JPWO2012115129A1 - Polymerizable liquid crystal compound, polymerizable liquid crystal composition, and alignment film - Google Patents

Abstract

A polymerizable liquid crystal compound represented by the following formula [1], a polymerizable liquid crystal composition containing the same, a polymer obtained therefrom, a coating film, an alignment film, and an optical member provided with the alignment film are provided. (In the formula, X 1, X 2, X 3 and X 4 each independently represent a hydrogen atom or a fluorine atom, and R represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an alkoxy group, or an alkoxycarbonyl group. , G represents -C (= O) O- or -OC (= O)-group, and n represents an integer of 4 to 10.)

Description

  The present invention relates to a polymerizable liquid crystal compound having polymerizability and liquid crystallinity, a composition containing the same, and a polymer and an alignment film obtained using these, for example, optical characteristics of a display device, a recording material, etc. The present invention relates to a polymerizable liquid crystal compound, a composition containing the polymerizable liquid crystal compound, a polymer containing the same, and a polymer and an alignment film which can be suitably used for optical compensation films such as polarizing plates and retardation plates for liquid crystal displays .

Due to demands for improving the display quality and weight reduction of liquid crystal display devices, there is an increasing demand for polymer films with controlled internal molecular orientation structures as optical compensation films such as polarizing plates and retardation plates. In order to meet this demand, development of a film utilizing the optical anisotropy of the polymerizable liquid crystal compound has been made.
The polymerizable liquid crystal compound used here is generally a liquid crystal compound having a polymerizable group and a liquid crystal structure part (structure part having a spacer part and a mesogen part), and an acrylic group is widely used as the polymerizable group. ing.

Such a polymerizable liquid crystal compound is generally made into a polymer (film) by a method of polymerizing by irradiation with radiation such as ultraviolet rays.
For example, a method in which a specific polymerizable liquid crystal compound having an acrylic group is supported between supports and a polymer is obtained by irradiating radiation while maintaining the compound in a liquid crystal state (see Patent Document 1), or an acrylic group is used. A method is known in which a photopolymerization initiator is added to a mixture of two kinds of polymerizable liquid crystal compounds, or a composition in which chiral liquid crystals are mixed with this mixture, and a polymer is obtained by irradiation with ultraviolet rays (Patent Document 2). reference).

The polymer (film) obtained by each of the above methods is a display device used in a high-temperature environment such as in a car as well as a display device such as a monitor or a television as a polarizing plate or a retardation film. Mounted on. For this reason, maintaining transparency in a high temperature environment is very important as a display device material.
However, when the film obtained from the polymerizable liquid crystal compound has a glass transition temperature (hereinafter referred to as Tg) that is lower than the temperature of the environment in which it is used, particularly in a high temperature environment, microscopic fluctuations of molecules occur. Therefore, the orientation may be disturbed, and the optical anisotropy may be significantly reduced.

Furthermore, in the field of displays, in recent years, studies on process simplification using these materials as In Cell retardation films have been actively promoted. The material used for this In Cell technology is required to have higher thermal stability and chemical resistance.
On the other hand, various alignment films such as horizontal, vertical, and hybrid alignment are obtained depending on the alignment mode of the polymerizable liquid crystal compound, and hybrid alignment films showing various average tilt angles have also been reported (see Patent Document 3). If the average tilt angle of the obtained film can be controlled with a low additive amount of the liquid crystal composition, it can be widely applied in the liquid crystal display field.

JP-A-62-70407 JP-A-9-208957 WO08 / 052376 pamphlet

  The present invention has been made in view of such circumstances, has excellent optical anisotropy, maintains a stable retardation value and transparency even at high temperatures, and is excellent in chemical resistance and heat resistance. Polymerizable liquid crystal compound capable of giving polymer and controlling average angle of hybrid alignment film with low addition amount, polymerizable liquid crystal composition containing the same, and polymer and alignment film obtained from the polymerizable liquid crystal composition The purpose is to provide.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the predetermined polymerizable liquid crystal compound having an α-methylene-γ-butyrolactone moiety has liquid crystallinity and itself has excellent polymerizability. In addition, it is possible to control the average angle of the hybrid alignment film with a low addition amount, to provide a stable liquid crystalline composition, and to provide a polymer or film obtained from the liquid crystalline composition in terms of optical anisotropy and transparency. It has been found that it has excellent heat resistance, and the present invention has been completed.

（式中、Ｘ¹、Ｘ²、Ｘ³およびＸ⁴は、互いに独立して、水素原子またはフッ素原子を表し、Ｒは、水素原子、ハロゲン原子、シアノ基、アルキル基、アルコキシ基、またはアルコキシカルボニル基を表し、Ｇは−Ｃ（＝Ｏ）Ｏ−または−ＯＣ（＝Ｏ）−基を表し、ｎは４〜１０の整数を表す。）
２．１の重合性液晶化合物を含有する重合性液晶組成物、
３．さらに、一分子中に重合性基を１つ以上有する液晶性化合物を含有する２の重合性液晶組成物、
４．上記液晶性化合物が、下記式［２］または［３］で表される重合性基を一分子中に１つ以上有する化合物である３の重合性液晶組成物、

（式中、破線は結合手を表す。）
５．上記液晶性化合物が、下記式［４］および［５］で表される化合物からなる群より選ばれる少なくとも１種である３または４の重合性液晶組成物、

（式中、Ｘは、フッ素原子、シアノ基または炭素数４〜８の一価炭化水素基を表し、ｆ１およびｆ２はそれぞれ独立に２〜９の整数を表し、ｇは２〜９の整数を表し、Ｍ¹、Ｍ²およびＭ³は、それぞれ独立に下記式［２］または［３］で示される基を表す。）

（式中、破線は結合手を表す。）
６．２〜５のいずれかの重合性液晶組成物から得られる重合体、
７．２〜５のいずれかの重合性液晶組成物から得られる被膜、
８．２〜５のいずれかの重合性液晶組成物から得られる配向フィルム、
９．６の重合体または８の配向フィルムを備える光学部材、
１０．下記式［６］で表されることを特徴とする化合物

（式中、Ｙは−ＯＨまたは−ＣＯＯＨを表し、ｋは４〜１０の整数を表す。）
を提供する。That is, the present invention
1. A polymerizable liquid crystal compound represented by the following formula [1]:

(In the formula, X ¹ , X ² , X ³ and X ⁴ each independently represent a hydrogen atom or a fluorine atom, and R represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an alkoxy group, or an alkoxy group. Represents a carbonyl group, G represents a -C (= O) O- or -OC (= O)-group, and n represents an integer of 4 to 10.)
A polymerizable liquid crystal composition containing the polymerizable liquid crystal compound of 2.1,
3. Further, two polymerizable liquid crystal compositions containing a liquid crystal compound having one or more polymerizable groups in one molecule,
4). 3 polymerizable liquid crystal composition, wherein the liquid crystalline compound is a compound having one or more polymerizable groups represented by the following formula [2] or [3] in one molecule;

(In the formula, a broken line represents a bond.)
5. 3 or 4 polymerizable liquid crystal composition, wherein the liquid crystal compound is at least one selected from the group consisting of compounds represented by the following formulas [4] and [5]:

(In the formula, X represents a fluorine atom, a cyano group or a monovalent hydrocarbon group having 4 to 8 carbon atoms, f1 and f2 each independently represents an integer of 2 to 9, and g represents an integer of 2 to 9) And M ¹ , M ² and M ³ each independently represents a group represented by the following formula [2] or [3].)

(In the formula, a broken line represents a bond.)
A polymer obtained from the polymerizable liquid crystal composition according to any one of 6.2 to 5;
7.2 A film obtained from the polymerizable liquid crystal composition according to any one of 2 to 5,
8.2 An alignment film obtained from the polymerizable liquid crystal composition of any one of 2 to 5,
An optical member comprising a polymer of 9.6 or an oriented film of 8,
10. A compound represented by the following formula [6]

(In the formula, Y represents —OH or —COOH, and k represents an integer of 4 to 10).
I will provide a.

The polymerizable liquid crystal compound of the present invention and the composition containing the same provide not only excellent optical anisotropy but also a polymer having stable anisotropy and transparency in a high temperature environment.
The polymerizable liquid crystal compound of the present invention has an advantage that the tilt of optical anisotropy of a composition containing the polymerizable liquid crystal compound can be controlled with a small addition amount.
Therefore, a polymer obtained from the composition containing the polymerizable liquid crystal compound can be suitably used as an optically anisotropic film such as a polarizing plate or a retardation plate.

It is a figure which shows the retardation value angle dependence in wavelength 590nm of each film obtained in Examples 10-15 and the comparative example 1. FIG.

Terms used in this specification are as follows.
“Polymerizable liquid crystal compound” means a compound having a polymerizable portion such as an acrylic group or an α-methylene lactone ring and a liquid crystal structure portion in the molecule and exhibiting a liquid crystal phase. The “liquid crystal structure” means a structure having a spacer portion and a mesogen portion, which is generally used for representing liquid crystal molecules. “Liquid crystal composition” means a composition having a characteristic of exhibiting a liquid crystal phase. "Liquid crystallinity" means exhibiting a liquid crystal phase.
Hereinafter, the present invention will be described in more detail.

（式中、Ｘ¹、Ｘ²、Ｘ³およびＸ⁴は、互いに独立して、水素原子またはフッ素原子を表し、Ｒは、水素原子、ハロゲン原子、シアノ基、アルキル基、アルコキシ基、またはアルコキシカルボニル基を表し、Ｇは−Ｃ（＝Ｏ）Ｏ−または−ＯＣ（＝Ｏ）−基を表し、ｎは４〜１０の整数を表す。）[Polymerizable liquid crystal compound]
The polymerizable liquid crystal compound according to the present invention is represented by the following formula [1].

(In the formula, X ¹ , X ² , X ³ and X ⁴ each independently represent a hydrogen atom or a fluorine atom, and R represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an alkoxy group, or an alkoxy group. Represents a carbonyl group, G represents a -C (= O) O- or -OC (= O)-group, and n represents an integer of 4 to 10.)

The compound represented by the formula [1] is a polymerizable liquid crystal compound having a lactone ring and a liquid crystal structure site and having an α-methylene-γ-butyrolactone site.
α-Methylene-γ-butyrolactone is less influenced by steric hindrance among α-alkylidene-γ-butyrolactones having a polymerizable group, and can exhibit a very excellent effect of having high polymerizability. And it is effective in order to provide high Tg and heat resistance to the polymer obtained using this compound.

In the formula [1], the repeating part of the methylene group is a so-called spacer part. Here, n represents the number of repeating methylene groups, and is an integer of 4 to 10, preferably an integer of 4 to 6.
R in Formula [1] represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an alkoxy group, or an alkoxycarbonyl group.
Here, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. In the present invention, a fluorine atom is preferable.
The alkyl group may be linear, branched or cyclic, and the number of carbon atoms is not particularly limited, but in the present invention, a linear alkyl group having 1 to 10 carbon atoms is preferable.
Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, cyclobutyl group, n- Examples include a pentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, and an n-decyl group.

The alkyl group constituting the alkoxy group may be linear, branched or cyclic, and the carbon number is not particularly limited. In the present invention, the linear alkyl group having 1 to 10 carbon atoms is used. An alkoxy group having a group is preferred.
Specific examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, s-butoxy group, t-butoxy group, n-pentoxy group, and n-hexyl. An oxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, etc. are mentioned.

The alkyl group constituting the alkoxycarbonyl group may be linear, branched or cyclic, and the carbon number thereof is not particularly limited, but in the present invention, the linear alkyl group has 1 to 10 carbon atoms. Of these, an alkoxycarbonyl group having an alkyl group is preferred.
Specific examples of the alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, isobutoxycarbonyl group, s-butoxycarbonyl group, t-butoxycarbonyl. Group, n-pentoxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, n-nonyloxycarbonyl group, n-decyloxycarbonyl group and the like.
In the alkyl group, the alkoxy group, and the alkoxycarbonyl group, at least one of the hydrogen atoms may be further substituted with another substituent such as a halogen atom.

  As R, among the above substituents, a hydrogen atom, a halogen atom and an alkoxycarbonyl group are particularly preferable, and a hydrogen atom, a fluorine atom, and an alkoxycarbonyl group having a linear alkyl group having 1 to 5 carbon atoms are more preferable. .

  The polymerizable liquid crystal compound represented by the above formula [1] exhibits a liquid crystal phase such as a smectic phase or a nematic phase. This characteristic is useful in the field of application utilizing optical anisotropy such as a polarizing plate and a retardation plate.

Specific examples of the polymerizable liquid crystal compound include compounds represented by the following formulas (1) to (35), but are not limited thereto.

[Synthesis of polymerizable liquid crystal compound]
The polymerizable liquid crystal compound of the present invention can be synthesized by combining techniques in organic synthetic chemistry, and the synthesis method is not particularly limited.
A compound having an α-methylene-γ-butyrolactone structure is synthesized using, for example, a method proposed by Talaga et al. (P. Talaga, M. Schaeffer, C. Benezra and JL Stampf, Synthesis, 530 (1990)). Can do. As shown in the following synthesis scheme (A1), this method is a method of reacting 2- (bromomethyl) propenoic acid with aldehyde or ketone using SnCl _2. .
2- (Bromomethyl) acrylic acid can be obtained by a method proposed by Ramarajan et al. (K. Ramarajan, K. Kamalingam, DJ O'Donnell and KD Berlin, Organic Synthesis, vol. 61, 56-59 ( 1983)).

（式中、Ｒ'は一価の有機基を表し、Ａｍｂｅｒｌｙｓｔ（登録商標）１５は、ロームアンドハース社製イオン交換樹脂である。Ｅｔはエチル基を示す。）

(In the formula, R ′ represents a monovalent organic group, Amberlyst (registered trademark) 15 is an ion exchange resin manufactured by Rohm and Haas. Et represents an ethyl group.)

In the reaction of 2- (bromomethyl) acrylic acid using SnCl ₂ , an α-methylene-γ-butyrolactone structure can also be obtained by reaction with a corresponding acetal or ketal instead of an aldehyde or a ketone.
Examples of the acetal or ketal include compounds having a dimethyl acetal group, a diethyl acetal group, a 1,3-dioxane group, a 1,3-dioxolane group, and the like. A synthesis method and a protecting group in the case of using acetal or ketal are shown in the following synthesis scheme (A2).

（式中、Ｒ'は上記と同じ意味を表す。破線は結合手を表す。）

(In the formula, R ′ represents the same meaning as described above. The broken line represents a bond.)

  An intermediate for synthesizing the compound represented by the formula [1] can be synthesized by the method of the following synthesis scheme (B) or (C) applying the method of the above synthesis scheme (A1) or (A2). .

（式中、ｎは上記と同じ意味を表す。Ｍｅはメチル基を意味する。ＰＣＣはピリジニウムクロロクロマートを表す。）

(In the formula, n represents the same meaning as described above. Me represents a methyl group. PCC represents pyridinium chlorochromate.)

（式中、ｎは、上記と同じ意味を表す。）

(In the formula, n represents the same meaning as described above.)

  Next, as shown in the following synthesis scheme (D) or (E), the above intermediate and a phenolic compound are reacted to be esterified, whereby a polymerizable liquid crystal represented by the formula [1] A compound can be obtained.

（式中、ｎ、Ｘ¹〜Ｘ⁴およびＲは、上記と同じ意味を表す。ＤＣＣはジシクロヘキシルカルボジイミドを、ＤＭＡＰはＮ，Ｎ−ジメチル−４−アミノピリジンを表す。）

(In the formula, n, X ^{1 to} X ⁴ and R represent the same meaning as above. DCC represents dicyclohexylcarbodiimide, and DMAP represents N, N-dimethyl-4-aminopyridine.)

（式中、ｎ、Ｘ¹〜Ｘ⁴およびＲは、上記と同じ意味を表す。）

(In the formula, n, X ^{1 to} X ⁴ and R represent the same meaning as described above.)

[Polymerizable liquid crystal composition]
The polymerizable liquid crystal composition according to the present invention only needs to contain at least one polymerizable liquid crystal compound represented by the above formula [1], but in the polymerizable liquid crystal composition of the present invention, the formula [1 ] And a compound having a liquid crystal structure site (hereinafter referred to as a specific compound) are mixed to obtain a hybrid alignment film, so that the polymerizable liquid crystal represented by the formula [1] What contains at least 1 sort (s) of a compound and the said specific compound is suitable.
In addition, the specific compound to mix can also be used individually by 1 type or in combination of multiple types.

At this time, the specific compound may or may not have a polymerizable group such as an acryl group or a lactone ring. The specific compound having a polymerizable group may be monofunctional or polyfunctional.
Such a specific compound is a compound having no polymerizable group and exhibiting liquid crystallinity, a compound having a polymerizable group and exhibiting liquid crystallinity, and is a compound other than the polymerizable liquid crystal compound of the present invention.

（式中、破線は結合手を表す。）Examples of the polymerizable group that the specific compound may have include a group represented by the following formula [2] or [3].

(In the formula, a broken line represents a bond.)

（式中、Ｍ¹、Ｍ²およびＭ³は、それぞれ独立に上記式［２］または［３］で表される基である。Ｘはフッ素原子、シアノ基または炭素数４〜８の１価炭化水素基である。ｆ１およびｆ２はそれぞれ独立に２〜９の整数を表し、ｇは２〜９の整数を表す。）As the specific compound having a polymerizable group, a compound represented by the following formula [4] or [5] is particularly preferable.

(In the formula, M ¹ , M ² and M ³ are each independently a group represented by the above formula [2] or [3]. X is a fluorine atom, a cyano group or a monovalent group having 4 to 8 carbon atoms. (It is a hydrocarbon group. F1 and f2 each independently represents an integer of 2 to 9, and g represents an integer of 2 to 9.)

  The blending ratio of the specific compound is not particularly limited, but is 200 to 1,900 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound of the formula [1], preferably the polymerizable of the formula [1]. It is 400-900 mass parts with respect to 100 mass parts of liquid crystal compounds.

  Specific examples of the specific compound include compounds represented by the following formulas (36) to (126) described in WO06 / 115033 pamphlet and WO06 / 115112 pamphlet, and nematic liquid crystals. , Ferroelectric liquid crystals, and commercially available liquid crystal compositions, but are not limited thereto.

A photopolymerization initiator, a thermal polymerization initiator, a photosensitizer and the like can be added to the polymerizable liquid crystal composition of the present invention for the purpose of improving the polymerization reactivity.
Examples of the photopolymerization initiator include benzoin ethers such as benzoin methyl ether, acetophenones such as diethoxyacetophenone, and benzyl ketals such as benzyldimethyl ketal. The said photoinitiator can also be used individually by 1 type or in combination of multiple types.
The addition amount of the photopolymerization initiator is 100 mass of the total amount of the polymerizable liquid crystal compound represented by the formula [1] and the specific compound exhibiting liquid crystallinity (hereinafter, both are collectively referred to as a total liquid crystal compound). 5 parts by mass or less is preferable with respect to parts, and more preferably 0.5 to 2.0 parts by mass.

Examples of the thermal polymerization initiator include 2,2′-azobisisobutyronitrile. The thermal polymerization initiator can be used alone or in combination of two or more, and the addition amount thereof is preferably 5 parts by mass or less, more preferably 0.5-2. 0 parts by mass.
Examples of the photosensitizer include anthracene photosensitizers such as anthracene. The photosensitizer can be used alone or in combination of two or more, and the addition amount is preferably 5 parts by mass or less with respect to 100 parts by mass of the total liquid crystalline compounds.
The photopolymerization initiator can be used in combination with at least one of a thermal polymerization initiator and a photosensitizer.

A stabilizer may be added to the polymerizable liquid crystal composition of the present invention for the purpose of improving its storage stability.
Examples of the stabilizer include hydroquinone monoalkyl ethers such as hydroquinone and hydroquinone monomethyl ether, and 4-t-butylcatechol. The stabilizer can be used alone or in combination of two or more, and the addition amount is preferably 0.1 parts by mass or less with respect to 100 parts by mass of the total liquid crystal compounds.

In addition, an adhesion promoter may be added to the polymerizable liquid crystal composition of the present invention for the purpose of improving the adhesion to the substrate.
Examples of the adhesion promoter include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane; trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylvinylethoxysilane, diphenyldimethoxysilane, phenyl Alkoxysilanes such as triethoxysilane; silazanes such as hexamethyldisilazane, N, N′-bis (trimethylsilyl) urea, dimethyltrimethylsilylamine, trimethylsilylimidazole; vinyltrichlorosilane, γ-chloropropyltrimethoxysilane, γ- Aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysila Silanes such as γ- (N-piperidinyl) propyltrimethoxysilane; benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazole, thiouracil, mercapto Heterocyclic compounds such as imidazole and mercaptopyrimidine; urea compounds such as 1,1-dimethylurea and 1,3-dimethylurea; thiourea compounds and the like.
The adhesion promoter can be used alone or in combination of two or more, and the amount added is preferably 1 part by mass or less with respect to 100 parts by mass of the total liquid crystalline compound.

Furthermore, an organic solvent can be added to the polymerizable liquid crystal composition of the present invention for the purpose of adjusting the viscosity. In this case, liquid crystal properties may not be exhibited in a state containing an organic solvent.
Examples of the organic solvent include ethers such as tetrahydrofuran and dioxane; aromatic hydrocarbons such as benzene, toluene and xylene; polar solvents such as N, N-dimethylformamide and N-methyl-2-pyrrolidone; , Esters such as butyl acetate and ethyl lactate; methyl 3-methoxypropionate, methyl 2-methoxypropionate, ethyl 3-methoxypropionate, ethyl 2-methoxypropionate, ethyl 3-ethoxypropionate, 2-ethoxypropion Alkoxy esters such as ethyl acid; Glycol dialkyl ethers such as ethylene glycol dimethyl ether and propylene glycol dimethyl ether; Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol Diglycol dialkyl ethers such as tilethyl ether and dipropylene glycol dimethyl ether; glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether and propylene glycol monoethyl ether; diethylene glycol monomethyl ether and diethylene glycol Diglycol monoalkyl ethers such as monoethyl ether, dipropylene glycol monomethyl ether and dipropylene glycol monoethyl ether; glycol monoalkyl ether esters such as propylene glycol monomethyl ether acetate, carbitol acetate and ethyl cellosolve acetate; cyclohexanone, methyl ethyl Ketone, methyl isobutyl ketone and 2-heptanone. These organic solvents can be used alone or in combination of two or more.
Among these, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate and the like are preferable from the viewpoint of safety to the global environment and the working environment.
In addition, it is suitable that the usage-amount of an organic solvent shall be about 60-95 mass% in a polymeric liquid crystal composition.

In addition, a surfactant may be added to the polymerizable liquid crystal composition of the present invention for the purpose of improving the affinity with the substrate. The surfactant is not particularly limited, and examples thereof include a fluorine-based surfactant, a silicone-based surfactant, a nonionic surfactant, and the like, but a fluorine-based interface having a high effect of improving affinity with a substrate. An activator is preferred.
Specific examples of the above-mentioned fluorosurfactants (hereinafter referred to as trade names), EFTOP EF301, EF303, EF352 (manufactured by Tochem Products), MegaFuck F171, F173, R-30 (manufactured by DIC Corporation) ), FLORARD FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.) and the like. It is not limited. In addition, surfactant can also be used individually by 1 type or in combination of multiple types, and the addition amount is 5 mass parts or less with respect to 100 mass parts of total liquid crystalline compounds.

Preferred examples of the polymerizable liquid crystal composition of the present invention include 100 parts by mass of the polymerizable liquid crystal compound represented by the formula [1], 400 to 900 parts by mass of the specific compound exhibiting liquid crystallinity, and 5 parts by mass or less of the photoinitiator. However, the present invention is not limited to this.
The polymerizable liquid crystal composition described above can be suitably used as a composition for forming an orientation film or a coating solution.

The preparation method of the polymerizable liquid crystal composition of the present invention is not particularly limited, and each component constituting the polymerizable liquid crystal composition may be mixed at one time or sequentially. The order of adding the components in the sequential mixing is arbitrary.
In addition, when using multiple types of compounds for one component, the mixture which mixed them previously and other components may be mixed, and you may mix with another component separately, respectively.
The polymerizable liquid crystal composition of the present invention avoids unintentional induction of thermal polymerization in photopolymerization in a liquid crystal state and facilitates fixing of a uniform alignment state of molecules when producing an optical anisotropic body. It is preferable that the liquid crystal phase exhibits an entropy at room temperature (20 to 40 ° C., the same applies hereinafter). Further, when the polymerizable liquid crystal composition contains an organic solvent, it is preferable that an enantiomeric liquid crystal phase is exhibited at room temperature when the solvent is removed.

[Polymer and film]
A polymer can be obtained by subjecting the polymerizable liquid crystal composition of the present invention described above to light irradiation or heat treatment.
In addition, a film can be obtained by light irradiation treatment in a state where the polymerizable liquid crystal composition is sandwiched between two substrates, or in a state where the polymerizable liquid crystal composition is applied to the substrate by a spin coat method or a cast method. It is done.
At this time, a plastic sheet or film such as glass, quartz, a color filter, or triacetyl cellulose (TAC) can be used for the substrate. One of the two substrates is a belt on which a functional thin film such as ITO is formed, or a metal, such as glass, plastic sheet, plastic film or stainless steel, chromium or aluminum, is plated or vapor-deposited. Alternatively, it is possible to use a drum.

  For the purpose of improving the hybrid orientation of the resulting film, the substrate to be used is preferably subjected to an orientation treatment for obtaining a tilt. As an alignment treatment method, an alignment material containing a polyimide precursor, polyimide, polyvinyl cinnamate, etc. is applied, and an alignment treatment is performed by obliquely irradiating with rubbing or polarized ultraviolet rays, and an oblique deposition film of silicon dioxide is formed. Can be appropriately selected from known methods such as a method for forming an LB film and a method for forming an LB film.

In the method of sandwiching the polymerizable liquid crystal composition between two substrates, a cell in which a gap is formed between the two substrates by using a spacer or the like is produced, and a method using a capillary phenomenon, a pressure reduction of the gap in the cell, or the like. After injecting the polymerizable liquid crystal composition into the cell by the method, the light is irradiated to polymerize it.
As a simpler method, a polymerizable liquid crystal composition is placed on a substrate provided with a spacer and the like, and a cell is produced by stacking the other substrate on the substrate, and light is irradiated to polymerize the cell. There is also a method. At that time, the polymerizable liquid crystal composition may be fluidized, or may be fluidized by heating after being placed on the substrate. It is necessary to fluidize the liquid crystal composition.
In the method of sandwiching the polymerizable liquid crystal composition between two substrates, in order to obtain hybrid alignment, one of the substrates needs to be processed without alignment treatment or to obtain vertical alignment.

In the method of applying the polymerizable liquid crystal composition, a step of heating with a hot plate or the like may be added as needed during the step of applying the polymerizable liquid crystal composition and the step of polymerizing with light or heat. This step is particularly effective as a means for removing the organic solvent from the composition when a polymerizable liquid crystal composition (coating liquid) containing the organic solvent is used.
In any of the above methods, an oriented film having optical anisotropy can be obtained by polymerization in a state where the polymerizable liquid crystal composition exhibits a liquid crystal phase.

In order to obtain a polymer in a multi-domain state having different orientations for adjacent domains, a method of multi-domaining in a polymerization process or a method of multi-domaining a substrate is used.
The method of forming a multi-domain by a polymerization method is a method in which a polymerizable liquid crystal composition in a liquid crystal state is exposed to ultraviolet rays through a mask to form a polymerized domain, and the remaining domains are polymerized in an isotropic liquid state. Etc.
In addition, examples of the method of multi-domaining the substrate include a method of rubbing an alignment material formed on the substrate through a mask, and a method of irradiating ultraviolet rays through the mask.
By these methods, it is possible to obtain a multi-domained substrate in which the rubbed domain and the domain irradiated with ultraviolet rays are subjected to orientation treatment, and the others are untreated portions. The polymerizable liquid crystal composition formed on the multi-domained substrate is multi-domained under the influence of the alignment material layer.
In addition to the above alignment treatment method, a method using an electric field or a magnetic field may be used.

  By using the polymerizable liquid crystal composition of the present invention, a film having optical anisotropy can be obtained, and this film can be suitably used for a polarizing plate, a retardation plate and the like. Moreover, since this film has good transparency at high temperatures, it can be suitably used for electronic devices used in high-temperature environments such as in-vehicle display devices.

Hereinafter, although a synthesis example, an Example, and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to the following Example. In addition, the measurement method and measurement conditions of each physical property in the examples are as follows.
[1] NMR
The compound was dissolved in deuterated chloroform (CDCl ₃ ) or deuterated dimethyl sulfoxide (DMSO-d6), and ¹ H-NMR was measured using a nuclear magnetic resonance apparatus (300 MHz, manufactured by Diol).
[2] Observation of liquid crystal phase The liquid crystal phase is identified by heating the sample on a hot stage (MATS-2002S, manufactured by Tokai Hit) and using a polarizing microscope (manufactured by Nikon). It was. The phase transition temperature was measured using a differential scanning calorimeter (DSC3100SR, hereinafter referred to as DSC) manufactured by Bruker AXS Co., Ltd. under a scan rate of 10 ° C./min.
[3] Haze value The haze value of the film was measured using Tokyo Denshoku Spectral Haze Meter (TC-1800H).
[4] Retardation value of film The retardation value of wavelength 590nm was measured using the retardation measuring apparatus (RETS-100, Otsuka Electronics Co., Ltd. product).
[5] Average Tilt Angle of Film The average tilt angle at a wavelength of 590 nm was measured using an AxoScan ^™ Mueller Matrix Polarimeter (manufactured by AXOMETRIX).

[Synthesis Example 1] Synthesis of polymerizable liquid crystal compound (E1) [1] Synthesis of intermediate compound (A1)

In a 500 mL eggplant flask equipped with a condenser tube, 9.8 g (50.0 mmol) of 4-cyano-4′-hydroxybiphenyl, 7.0 g (50.0 mmol) of 3-bromo-1-propanol, and 13.8 g (100 mmol) of potassium carbonate. , And 150 mL of acetone were added to form a mixture, which was reacted at 64 ° C. with stirring for 48 hours. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain a yellow wet solid. Thereafter, this solid and 140 mL of water were mixed, and 100 mL of diethyl ether was added thereto for extraction. Extraction was performed three times. The separated organic layer was dried by adding anhydrous magnesium sulfate, filtered, and then the solvent was distilled off under reduced pressure to obtain a yellow solid. This solid was purified by recrystallization using a mixed solvent of hexane / ethyl acetate = 2/1 (v / v) to obtain 8.7 g of a white solid. The NMR measurement result of this solid is shown below. From this result, it was confirmed that this white solid is an intermediate compound (A1) (yield 70%).
¹ H-NMR (CDCl ₃ ) δ: 2.09 (m, 2H), 3.90 (t, 2H), 4.20 (t, 2H), 6.99 (d, 2H), 7.52 (d, 2H), 7.66 (m, 4H )

[2] Synthesis of polymerizable liquid crystal compound (E1)

12.0 g of the intermediate compound (A1) obtained above was dissolved in 40 mL of tetrahydrofuran (THF) together with 7.7 mL of triethylamine and a small amount of BHT (2,6-di-tert-butyl-p-cresol) and brought to room temperature. Then, a solution obtained by dissolving 4.6 mL of acryloyl chloride in 40 mL of THF was added dropwise over 15 minutes while cooling with a water bath. After dropping, the mixture was stirred for 30 minutes, and the water bath was removed, and stirring was continued overnight while returning to room temperature, and the precipitated triethylamine hydrochloride was filtered. About 3/4 of THF was distilled off from the obtained filtrate, 50 mL of methylene chloride was added, and the organic layer was washed successively with 50 mL of saturated aqueous sodium bicarbonate, 50 mL of 0.5 mol / L hydrochloric acid, and 50 mL of saturated brine. After drying with magnesium sulfate, the solvent was distilled off to obtain a product. After recrystallization from ethanol, 6.0 g of a polymerizable liquid crystal compound (E1) was obtained.
¹ H-NMR (CDCl ₃ ) δ: 2.20 (m, 2H), 4.10 (t, 2H), 4.40 (t, 2H), 5.81 (d, 1H), 6.15 (m, 1H), 6.41 (d, 1H ), 6.99 (d, 2H), 7.55 (d, 2H), 7.66 (m, 4H)

[Synthesis Example 2] Synthesis of polymerizable liquid crystal compound (E2) [1] Synthesis of intermediate compound (A2)

In a 100 mL eggplant flask equipped with a condenser tube, 5.0 g (25.6 mmol) of 4-cyano-4′-hydroxybiphenyl, 4.6 g (25.6 mmol) of 6-bromo-1-hexanol, 7.0 g (50 mmol) of potassium carbonate. And acetone (50 mL) were added to form a mixture, which was reacted at 64 ° C. with stirring for 24 hours. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain a yellow wet solid. Then, this solid and 70 mL of water were mixed, and 50 mL of diethyl ether was added and extracted. Extraction was performed three times.
The separated organic layer was dried by adding anhydrous magnesium sulfate, filtered, and then the solvent was distilled off under reduced pressure to obtain a yellow solid. This solid was dissolved in 3 mL of ethyl acetate and purified by silica gel column chromatography (column: silica gel 60, 0.063-0.200 mm, manufactured by Merck, eluent: hexane / ethyl acetate = 1/1 (v / v)). did. The solvent was distilled off from the resulting solution to obtain 6.9 g of a white solid. The NMR measurement result of this solid is shown below. From this result, it was confirmed that this white solid was an intermediate compound (A2) (yield 91%).
¹ H-NMR (DMSO-d6) δ: 1.26 (m, 6H), 1.69 (m, 2H), 3.37 (t, 2H), 4.03 (t, 2H), 7.06 (d, 2H), 7.69 (d, 2H), 7.85 (m, 4H)

[2] Synthesis of intermediate compound (B2)

Next, 2.95 g of the intermediate compound (A2) obtained above was added to a 200 mL three-necked flask equipped with a cooling tube while adding 2.2 g (10.0 mmol) of PCC and 30.0 mL of CH ₂ Cl ₂ and stirring and mixing them. A solution prepared by dissolving (10.0 mmol) in 50.0 mL of CH ₂ Cl ₂ was added dropwise and further stirred at 40 ° C. for 0.5 hour. Thereafter, 90 mL of diethyl ether was added to the solution excluding the oily substance adhering to the wall of the flask and filtered under reduced pressure, and then the solvent was distilled off under reduced pressure to obtain a dark green wet solid.
This solid was dissolved in 3 mL of ethyl acetate and purified by silica gel column chromatography (column: silica gel 60, 0.063-0.200 mm, manufactured by Merck, eluent: hexane / ethyl acetate = 1/1 (v / v)). . The solvent of the obtained solution was distilled off to obtain 2.8 g of a colorless solid. The NMR measurement result of this solid is shown below. From this result, it was confirmed that this colorless solid was an intermediate compound (B2) (yield 93%).
¹ H-NMR (CDCl ₃ ) δ: 1.84 (m, 6H), 2.50 (m, 2H), 4.02 (m, 2H), 6.99 (d, 2H), 7.53 (d, 2H), 7.91 (m, 4H ), 9.80 (s, 1H)

[3] Synthesis of polymerizable liquid crystal compound (E2)

Finally, in a 50 mL eggplant flask equipped with a cooling tube, 3.0 g (10.0 mmol) of the intermediate compound (B2) obtained above, 1.65 g (10.0 mmol) of 2- (bromomethyl) acrylic acid, Amberlyst (registered) 1.6 g of THF, 16.0 mL of THF, 1.9 g (10.0 mmol) of tin (II) chloride, and 4.0 mL of pure water were added to form a mixture, and the mixture was reacted by stirring at 70 ° C. for 7 hours. After completion of the reaction, the reaction solution was filtered under reduced pressure and mixed with 30 mL of pure water, and 50 mL of diethyl ether was added thereto for extraction. Extraction was performed three times.
The organic layer after extraction was dried by adding anhydrous magnesium sulfate, and the solvent was distilled off from the solution after filtration under reduced pressure to obtain a yellow solid. This solid was dissolved in 2 mL of ethyl acetate and purified by silica gel column chromatography (column: silica gel 60, 0.063-0.200 mm, manufactured by Merck, eluent: hexane / ethyl acetate = 2/1 (v / v)). did. The solvent of the obtained solution was distilled off to obtain 1.5 g of a white solid. The NMR measurement result of this solid is shown below. From this result, it was confirmed that this white solid was the target polymerizable liquid crystal compound (E2) (yield 41%).
¹ H-NMR (CDCl ₃ ) δ: 1.57 (m, 6H), 1.85 (m, 2H), 2.60 (m, 1H), 3.05 (m, 1H), 4.01 (t, 2H), 4.54 (m, 1H ), 5.63 (m, 1H), 6.23 (m, 1H), 7.00 (d, 2H), 7.52 (d, 2H), 7.68 (m, 4H)
As a result of observing the liquid crystal properties of this polymerizable liquid crystal compound (E2), it became an isotropic liquid state at 84 ° C., and transitioned to a liquid crystal phase (nematic phase) at 61 ° C. when the temperature decreased.

[Synthesis Example 3] Synthesis of polymerizable liquid crystal compound (E3) [1] Synthesis of intermediate compound (A3)

In a 200 mL eggplant flask with a condenser tube, methyl 4-hydroxybenzoate (7.61 g, 50.0 mmol), 6-bromo-1-hexanol (9.1 g, 50.0 mmol), potassium carbonate (13.8 g, 100 mmol), and acetone 70 mL was added to make a mixture, and the mixture was reacted at 64 ° C. with stirring for 24 hours. After completion of the reaction, the reaction solution was filtered under reduced pressure, and the solvent was distilled off under reduced pressure to obtain a yellow wet solid. This solid was purified by silica gel column chromatography (column: silica gel 60, 0.063-0.200 mm, manufactured by Merck, eluent: hexane / ethyl acetate = 1/1 (v / v)). The solvent was distilled off from the resulting solution to obtain 11.3 g of a white solid. The NMR measurement result of this solid is shown below. From this result, it was confirmed that this white solid was an intermediate compound (A3) (yield 90%).
¹ H-NMR (CDCl ₃ ) δ: 1.3-1.7 (m, 8H), 3.67 (m, 2H), 3.88 (s, 3H), 4.03 (t, 2H), 6.91 (d, 2H), 7.99 (d , 2H)

[2] Synthesis of intermediate compound (B3)

Next, in a 100 mL three-necked flask equipped with a condenser tube, 2.2 g (10.0 mmol) of PCC and 15.0 mL of CH ₂ Cl ₂ were added and stirred and mixed. A solution prepared by dissolving 5 g (10.0 mmol) in 15.0 mL of CH ₂ Cl _{2 was} added dropwise, and the mixture was further stirred at room temperature for 6 hours. Thereafter, 90 mL of diethyl ether was added to the solution excluding the oily substance adhering to the flask wall and filtered under reduced pressure, and then the solvent was distilled off under reduced pressure to obtain a dark green wet solid.
This solid was purified by silica gel column chromatography (column: silica gel 60, 0.063-0.200 mm, manufactured by Merck & Co., eluent: hexane / ethyl acetate = 2/1 (v / v)). The solvent of the obtained solution was distilled off to obtain 1.3 g of a colorless solid. The result of having measured this solid by NMR is shown below. From this result, it was confirmed that this colorless solid was an intermediate compound (B3) (yield 50%).
¹ H-NMR (CDCl ₃ ) δ: 1.3-1.8 (m, 6H), 2.49 (t, 2H), 3.88 (s, 3H), 3.99 (t, 2H), 6.87 (d, 2H), 7.99 (d , 2H), 9.78 (s, 1H)

[3] Synthesis of intermediate compound (C3)

Next, 1.25 g (5.0 mmol) of the intermediate compound (B3) obtained above, 0.83 g (5.0 mmol) of 2- (bromomethyl) acrylic acid, Amberlyst (registered) Trademark) 15 (0.8 g), THF 8.0 mL, tin (II) chloride 0.95 g (5.0 mmol), and pure water 2.0 mL were added to form a mixture, and the mixture was reacted by stirring at 70 ° C. for 5 hours. After completion of the reaction, the reaction solution was filtered under reduced pressure and mixed with 40 mL of pure water, and 50 mL of diethyl ether was added thereto for extraction. Extraction was performed three times.
The organic layer after extraction was dried by adding anhydrous magnesium sulfate, and the solvent was distilled off from the solution after filtration under reduced pressure to obtain 1.5 g of a colorless solid. The NMR measurement result of this solid is shown below. From this result, it was confirmed that this colorless solid was an intermediate compound (C3) (yield 94%).
¹ H-NMR (DMSO-d6) δ: 1.3-1.8 (m, 8H), 2.62 (m, 1H), 3.04 (s, 1H), 3.81 (s, 3H), 4.05 (t, 2H), 4.54 ( m, 1H), 5.70 (s, 1H), 6.01 (s, 1H), 7.03 (d, 2H), 7.89 (d, 2H)

[4] Synthesis of intermediate compound (D3)

To a 100 mL eggplant flask equipped with a condenser tube, 35 mL of ethanol, 1.5 g (4.7 mmol) of the intermediate compound (C3) obtained above, and 5 mL of a 10% by mass aqueous sodium hydroxide solution were added to form a mixture. The reaction was allowed to stir for an hour. After completion of the reaction, 300 mL of water and the reaction solution were added to a 500 mL beaker, and the mixture was stirred for 30 minutes at room temperature. Then, 5 mL of a 10% by mass aqueous HCl solution was added dropwise, followed by filtration to obtain 1.3 g of a white solid.
Next, 1.1 g of the obtained white solid, 1.0 g of Amberlyst (registered trademark) 15 and 20.0 mL of THF were added to a 50 mL eggplant flask equipped with a cooling tube to form a mixture, and the reaction was stirred at 70 ° C. for 5 hours. I let you. After completion of the reaction, the solvent was distilled off from the solution after filtering the reaction solution under reduced pressure to obtain a yellow solid. The yellow solid was purified by recrystallization (hexane / ethyl acetate = 1/1 (v / v)) to obtain 0.9 g of a white solid. The NMR measurement result of this solid is shown below. From this result, it was confirmed that this white solid is an intermediate compound (D3) (yield 71%).
¹ H-NMR (DMSO-d6) δ: 1.2-1.8 (m, 8H), 2.60 (m, 1H), 3.09 (m, 1H), 4.04 (m, 2H), 4.55 (m, 1H), 5.69 ( s, 1H), 6.02 (s, 1H), 6.99 (d, 2H), 7.88 (d, 2H), 12.5 (s, broad, 1H)

[5] Synthesis of compound (P3)

19.2 g (138.0 mmol) of 3-bromo-1-propanol was dissolved in 100 mL of THF together with 18.9 mL of triethylamine and a small amount of BHT, stirred at room temperature, and 12.2 mL (150 mmol) dissolved in 50 mL of THF under cooling with a water bath. ) Acryloyl chloride was added dropwise over 15 minutes and stirred for 30 minutes, and the water bath was removed and stirring was continued overnight while returning to room temperature. The precipitated TEA hydrochloride was filtered, THF was distilled off from the filtrate, 100 mL of diethyl ether was added, and the organic layer was successively added to each 80 mL saturated aqueous sodium bicarbonate solution, 0.5 mol / L hydrochloric acid, and saturated brine. After washing with magnesium sulfate, the solvent was distilled off to obtain 18.2 g of Compound (P3). The result of having measured this solid by NMR is shown below.
¹ H-NMR (CDCl ₃ ) δ: 2.20 (m, 2H), 3.45 (t, 2H), 4.33 (t, 2H), 5.84 (d, 1H), 6.13 (m, 1H), 6.44 (d, 1H )

[6] Synthesis of intermediate compound (G3)

To a 500 mL eggplant flask equipped with a cooling cabinet, 17.6 g (94.3 mmol) of biphenol, 18.2 g (94.3 mmol) of compound (P3), 24.0 g (190 mmol) of potassium carbonate, and 250 mL of acetone were added to form a mixture, and the temperature was The reaction was carried out with stirring at 54 ° C. for 20 hours. After completion of the reaction, the reaction solution was filtered under reduced pressure, and the solvent was distilled off under reduced pressure to obtain a yellow wet solid. This solid was purified by column chromatography (column: silica gel 60, 0.063-0.200 mm, manufactured by Merck & Co., eluent: hexane / ethyl acetate = 2/1 (v / v)). The solvent was distilled off from the solution obtained here to obtain 6.1 g of a white solid. The result of having measured this solid by NMR is shown below. From this result, it was confirmed that this white solid was an intermediate compound (G3) (yield 22%).
¹ H-NMR (CDCl ₃ ) δ: 2.21 (m, 2H), 4.13 (t, 2H), 4.40 (t, 2H), 4.99 (s, 1H), 5.87 (d, 1H), 6.15 (m, 1H ), 6.40 (d, 1H), 6.87 (d, 2H), 6.99 (d, 2H), 7.46 (m, 4H)

[7] Synthesis of polymerizable liquid crystal compound (E3)

6.1 g (20.0 mmol) of the intermediate compound (D3) obtained above, 6.0 g (20.0 mmol) of the intermediate compound (G3), 0.08 g of DMAP, and a small amount of BHT were stirred at room temperature with chlorination. After DCC 4.7 g (23.0 mmol) suspended in 10 mL of methylene and dissolved in 20 mL of methylene chloride was added thereto and stirred overnight, the precipitated DCC urea was filtered off, and the filtrate was sequentially added to each 60 mL of 0 mL. Washed twice with 5 mol / L hydrochloric acid, saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over magnesium sulfate, evaporated to remove the solvent, and recrystallized with ethanol to obtain a polymerizable liquid crystal compound (E3) 8. 8 g was obtained (yield 75%).
¹ H-NMR (CDCl ₃ ) δ: 1.53 (m, 6H), 1.81 (m, 2H), 2.20 (m, 2H), 2.60 (m, 1H), 3.07 (m, 1H), 4.06 (t, 2H ), 4.12 (t, 2H), 4.40 (t, 2H), 4.54 (m, 1H), 5.63 (d, 1H), 5.85 (d, 1H), 6.10 (m, 1H), 6.24 (d, 1H) , 6.42 (d, 1H), 6.97 (d, 2H), 7.25 (m, 2H), 7.54 (m, 2H), 7.59 (m, 2H), 8.17 (d, 2H)
As a result of observing the liquid crystal phase of the polymerizable liquid crystal compound (E3), at the time of temperature rise, the phase transitioned to the smectic X phase at 109 ° C., the phase transition to the nematic phase at 144 ° C., and the isotropic liquid state at 168 ° C. It became.

[Example 1] Synthesis of compound (Z1) [1] Synthesis of intermediate compound (P1)

In a 200 mL eggplant flask with a condenser tube, 12.1 g (50.0 mmol) of 4- (4-hydroxyphenyl) benzoic acid ethyl ester, 11-bromo-1-undecanol, 12. 5 g (50.0 mmol), potassium carbonate 13.8 g (100 mmol), and acetone 100 mL were added to form a mixture, and the mixture was reacted at 64 ° C. with stirring for 24 hours. After completion of the reaction, the reaction solution was poured into 300 mL of pure water to obtain 20.3 g of a white solid. The result of having measured this solid by NMR is shown below. From this result, it was confirmed that this white solid was an intermediate compound (P1) (yield 98%).
¹ H-NMR (CDCl ₃ ) δ: 1.3-1.7 (m, 19H), 1.81 (m, 2H), 3.67 (m, 2H), 4.02 (m, 2H), 4.42 (t, 2H), 6.97 (d , 2H), 7.57 (d, 2H), 7.62 (d, 2H), 8.09 (d, 2H)

[2] Synthesis of intermediate compound (Q1)

Next, in a 500 mL three-necked flask equipped with a condenser tube, 11 g (51 mmol) of PCC and 100 mL of CH ₂ Cl ₂ were stirred and mixed, and 20 g (49 mmol) of the intermediate compound (P1) obtained above was added to CH ₂ Cl ₂ A solution dissolved in 100 mL was added dropwise and further stirred at room temperature for 5 hours. Thereafter, 100 mL of diethyl ether was added to the solution excluding the oily substance adhering to the wall of the flask and filtered under reduced pressure, and then the solvent was distilled off under reduced pressure to obtain a dark green wet solid.
This solid was purified by silica gel column chromatography (column: silica gel 60, 0.063-0.200 mm, manufactured by Merck & Co., eluent: ethyl acetate). The solvent of the obtained solution was distilled off to obtain 12.4 g of a colorless solid. The result of having measured this solid by NMR is shown below. From this result, it was confirmed that this colorless solid was intermediate compound (Q1) (yield 62%).
¹ H-NMR (CDCl ₃ ) δ: 1.20-1.65 (m, 19H), 1.81 (m, 2H), 2.41 (t, 2H), 4.11 (t, 2H), 4.42 (m, 2H), 6.99 (d , 2H), 7.57 (d, 2H), 7.63 (d, 2H), 8.01 (d, 2H), 9.77 (s, 1H)

[3] Synthesis of intermediate compound (R1)

Next, 12.4 g (30 mmol) of the intermediate compound (Q1) obtained above, 5.4 g (33 mmol) of 2- (bromomethyl) acrylic acid, 75 mL of THF, and tin (II) chloride were added to a 200 mL eggplant flask equipped with a cooling tube. 6.3 g (33 mmol) and 10 mL of a 10% by mass aqueous HCl solution were added to form a mixture, which was stirred at 70 ° C. for 24 hours for reaction. After completion of the reaction, the reaction solution was poured into 300 mL of pure water to obtain 15 g of a white solid. The result of having measured this solid by NMR is shown below. From this result, it was confirmed that this white solid was the target intermediate compound (R1).
¹ H-NMR (CDCl ₃ ) δ: 1.30 (m, 12H), 1.41 (t, 3H), 1.47 (m, 12H), 1.58 (m, 2H), 1.81 (m, 2H), 2.54 (m, 1H ), 3.06 (m, 1H), 4.13 (m, 2H), 4.48 (m, 2H), 4.55 (m, 1H), 5.66 (s, 1H), 6.23 (s, 1H), 7.00 (d, 2H) , 7.55 (d, 2H), 7.66 (d, 2H), 8.11 (d, 2H)

[4] Synthesis of compound (Z1)

To a 500 mL eggplant flask equipped with a condenser tube, 200 mL of ethanol, 15 g of the intermediate compound (R1) obtained above, and 80 mL of 10% by mass aqueous sodium hydroxide solution were added to form a mixture, and the mixture was reacted at 85 ° C. with stirring for 5 hours. . After completion of the reaction, 500 mL of water and the reaction solution were added to a 1,000 mL beaker and stirred at room temperature for 30 minutes, and then 50 mL of a 10% by mass aqueous HCl solution was added dropwise, followed by filtration to obtain a white solid.
Next, the obtained white solid, 200 mL of THF, and a 10% by mass HCl aqueous solution were added to a 50 mL eggplant flask with a condenser tube to form a mixture, and the mixture was stirred at 70 ° C. for 5 hours to be reacted. After completion of the reaction, 500 mL of water and a reaction solution were added to a 1,000 mL beaker and filtered to obtain 12 g of a white solid. The result of having measured this solid by NMR is shown below. From this result, it was confirmed that this white solid was the target compound (Z1) (yield 89%, yield from Q1).
¹ H-NMR (DMSO-d6) δ: 1.32 (m, 14H), 1.57 (m, 2H), 1.71 (m, 2H), 2.54 (m, 1H), 3.09 (m, 1H), 4.01 (m, 2H), 4.55 (m, 1H), 5.69 (s, 1H), 6.02 (s, 1H), 7.05 (d, 2H), 7.67 (d, 2H), 7.73 (d, 2H), 7.97 (d, 2H ), 12.89 (s, broad, 1H)

[Example 2] Synthesis of compound (Z2) [1] Synthesis of intermediate compound (P2)

In a 500 mL eggplant flask equipped with a condenser tube, 15.0 g (72 mmol) of ethyl 4- (4-hydroxyphenyl) benzoate, 17.4 g (50.0 mmol) of 4-bromobutyl-1,3-dioxolane, 19.3 g of potassium carbonate ( 140 mmol), and 200 mL of acetone were added to form a mixture, which was reacted at 64 ° C. for 48 hours with stirring. After completion of the reaction, the reaction solution was poured into 500 mL of pure water to obtain 26.1 g of a white solid. The result of having measured this solid by NMR is shown below. From this result, it was confirmed that this white solid was an intermediate compound (P2) (yield 98%).
¹ H-NMR (CDCl ₃ ) δ: 1.41 (t, 3H), 1.55-2.00 (m, 6H), 3.86 (m, 2H), 3.99 (m, 4H), 4.39 (m, 2H), 4.89 (m , 1H), 6.97 (d, 2H), 7.61 (m, 4H), 8.07 (d, 2H)

[2] Synthesis of intermediate compound (R2)

Next, 18.5 g (50 mmol) of the intermediate compound (P2) obtained above, 9.1 g (55 mmol) of 2- (bromomethyl) acrylic acid, 114 mL of THF, and tin (II) chloride were added to a 300 mL eggplant flask equipped with a cooling tube. 10.4 g (55 mmol) and 36 mL of a 10% by mass aqueous HCl solution were added to form a mixture, and the reaction was stirred at 70 ° C. for 20 hours. After completion of the reaction, the reaction solution was poured into 500 mL of pure water to obtain 18.7 g of a white solid. The result of having measured this solid by NMR is shown below. From this result, it was confirmed that this colorless solid was an intermediate compound (R2) (yield 95%).
¹ H-NMR (CDCl ₃ ) δ: 1.42 (t, 3H), 1.60-1.95 (m, 6H), 2.64 (m, 1H), 3.11 (s, 1H), 4.03 (t, 2H), 4.42 (m , 2H), 4.58 (m, 1H), 5.64 (s, 1H), 6.24 (s, 1H), 6.99 (d, 2H), 7.63 (m, 4H), 8.12 (d, 2H)

[3] Synthesis of compound (Z2)

To a 500 mL eggplant flask equipped with a condenser tube, 200 mL of ethanol, 18.7 g (47 mmol) of the intermediate compound (R2) obtained above, and 50 mL of 10% by mass aqueous sodium hydroxide solution were added to form a mixture, and the mixture was stirred at 85 ° C. for 5 hours. While reacting. After completion of the reaction, water (600 mL) and the reaction solution were added to a 1,000 mL beaker, stirred for 30 minutes at room temperature, and then filtered to obtain a white solid.
Next, the obtained white solid, 200 mL of THF, and 50 mL of 10% by mass HCl aqueous solution were added to a 500 mL eggplant flask equipped with a cooling tube to form a mixture, and the mixture was reacted by stirring at 70 ° C. for 5 hours. After completion of the reaction, the reaction solution was poured into 500 mL of pure water to obtain 15.9 g of a white solid. The result of having measured this solid by NMR is shown below. From this result, it was confirmed that this white solid was the target compound (Z2) (yield 92%).
¹ H-NMR (DMSO-d6) δ: 1.50 (m, 2H), 1.75 (m, 4H), 2.58 (m, 1H), 3.12 (m, 1H), 4.04 (m, 2H), 4.59 (m, 1H), 5.72 (s, 1H), 6.03 (s, 1H), 7.04 (d, 2H), 7.76 (m, 4H), 7.97 (d, 2H), 12.91 (s, broad, 1H)

[Example 3] Synthesis of polymerizable liquid crystal compound (Z3)

1.0 g (2.7 mmol) of the compound (Z2) obtained in Example 2, 0.3 g (3.1 mmol) of phenol, 0.010 g of DMAP, and a small amount of BHT were suspended in 20 mL of methylene chloride at room temperature with stirring. A solution in which 0.7 g (3.5 mmol) of DCC was dissolved in 5 mL of methylene chloride was added thereto and stirred overnight. The precipitated DCC urea was filtered off, and the filtrate was washed twice with 50 mol of 0.5 mol / L hydrochloric acid, 50 mL of saturated aqueous sodium hydrogen carbonate solution and 50 mL of saturated brine successively, dried over magnesium sulfate, and the solvent was removed. Distilled off and purified by recrystallization with ethanol to obtain 0.4 g of the target polymerizable liquid crystal compound (Z3) (yield 36%).
¹ H-NMR (CDCl ₃ ) δ: 1.6-1.9 (m, 6H), 2.63 (m, 1H), 3.07 (m, 1H), 4.06 (t, 2H), 4.57 (m, 1H), 5.64 (d , 1H), 6.24 (d, 1H), 6.99 (d, 2H), 7.24 (d, 3H), 7.45 (m, 2H), 7.59 (m, 2H), 7.71 (m, 2H), 8.25 (d, 2H)
As a result of observing the liquid crystal phase of the polymerizable liquid crystal compound (Z3), at the time of temperature increase, the liquid crystal phase changed to a smectic phase at 101 ° C., changed to a nematic phase at 114 ° C., and thermally polymerized at 122 ° C.

[Example 4] Synthesis of polymerizable liquid crystal compound (Z4)

Compound (Z2) 2.0 g (5.5 mmol) obtained in Example 2, Compound (Q4) (methyl 4-hydroxybenzoate, manufactured by Tokyo Chemical Industry Co., Ltd.) 0.9 g (6.0 mmol), DMAP0 0.005 g and a small amount of BHT were suspended in 25 mL of methylene chloride under stirring at room temperature, and a solution of 1.4 g (7.0 mmol) of DCC dissolved in 5 mL of methylene chloride was added thereto and stirred overnight. The precipitated DCC urea was filtered off, and the filtrate was washed twice with 50 mol of 0.5 mol / L hydrochloric acid, 50 mL of saturated aqueous sodium hydrogen carbonate solution and 50 mL of saturated brine successively, dried over magnesium sulfate, and the solvent was removed. Distilled off and purified by recrystallization with ethanol to obtain 2.1 g of the target polymerizable liquid crystal compound (Z4) (76% yield).
¹ H-NMR (CDCl ₃ ) δ: 1.60 to 1.95 (m, 6H), 2.61 (m, 1H), 3.07 (m, 1H), 3.98 (s, 3H), 4.01 (t, 2H), 4.54 (m , 1H), 5.64 (d, 1H), 6.25 (d, 1H), 6.99 (d, 2H), 7.26 (d, 2H), 7.62 (m, 2H), 7.71 (m, 2H), 8.15 (d, 2H), 8.24 (d, 2H)
In addition, as a result of observing the liquid crystal phase of the polymerizable liquid crystal compound (Z4), the phase transitioned to the smectic phase at 105 ° C. during the temperature increase, and thermal polymerization was performed at 130 ° C.

[Example 5] Synthesis of polymerizable liquid crystal compound (Z5)

Compound (Z1) 3.0 g (6.7 mmol) obtained in Example 1, Compound (Q5) (2,3-difluorophenol, manufactured by Tokyo Chemical Industry Co., Ltd.) 0.9 g (6.7 mmol), DMAP0 .05 g and a small amount of BHT were suspended in 30 mL of methylene chloride under stirring at room temperature, and a solution of 1.9 g (9.0 mmol) of DCC dissolved in 10 mL of methylene chloride was added and stirred overnight. The precipitated DCC urea was filtered off, and the filtrate was washed twice with 50 mol of 0.5 mol / L hydrochloric acid, 50 mL of saturated aqueous sodium hydrogen carbonate solution and 50 mL of saturated brine successively, dried over magnesium sulfate, and the solvent was removed. Distilled off and purified by recrystallization with ethanol to obtain 2.9 g of the target polymerizable liquid crystal compound (Z5) (yield 77%).
¹ H-NMR (CDCl ₃ ) δ: 1.25-1.95 (m, 18H), 2.55 (m, 1H), 3.08 (m, 1H), 4.04 (t, 2H), 4.54 (m, 1H), 5.62 (d , 1H), 6.23 (d, 1H), 6.99 (d, 2H), 7.13 (m, 3H), 7.62 (m, 2H), 7.72 (m, 2H), 8.23 (d, 2H)
In addition, as a result of observing the liquid crystal phase of the polymerizable liquid crystal compound (Z5), the phase transitioned to the smectic A phase at 91 ° C. at the time of temperature rise, and an isotropic liquid state was obtained at 106 ° C.

[Example 6] Synthesis of polymerizable liquid crystal compound (Z6) [1] Synthesis of intermediate compound (Q6)

In a 100 mL eggplant flask equipped with a condenser tube, 5.0 g (32 mmol) of compound (P6) (2-fluoro-4-hydroxybenzoic acid, manufactured by Tokyo Chemical Industry Co., Ltd.), 50 ml (55 mmol) of n-butanol, and 2 mL of sulfuric acid were added. The mixture was added and stirred at 105 ° C. for 2 hours for reaction. After completion of the reaction, the reaction solution was poured into 500 mL of pure water, and extracted with 100 mL of diethyl ether. To the organic layer after extraction, anhydrous magnesium sulfate was added and dried, and the solvent was distilled off from the solution after filtration under reduced pressure to obtain 6.6 g of a white solid. The result of having measured this solid by NMR is shown below. From this result, it was confirmed that this solid was an intermediate compound (Q6) (yield 97%).
¹ H-NMR (CDCl ₃ ) δ: 0.98 (t, 3H), 1.47 (m, 2H), 1.74 (m, 2H), 4.32 (m, 2H), 6.27 (s, 1H), 6.47 (m, 2H ), 7.88 (m, 1H)

[2] Synthesis of polymerizable liquid crystal compound (Z6)

2.3 g (5.0 mmol) of the compound (Z1) obtained in Example 1, 1.1 g (5.0 mmol) of the intermediate compound (Q6) obtained above, 0.040 g of DMAP, and a small amount of BHT were mixed at room temperature. The mixture was suspended in 20 mL of methylene chloride with stirring at, and a solution of 1.4 g (7.0 mmol) of DCC dissolved in 5 mL of methylene chloride was added thereto and stirred overnight. The precipitated DCC urea was filtered off, and the filtrate was washed twice with 50 mol of 0.5 mol / L hydrochloric acid, 50 mL of saturated aqueous sodium hydrogen carbonate solution and 50 mL of saturated brine successively, dried over magnesium sulfate, and the solvent was removed. Distilled off and purified by recrystallization with ethanol to obtain 2.5 g of the target polymerizable liquid crystal compound (Z6) (yield 76%).
¹ H-NMR (CDCl ₃ ) δ: 1.15 (t, 3H), 1.25-1.90 (m, 22H), 2.56 (m, 1H), 3.10 (m, 1H), 4.05 (t, 2H), 4.37 (t , 2H), 4.56 (m, 1H), 5.63 (d, 1H), 6.24 (d, 1H), 7.02 (d, 2H), 7.14 (m, 2H), 7.60 (d, 2H), 7.72 (d, 2H), 8.05 (m, 1H), 8.23 (d, 2H)
As a result of observing the liquid crystal phase of the polymerizable liquid crystal compound (Z6), the phase transitioned to the smectic A phase at 58 ° C. during the temperature increase, and a thermal polymerization reaction was performed at 127 ° C.

[Example 7] Synthesis of polymerizable liquid crystal compound (Z7)

2.5 g (7.4 mmol) of the compound (Z2) obtained in Example 2, 0.84 g (7.5 mmol) of 4-fluorophenol, 0.1 g of DMAP, and a small amount of BHT were stirred at room temperature with methylene chloride. A solution in which 2.1 g (10.0 mmol) of DCC was dissolved in 10 mL of methylene chloride was added thereto, and the mixture was stirred overnight. The precipitated DCC urea was filtered off, and the filtrate was washed twice with 50 mol of 0.5 mol / L hydrochloric acid, 50 mL of saturated aqueous sodium hydrogen carbonate solution and 50 mL of saturated brine successively, dried over magnesium sulfate, and the solvent was removed. Distilled off and purified by recrystallization with ethanol to obtain 1.4 g of the target polymerizable liquid crystal compound (Z7) (yield 41%).
¹ H-NMR (CDCl ₃ ) δ: 1.67 (m, 2H), 1.80 (m, 2H), 1.90 (m, 2H), 2.64 (m, 1H), 3.10 (m, 1H), 4.04 (m, 2H ), 4.57 (m, 1H), 5.65 (m, 1H), 6.25 (m, 1H), 6.99 (d, 2H), 7.10 (m, 2H), 7.20 (m, 2H), 7.61 (d, 2H) , 7.71 (d, 4H), 8.24 (d, 2H)
In addition, as a result of observing the liquid crystal phase of the polymerizable liquid crystal compound (Z7), at the time of temperature increase, the phase transitioned to the smectic phase at 79 ° C., the phase transition to the nematic phase at 120 ° C., and the thermal polymerization reaction at 129 ° C.

[Example 8] Synthesis of compound (Z8) [1] Synthesis of intermediate compound (P8)

To a 500 mL eggplant flask equipped with a condenser tube, add 18.6 g (100 mmol) of biphenol, 10.0 g (48 mmol) of 4-bromobutyl-1,3-dioxolane, 13.8 g (100 mmol) of potassium carbonate, and 200 mL of acetone to obtain a mixture. The reaction was carried out at 64 ° C. with stirring for 24 hours. After completion of the reaction, the reaction solution was poured into 500 mL of pure water to obtain a white solid. This solid was mixed with 150 mL of methanol, and after filtration, the solvent was distilled off to obtain a white solid. Next, this solid was mixed with 70 mL of chloroform, and after filtration, the solvent was distilled off to obtain 7.2 g of a white solid. The result of having measured this solid by NMR is shown below. From this result, it was confirmed that this white solid was an intermediate compound (P8) (yield 48%).
¹ H-NMR (CDCl ₃ ) δ: 1.62 (m, 2H), 1.76 (m, 2H), 1.87 (m, 2H), 3.85 (m, 2H), 4.00 (m, 4H), 4.90 (m, 1H ), 6.87 (m, 4H), 7.42 (m, 4H)

[2] Synthesis of compound (Z8)

Next, in a 300 mL eggplant flask equipped with a cooling tube, 7.2 g (23 mmol) of the intermediate compound (P8) obtained above, 4.1 g (25 mmol) of 2- (bromomethyl) acrylic acid, 60 mL of THF, tin (II) chloride 4.7 g (25 mmol) and 19 mL of a 10% by mass aqueous HCl solution were added to form a mixture, which was stirred at 70 ° C. for 5 hours to be reacted. After completion of the reaction, the reaction solution was poured into 200 mL of pure water to obtain 6.1 g of a white solid.
The result of having measured this solid by NMR is shown below. From this result, it was confirmed that this white solid was the target compound (Z8) (yield 78%).
¹ H-NMR (CDCl ₃ ) δ: 1.60-1.95 (m, 6H), 2.64 (m, 1H), 3.11 (s, 1H), 4.02 (t, 2H), 4.60 (m, 1H), 4.82 (s , 1H), 5.64 (s, 1H), 6.24 (s, 1H), 6.94 (d, 2H), 7.44 (m, 4H)

[Example 9] Synthesis of polymerizable liquid crystal compound (Z9)

0.9 g (2.5 mmol) of the compound (Z8) obtained in Example 8, 0.45 g (2.5 mmol) of 4-fluorobenzoic acid, 0.03 g of DMAP, and a small amount of BHT were stirred at room temperature with stirring. A solution obtained by suspending in 15 mL of methylene and dissolving 0.7 g (3.5 mmol) of DCC in 5 mL of methylene chloride was added thereto and stirred overnight. The precipitated DCC urea was filtered off, and the filtrate was washed twice with 50 mol of 0.5 mol / L hydrochloric acid, 50 mL of saturated aqueous sodium hydrogen carbonate solution and 50 mL of saturated brine successively, dried over magnesium sulfate, and the solvent was removed. Distilled off and purified by recrystallization with ethanol to obtain 0.9 g of the target polymerizable liquid crystal compound (Z9) (yield 82%). The result of having measured this solid by NMR is shown below. From this result, it was confirmed that it was a polymerizable liquid crystal compound (Z9).
¹ H-NMR (CDCl ₃ ) δ: 1.59 (m, 2H), 1.70 (m, 2H), 1.86 (m, 2H), 2.59 (m, 1H), 3.08 (m, 1H), 4.00 (m, 2H) ), 4.57 (m, 1H), 5.64 (m, 1H), 6.25 (m, 1H), 6.96 (d, 2H), 7.20 (m, 4H), 7.50 (d, 2H), 7.60 (d, 2H) , 8.20 (m, 2H)
In addition, as a result of observing the liquid crystal phase of the polymerizable liquid crystal compound (Z9), at the time of temperature increase, the phase transitioned to a smectic phase at 99 ° C., the phase transition to a nematic phase at 112 ° C., and a thermal polymerization reaction at 123 ° C.

[Examples 10 to 15, Comparative Example 1] Polymerizable liquid crystal composition and polymer (film) thereof
The compounds used in the following examples and comparative examples are as follows. The compositions of the compositions prepared in Examples 10 to 15 and Comparative Example 1 are shown in Table 1 (unit: mg).

[Example 10] Polymerizable liquid crystal composition and polymer (film) thereof
Polymerizable liquid crystal compound (E1) 120 mg, polymerizable liquid crystal compound (E2) 90 mg, polymerizable liquid crystal compound (E3) 60 mg, polymerizable liquid crystal compound (Z3) 30 mg, Irgacure 369 manufactured by Ciba Geigy Co., Ltd. (trade name) ) 4 mg and 0.6 mg of surfactant R30 (manufactured by DIC Corporation) were dissolved in 0.7 g of cyclohexanone to obtain a polymerizable liquid crystal composition.
This polymerizable liquid crystal composition is applied to the liquid crystal alignment film surface of the substrate with a liquid crystal alignment film by spin coating (1,000 rpm, 20 seconds), pre-baked on a hot plate at 100 ° C. for 60 seconds, and then allowed to cool to room temperature. did. At this time, the polymerizable composition on the substrate was in a liquid crystal state. The substrate with a liquid crystal alignment film used here was coated with a liquid crystal alignment agent (SE-1410 manufactured by Nissan Chemical Industries, Ltd.) on the ITO surface of a glass substrate with ITO by spin coating, and baked at 230 ° C. to obtain a thickness. A 100-nm thin film is formed and then subjected to a rubbing treatment.

Next, the coating film formed on the substrate with a liquid crystal alignment film was irradiated with light having a strength of 2,000 mJ / cm ² using a metal halide lamp in a nitrogen atmosphere to polymerize the polymerizable liquid crystal composition. . The obtained film had a film thickness of 1.9 μm, and when observed with a polarizing microscope, it was confirmed that the film was horizontally oriented on the substrate surface. And the retardation value was 302 nm and haze value was 0.32.
When this film was heated on a hot plate at 160 ° C. for 30 minutes, the film thickness was 1.7 μm, the retardation value was 238 nm, and the haze value was 0.17. Further, when the film heated at 160 ° C. for 30 minutes was heated on a hot plate at 200 ° C. for 1 hour, the film thickness was 1.6 μm, the retardation value was 213 nm, and the haze value was 0.08. It was.

[Example 11] Polymerizable liquid crystal composition and polymer (film) thereof
A polymerizable liquid crystal composition was obtained in the same manner as in Example 10 except that the polymerizable liquid crystal compound (Z3) was changed to the polymerizable liquid crystal compound (Z4).
Using this polymerizable liquid crystal composition, a film was obtained in the same manner as in Example 10. The composition on the substrate after pre-baking was in a liquid crystal state.
The obtained film had a thickness of 1.8 μm, and when observed with a polarizing microscope, it was confirmed that the film was horizontally oriented on the substrate surface. And the retardation value was 29 nm and haze value was 0.24.
When this film was heated on a hot plate at 160 ° C. for 30 minutes, the film thickness was 1.7 μm, the retardation value was 30 nm, and the haze value was 0.24. Furthermore, when the film after heating at 160 ° C. for 30 minutes was heated on a hot plate at 200 ° C. for 1 hour, the film thickness was 1.6 μm, the retardation value was 33 nm, and the haze value was 0.16. It was.

[Example 12] Polymerizable liquid crystal composition and polymer (film) thereof
90 mg of polymerizable liquid crystal compound (E1), 90 mg of polymerizable liquid crystal compound (E2), 60 mg of polymerizable liquid crystal compound (E3), 60 mg of polymerizable liquid crystal compound (Z4), Irgacure 369 manufactured by Ciba Geigy Co., Ltd. (trade name) ) 4 mg and 0.6 mg of surfactant R30 (manufactured by DIC Corporation) were dissolved in 0.7 g of cyclohexanone to obtain a polymerizable liquid crystal composition.
Using this polymerizable liquid crystal composition, a film was obtained in the same manner as in Example 10. The composition on the substrate after pre-baking was in a liquid crystal state.
The obtained film had a thickness of 1.8 μm, and when observed with a polarizing microscope, it was confirmed that the film was horizontally oriented on the substrate surface. And the retardation value was 1 nm and haze value was 0.00.
When this film was heated on a hot plate at 160 ° C. for 30 minutes, the film thickness was 1.7 μm, the retardation value was 1 nm, and the haze value was 0.09. Furthermore, when the film after heating at 160 ° C. for 30 minutes was heated on a hot plate at 200 ° C. for 1 hour, the film thickness was 1.6 μm, the retardation value was 1 nm, and the haze value was 0.01. It was.

[Example 13] Polymerizable liquid crystal composition and polymer (film) thereof
A polymerizable liquid crystal composition was obtained in the same manner as in Example 12 except that the polymerizable liquid crystal compound (Z4) was changed to the polymerizable liquid crystal compound (Z5).
Using this polymerizable liquid crystal composition, a film was obtained in the same manner as in Example 10. The composition on the substrate after pre-baking was in a liquid crystal state.
The obtained film had a film thickness of 1.9 μm, and when observed with a polarizing microscope, it was confirmed that the film was horizontally oriented on the substrate surface. And the retardation value was 2 nm and haze value was 0.21.
When this film was heated on a hot plate at 160 ° C. for 30 minutes, the film thickness was 1.7 μm, the retardation value was 2 nm, and the haze value was 0.14. Furthermore, when the film after heating at 160 ° C. for 30 minutes was heated on a hot plate at 200 ° C. for 1 hour, the film thickness was 1.6 μm, the retardation value was 2 nm, and the haze value was 0.08. It was.

[Example 14] Polymerizable liquid crystal composition and polymer (film) thereof
A polymerizable liquid crystal composition was obtained in the same manner as in Example 10 except that the polymerizable liquid crystal compound (Z3) was changed to the polymerizable liquid crystal compound (Z7).
Using this polymerizable liquid crystal composition, a film was obtained in the same manner as in Example 10. The composition on the substrate after pre-baking was in a liquid crystal state.
The obtained film had a thickness of 1.8 μm, and when observed with a polarizing microscope, it was confirmed that the film was horizontally oriented on the substrate surface. And the retardation value was 305 nm and haze value was 0.29.
When this film was heated on a hot plate at 160 ° C. for 30 minutes, the film thickness was 1.7 μm, the retardation value was 260 nm, and the haze value was 0.24. Further, when the film heated at 160 ° C. for 30 minutes was heated on a hot plate at 200 ° C. for 1 hour, the film thickness was 1.6 μm, the retardation value was 232 nm, and the haze value was 0.16. It was.

[Example 15] Polymerizable liquid crystal composition and polymer (film) thereof
A polymerizable liquid crystal composition was obtained in the same manner as in Example 12 except that the polymerizable liquid crystal compound (Z4) was changed to the polymerizable liquid crystal compound (Z7).
Using this polymerizable liquid crystal composition, a film was obtained in the same manner as in Example 10. The composition on the substrate after pre-baking was in a liquid crystal state.
The obtained film had a thickness of 1.8 μm, and when observed with a polarizing microscope, it was confirmed that the film was horizontally oriented on the substrate surface. And the retardation value was 86 nm and haze value was 0.09.
When this film was heated on a hot plate at 160 ° C. for 30 minutes, the film thickness was 1.7 μm, the retardation value was 86 nm, and the haze value was 0.08. Further, when the film after heating at 160 ° C. for 30 minutes was heated on a hot plate at 200 ° C. for 1 hour, the film thickness was 1.6 μm, the retardation value was 85 nm, and the haze value was 0.08. It was.

[Comparative Example 1] Polymerizable liquid crystal composition and polymer (film) thereof
Polymerizable liquid crystal compound (E1) 120 mg, polymerizable liquid crystal compound (E2) 120 mg, polymerizable liquid crystal compound (E3) 60 mg, Ciba Geigy's Irgacure 369 (trade name) 4 mg as a photopolymerization initiator, and a surfactant. 0.6 mg of R30 (manufactured by DIC Corporation) was dissolved in 0.7 g of cyclohexanone to obtain a polymerizable liquid crystal composition.
Using this polymerizable liquid crystal composition, a film was obtained in the same manner as in Example 10. The composition on the substrate after pre-baking was in a liquid crystal state.
The obtained film had a film thickness of 1.9 μm, and when observed with a polarizing microscope, it was confirmed that the film was horizontally oriented on the substrate surface. And the retardation value was 299 nm and haze value was 0.09.
When this film was heated on a hot plate at 160 ° C. for 30 minutes, the film thickness was 1.7 μm, the retardation value was 234 nm, and the haze value was 0.08. Furthermore, when the film after heating at 160 ° C. for 30 minutes was heated on a hot plate at 200 ° C. for 1 hour, the film thickness was 1.7 μm, the retardation value was 205 nm, and the haze value was 0.08. It was.

A summary of Examples 10-15 and Comparative Example 1 is shown in Table 2.
Moreover, the retardation value angle dependency in the wavelength of 590 nm of the film produced in the said Examples 10-15 and the comparative example 1 is shown in FIG.
Furthermore, Table 2 shows the results of measuring the average tilt angle of the wavelength 590 nm of the films prepared in Examples 10 to 15 and the comparative example.

ベーク１：１６０℃，３０分間加熱後
ベーク２：１６０℃，３０分間加熱→２００℃，１時間加熱

Bake 1: 160 ° C for 30 minutes and then bake 2: 160 ° C for 30 minutes → 200 ° C for 1 hour

  As shown in Table 2, in the films prepared in Examples 10 to 15, the haze after baking is kept low (that is, the thermal stability is high), and the polymerizable liquid crystal compound of the present invention is added. It was found that the average angle can be controlled.

Claims (10)

A polymerizable liquid crystal compound represented by the following formula [1].

(In the formula, X ¹ , X ² , X ³ and X ⁴ each independently represent a hydrogen atom or a fluorine atom, and R represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an alkoxy group, or an alkoxy group. Represents a carbonyl group, G represents a -C (= O) O- or -OC (= O)-group, and n represents an integer of 4 to 10.)   A polymerizable liquid crystal composition comprising the polymerizable liquid crystal compound according to claim 1.   The polymerizable liquid crystal composition according to claim 2, further comprising a liquid crystal compound having one or more polymerizable groups in one molecule. The polymerizable liquid crystal composition according to claim 3, wherein the liquid crystal compound is a compound having at least one polymerizable group represented by the following formula [2] or [3] in one molecule.

(In the formula, a broken line represents a bond.) The polymerizable liquid crystal composition according to claim 3 or 4, wherein the liquid crystal compound is at least one selected from the group consisting of compounds represented by the following formulas [4] and [5].

(In the formula, X represents a fluorine atom, a cyano group or a monovalent hydrocarbon group having 4 to 8 carbon atoms, f1 and f2 each independently represents an integer of 2 to 9, and g represents an integer of 2 to 9) And M ¹ , M ² and M ³ each independently represents a group represented by the following formula [2] or [3].)

(In the formula, a broken line represents a bond.)   The polymer obtained from the polymeric liquid crystal composition of any one of Claims 2-5.   The film obtained from the polymeric liquid crystal composition of any one of Claims 2-5.   An alignment film obtained from the polymerizable liquid crystal composition according to claim 2.   An optical member comprising the polymer according to claim 6 or the oriented film according to claim 8. The compound represented by following formula [6].

(In the formula, Y represents —OH or —COOH, and k represents an integer of 4 to 10).

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