydrocarbon group and the hydrogen atom contained in the aromatic hydrocarbon group may independently be a halogen atom, -R ³ , - Substituting OR ⁴ , cyano or nitro, the -CH ₂ - contained in the alicyclic hydrocarbon group may be independently substituted with -O-, -S-, -NH- or -NR ⁵ -, the alicyclic hydrocarbon group -CH(-)- may be substituted with -N(-)-, and R ³ , R ⁴ and R ⁵ each independently represent an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group may be a fluorine atom. substituted, F. ¹ and F ² each independently represent a carbon number of 1 to 12 alkanediyl group, the hydrogen atom in the alkanediyl group may be contained in In each independently be substituted with a halogen atom or -OR ^6, -CH the alkanediyl group containing ₂ - may be independently substituted by -O- or -CO-, R ⁶ represents an alkyl group having 1 to 4 carbon atoms, which The hydrogen atom contained in the alkyl group may be substituted by a fluorine atom, and P ¹ and P ² each independently represent a hydrogen atom or a polymerizable group, but at least one of P ¹ and P ² represents a polymerizable group, and J ¹ represents a hydrogen atom. Or an alkyl group having 1 to 3 carbon atoms, and J ² represents a hydrocarbon group having 3 to 25 carbon atoms having a monocyclic structure or a polycyclic structure, and -CH ₂ - contained in the hydrocarbon group may independently be -O-, -S -, -CO-, -CS- or -NR ⁷ -, the hydrogen atom contained in the hydrocarbon group may independently be an alkyl group having 1 to 6 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms or a carbon number The aromatic hydrocarbon group of 6 to 12 is substituted, and R ⁷ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The polymerizable liquid crystal compound according to claim 1, wherein the J ² system is represented by the following formula (b): In the formula (b), K represents a hydrocarbon group having a monocyclic structure or a polycyclic structure and having a carbon number of 1 to 11 together with -X ¹ C(=)X ² -, and the -CH ₂ - contained in the hydrocarbon group may be independently Substituting -O-, -S-, -CO-, -CS- or -NR ⁷ -, the hydrogen atom contained in the hydrocarbon group may independently be an alkyl group having 1 to 6 carbon atoms and a carbon number of 3 to 6 An alicyclic hydrocarbon group or an 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, and X ¹ and X ² each independently represent -CO-, -CS-, -S -, -O- or -NR ⁸ -, R ⁸ 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 12 carbon atoms, and * represents a combination key. The polymerizable liquid crystal compound according to claim 1 or 2, wherein J ² in the formula (a) is represented by any one of the formulae (c-1) to (c-5): In the formulae (c-1) to (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 each independently Representing an oxygen atom or a sulfur atom, and Z ¹¹ , Z ¹² , Z ²¹ , Z ²² , Z ³¹ , Z ⁴¹ , Z ⁵¹ , Z ⁵² , Z ⁵³ and Z ⁵⁴ each independently represent a hydrogen atom and an alkyl group having 1 to 6 carbon atoms. The group is an alicyclic hydrocarbon group having 3 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 11 carbon atoms, and * represents a bond. The polymerizable liquid crystal compound according to any one of claims 1 to 3, wherein G ¹ and G ² are trans-cyclohexane-1,4-diyl.  A retardation film comprising a polymer in an oriented state of the polymerizable liquid crystal compound according to any one of claims 1 to 4.    A polarizing plate comprising the retardation film described in claim 5 of the patent application.    An optical display comprising the polarizing plate of claim 6 of the patent application.