WO2013039053A1

WO2013039053A1 - Polymerizable liquid crystal composition and alignment film

Info

Publication number: WO2013039053A1
Application number: PCT/JP2012/073161
Authority: WO
Inventors: ダニエルアントニオ櫻葉汀; 真畑中
Original assignee: 日産化学工業株式会社
Priority date: 2011-09-15
Filing date: 2012-09-11
Publication date: 2013-03-21
Also published as: CN103827155B; KR102045532B1; JP5958471B2; JPWO2013039053A1; TW201326372A; TWI555826B; KR20140062483A; CN103827155A

Abstract

Provided is a polymerizable liquid crystal composition characterized in comprising: (A) at least one species selected from polymerizable liquid crystal compounds represented by formula [1]; (B) at least one species selected from polymerizable liquid crystal compounds represented by formula [2]; and (C) at least one species selected from polyvalent acrylate compounds having at least one type of structure selected from the group consisting of a trimethylolpropane structure, a pentaerythritol structure, and an ethylene glycol structure, or a structure in which at least one species selected from the above structures is condensed. (In the formulae, R¹, R³, and R⁴ are each independently an organic group represented by formula [3] or [4] (in which X is hydrogen or methyl, and the dashed lines are atomic bonds); R² is hydrogen, halogen, cyano, or methoxy; n1, n2, and n3 are each independently an integer 2-10; q is 0 or 1; p is 1 when q is 0, and is 0 or 1 when q is 1; r is 1 or 2; and s is 1 when r is 1, and is 0 when r is 2.)

Description

Polymerizable liquid crystal composition and alignment film

The present invention relates to a polymerizable liquid crystal composition, a polymer obtained using the polymerizable liquid crystal composition, and an alignment film. Specifically, a polymerizable liquid crystal composition that can be suitably used for a material having optical characteristics such as a display device or a recording material, in particular, an optical compensation film such as a polarizing plate for a liquid crystal display or a retardation plate, and obtained using the same. The present invention relates to a polymer and a hybrid alignment film obtained by using these.

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 (Patent Document 1), or having an acrylic group There is known a method of obtaining a polymer by adding a photopolymerization initiator to a mixture of two kinds of polymerizable liquid crystal compounds or a composition obtained by mixing a chiral liquid crystal with this mixture and irradiating ultraviolet rays (Patent Document 2).

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, since a film obtained from a polymerizable liquid crystal compound has a glass transition temperature (hereinafter referred to as Tg) that is lower than the temperature of the use environment, particularly in a high temperature environment, molecular fluctuations occur. The orientation may be disturbed, and the optical anisotropy may be significantly reduced.

Furthermore, in the field of displays, in recent years, studies on simplification of processes 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 exhibiting various average tilt angles have been reported (Patent Document 3).

By the way, if the orientation mode (for example, horizontal or hybrid) of the obtained film can be easily controlled by adding a small amount of a specific compound to the liquid crystal composition, it can be widely applied in the liquid crystal display field.
If a single material can be used to change the process and a horizontal or hybrid alignment film can be easily created, a wide range of applications can be expected in the liquid crystal display field.

Patent Document 4 describes that a polyfunctional polymerizable compound having no liquid crystallinity can be added to a liquid crystal composition using a polymerizable liquid crystal compound having an acrylic group (0 to 20%). However, the addition of the polyfunctional polymerizable compound is for the purpose of improving the heat resistance of the film, and it is not described that the alignment mode can be controlled.

It has also been reported that the tilt angle can be controlled by combining polymerizable liquid crystal compounds for vertical and horizontal alignment films. Among them, it has been reported that the tilt angle of the O-plate film can be controlled, but no data other than the tilt angle (Δnd, haze value, etc.) has been reported (Patent Document 3).

JP-A-62-70407 JP-A-9-208957 International Publication No. 2008/052376 International Publication No. 98/04651

The present invention has been made in view of such circumstances, and has excellent optical anisotropy, and the retardation value and transparency are stably maintained even at high temperatures, and is excellent in chemical resistance and heat resistance. An object of the present invention is to provide a polymerizable liquid crystal composition in which a polymer is provided and the alignment mode is easily controlled, a polymer obtained by using the composition, and a hybrid alignment film obtained by using these.

As a result of intensive studies to solve the above problems, the present inventors add a small amount of a certain polyvalent acrylate compound to a polymerizable liquid crystal composition for a horizontal alignment film containing a certain polymerizable liquid crystal compound. Thus, it was found that the orientation mode can be easily controlled. Furthermore, a stable polymerizable liquid crystal composition can be obtained, a polymer or film obtained from the polymerizable liquid crystal composition has excellent optical anisotropy and heat resistance, and a hybrid alignment film can be obtained. As a result, the present invention has been completed.

That is, the present invention
1. (A) at least one selected from polymerizable liquid crystal compounds represented by the following formula [1],
(B) at least one selected from polymerizable liquid crystal compounds represented by the following formula [2], and (C) at least one structure selected from a trimethylolpropane structure, a pentaerythritol structure, and an ethylene glycol structure, or from these Containing at least one selected from polyhydric acrylate compounds obtained from polyhydric alcohols having 3 to 50 oxygen atoms in total and acrylic acid or derivatives thereof, having a structure in which at least one selected is condensed. A polymerizable liquid crystal composition characterized by

[Wherein R ¹ , R ³ and R ⁴ each independently represents the following formula [3] or [4]

(In the formula, X is a hydrogen atom or a methyl group. The broken line is a bond.)
It is an organic group represented by. R ² is a hydrogen atom, a halogen atom, a cyano group or a methoxy group. n1, n2 and n3 are each independently an integer of 2 to 10. q is 0 or 1. p is 1 when q is 0, and 0 or 1 when q is 1. r is 1 or 2; s is 1 when r is 1 and 0 when r is 2. ]
2. 1 polymerizable liquid crystal composition, wherein the polyvalent acrylate compound (C) is represented by the following formula [5] or [6]:

(In the formula, R ⁵ represents a methyl group, or the following formula [7] or [8].

It is an organic group represented by. n4 to n10 are each independently an integer of 0 to 10. n11 is an integer of 4 to 10. A broken line is a bond. )
3. The polymerizable liquid crystal compound (B) is a polymerizable liquid crystal composition of 1 or 2 represented by the following formula [9]:

(Wherein n2, n3, r and s are the same as above)
4. A polymer obtained from any one of the polymerizable liquid crystal compositions of 1 to 3,
5.1 A film obtained from the polymerizable liquid crystal composition of any one of 1 to 3,
6.1 A hybrid alignment film obtained from the polymerizable liquid crystal composition according to any one of 1 to 3;
An optical member comprising an oriented film of 7.6 is provided.

The polymerizable liquid crystal composition of the present invention not only has excellent optical anisotropy, but also gives a polymer having stable anisotropy and transparency in a high temperature environment. In addition, the polymerizable liquid crystal composition of the present invention has an advantage that the orientation mode (horizontal, hybrid) of a film obtained therefrom can be easily controlled by containing a small amount of the polyvalent acrylate compound (C). ing.
Therefore, the polymer obtained from the composition of the present invention 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 1-6. It is a figure which shows the retardation value angle dependence in wavelength 590nm of each film obtained by Comparative Examples 1-5. It is a figure which shows the retardation value angle dependency in wavelength 590nm of each film obtained in Examples 7-8.

Terms used in this specification are as follows.
“Polymerizable liquid crystal compound” means a compound having a polymerizable portion such as an acryl group and an α-methylene-γ-butyrolactone 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.

The polymerizable liquid crystal compounds (A) and (B) used in the present invention have a liquid crystal structure portion, and further have one or both of an acrylic group and an α-methylene-γ-butyrolactone structure.
α-Methylene-γ-butyrolactone is less affected by steric hindrance than α-alkylidene-γ-butyrolactone 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.

[Polymerizable liquid crystal compound (A)]
The polymerizable liquid crystal compound (A) used in the present invention is represented by the following formula [1].

In the formula [1], R ¹ represents the following formula [3] or [4]

(In the formula, X is a hydrogen atom or a methyl group. The broken line is a bond.)
It is an organic group represented by.

In the formula [1], R ² is a hydrogen atom, a halogen atom, a cyano group or a methoxy group. As the halogen atom, a fluorine atom is particularly preferable. R ² is preferably a hydrogen atom, a methoxy group or a cyano group, more preferably a hydrogen atom or a cyano group.
The repeating part of a methylene group is a part called a spacer part. n1 represents the number of repeating methylene groups and is independently an integer of 2 to 10, preferably an integer of 3 to 6.
q is 0 or 1. p is 1 when q is 0, and 0 or 1 when q is 1.

The polymerizable liquid crystal compound (A) 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 (A) include, but are not limited to, compounds represented by the following formulas (1) to (25). In the formula, Me represents a methyl group.

[Polymerizable liquid crystal compound (B)]
The polymerizable liquid crystal compound (B) used in the present invention is represented by the following formula [2].

In the formula [2], R ³ and R ⁴ have the same meaning as R ¹ described above and may be the same or different from each other. n2 and n3 each represents the number of repeating methylene groups, each independently an integer of 2 to 10, preferably an integer of 3 to 6. r is 1 or 2; s is 1 when r is 1 and 0 when r is 2.

In the formula [2], at least one of R ³ and R ⁴ is preferably an organic group represented by the formula [3]. As the polymerizable liquid crystal compound (B), a compound represented by the following formula [9] is particularly preferable.

(Wherein n2, n3, r and s are the same as above)

Specific examples of the polymerizable liquid crystal compound (B) include compounds represented by the following formulas (26) to (116), but are not limited thereto.

[Polyvalent acrylate compound (C)]
The polyvalent acrylate compound (C) used in the present invention has at least one structure selected from a trimethylolpropane structure, a pentaerythritol structure and an ethylene glycol structure, or a structure in which at least one selected from these is condensed. A polyvalent acrylate compound obtained from a polyhydric alcohol having 3 to 50 oxygen atoms and acrylic acid or a derivative thereof. Specific examples thereof include those represented by the following formula [5] or [6].

(In the formula, R ⁵ represents a methyl group or the following formula [7] or [8].

It is an organic group represented by. n4 to n10 are each independently an integer of 0 to 10. n11 is an integer of 4 to 10. A broken line is a bond. )

Specific examples of the polyvalent acrylate compound (C) include compounds represented by the following formulas (117) to (127), but are not limited thereto.

Commercially available products can be used as the polyvalent acrylate compound (C), and examples thereof include KAYARAD DPHA, PET30 manufactured by Nippon Kayaku Co., Ltd., ATM-35E manufactured by Shin-Nakamura Chemical Co., Ltd., and ADPH. .

[Polymerizable liquid crystal composition]
The polymerizable liquid crystal composition according to the present invention contains at least one polymerizable liquid crystal compound (A), at least one polymerizable liquid crystal compound (B), and at least one polyvalent acrylate compound (C). In addition, as a polyvalent acrylate compound (C), the compound represented by the said Formula [5] or [6] is preferable.

The content of the polymerizable liquid crystal compound (A) is 100 to 1,900 parts by mass, preferably 400 to 900 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound (B). The content of the polyvalent acrylate compound (C) is 0.5 to 5 with respect to 100 parts by mass of the total of the polymerizable liquid crystal compounds (A) and (B) (hereinafter collectively referred to as the total liquid crystal compound). Mass parts are preferred, more preferably 1 to 3 parts by mass.

In the polymerizable liquid crystal composition of the present invention, a photopolymerization initiator, a thermal polymerization initiator, and a photosensitizer can be added 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, benzyl ketals such as benzyldimethyl ketal, and the like. Such a photoinitiator may be used individually by 1 type or in combination of multiple types. The addition amount of the photopolymerization initiator is preferably 5 parts by mass or less, more preferably 0.5 to 2.0 parts by mass with respect to 100 parts by mass of the total liquid crystalline compounds.

Examples of the thermal polymerization initiator include 2,2'-azobisisobutyronitrile. The thermal polymerization initiator may be used alone or in combination of two or more. The addition amount is preferably 5 parts by mass or less, more preferably 0.5 to 2.0 parts by mass with respect to 100 parts by mass of the total liquid crystal compounds.

Examples of the photosensitizer include anthracene photosensitizers such as anthracene. A photosensitizer may be used alone or in combination of two or more. The addition amount is preferably 5 parts by mass or less with respect to 100 parts by mass of the total liquid crystal compounds.

The above-mentioned 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. A stabilizer may be used alone or in combination of two or more. 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. As adhesion promoters, chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, chloromethyldimethylchlorosilane, vinyltrichlorosilane; trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylvinylethoxysilane, diphenyldimethoxy Silane, phenyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ- (N-piperidinyl) propyl Alkoxysilanes such as trimethoxysilane; hexamethyldisilazane, N, N′-bis (trimethylsilyl) urea, dimethyltrimethylsilyl Silazanes such as amine and N-trimethylsilylimidazole; benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazole, thiouracil, mercaptoimidazole, mercaptopyrimidine, etc. Heterocyclic compounds; urea compounds such as 1,1-dimethylurea and 1,3-dimethylurea; and thiourea compounds.

The adhesion promoter may be used alone or in combination of two or more. The addition amount is preferably 1 part by mass or less with respect to 100 parts by mass of the total liquid crystal compounds.

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-ethoxypropionic acid Alkoxy esters such as ethyl; 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 ruethyl 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 Tons, methyl isobutyl ketone and 2-heptanone. 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.

These organic solvents may be used alone or in combination of two or more. The amount of the organic solvent used is preferably about 60 to 95% by mass in the polymerizable liquid crystal composition.

Further, 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 fluorine-based surfactants, silicone-based surfactants, nonionic surfactants, etc., but fluorine-based surfactants having a high effect of improving affinity with the substrate. Agents are preferred.

Specific examples of 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 (Sumitomo 3M Co., Ltd.), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.), etc. Not. The surfactants may be used alone or in combination of two or more.

As a preferred example of the polymerizable liquid crystal composition of the present invention, the polymerizable liquid crystal compound (A) is 400 to 900 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound (B). C) is 1 to 3 parts by mass relative to 100 parts by mass of the polymerizable liquid crystal compounds (A) and (B), and the photoinitiator is 100 parts by mass of the polymerizable liquid crystal compounds (A) and (B). Although what consists of 5 mass parts or less with respect to a part is mentioned, It is not limited to this.

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 shall apply 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.

The polymerizable liquid crystal composition of the present invention can be suitably used as a composition for forming an orientation film or a coating solution.

[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 applying a polymerizable liquid crystal composition to a substrate by spin coating, a casting method, or the like, and performing light irradiation treatment.

At this time, as the substrate, glass, quartz, a color filter, a plastic sheet such as triacetyl cellulose (TAC), a film, or the like can be used.

For the purpose of improving the hybrid orientation of the resulting film, the substrate to be used is preferably subjected to an orientation treatment so as to obtain 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 irradiating with rubbing or polarized ultraviolet rays obliquely, and a silicon dioxide oblique deposition film is formed. However, in order to produce a hybrid alignment film, it is preferable to use an alignment method capable of obtaining a tilt in any case.

In the method for producing a film, 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 polymerizing the polymerizable liquid crystal composition in a state of exhibiting a liquid crystal phase.

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. In addition, 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.

EXAMPLES 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 an Example. In addition, the measuring method and measuring conditions of each physical property in an Example 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 Co., Ltd.) and using a polarizing microscope (manufactured by Nikon Co., Ltd.). It was. The phase transition temperature was measured using a differential scanning calorimeter (DSC3100SR) manufactured by Bruker AXS Co., Ltd. at a scan speed of 10 ° C./min.
[3] Haze value The haze value of the film was measured using a specular haze meter (TC-1800H) manufactured by Tokyo Denshoku.
[4] Retardation value of film The retardation value at a wavelength of 590 nm was measured using a retardation measuring device (RETS-100, manufactured by Otsuka Electronics Co., Ltd.).
[5] Average Tilt Angle of Film The average tilt angle was measured using an AxoScan ^™ Mueller Matrix Polarimeter (manufactured by AXOMETRIX).

[Synthesis Example 1] Synthesis of polymerizable liquid crystal compound (A1) [1] Synthesis of intermediate compound (I1)

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, 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. for 48 hours with stirring. 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 was intermediate compound (I1) (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 (A1)

12.0 g of the intermediate compound (I1) obtained above was dissolved in 40 mL of tetrahydrofuran (THF) together with 7.7 mL of triethylamine and a small amount of 2,6-di-tert-butyl-p-cresol (BHT). The solution which stirred at room temperature and melt | dissolved acryloyl chloride 4.6mL in THF40mL was dripped over 15 minutes under cooling by 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 the THF was distilled off from the obtained filtrate, 50 mL of dichloromethane 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 the product. After recrystallization from ethanol, 6.0 g of a polymerizable liquid crystal compound (A1) 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 (A2) [1] Synthesis of intermediate compound (I2)

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 & Co., eluent: hexane / ethyl acetate = 1/1 (v / v)). Purified. 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 intermediate compound (I2) (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 (F2)

Next, intermediate compound (I2) obtained above in a state where 2.2 g (10.0 mmol) of pyridinium chlorochromate (PCC) and 30.0 mL of dichloromethane were added to a 200 mL three-necked flask equipped with a condenser and stirred and mixed. A solution prepared by dissolving 2.95 g (10.0 mmol) in 50.0 mL of dichloromethane was added dropwise, and the mixture was 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 & Co., eluent: hexane / ethyl acetate = 1/1 (v / v)). did. 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 (F2) (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 (A2)

Finally, in a 50 mL eggplant flask equipped with a cooling tube, 2.9 g (10.0 mmol) of the intermediate compound (F2) obtained above, 1.65 g (10.0 mmol) of 2- (bromomethyl) acrylic acid, Amberlyst (registered) Trademark) 15 (Rohm End Haas Co., Ltd.) 1.6 g, THF 16.0 mL, tin (II) chloride 1.9 g (10.0 mmol), and pure water 4.0 mL were added to form a mixture, and the mixture was at 70 ° C. for 7 hours. Stir to react. 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 & Co., 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 (A2) (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 (A2), it became an isotropic liquid state at 84 ° C., and phase transitioned to a liquid crystal phase (nematic phase) at 61 ° C. when the temperature was lowered.

[Synthesis Example 3] Synthesis of polymerizable liquid crystal compound (B1) [1] Synthesis of intermediate compound (I3)

In a 200 mL eggplant flask with a condenser tube, 7.61 g (50.0 mmol) of methyl 4-hydroxybenzoate, 9.1 g (50.0 mmol) of 6-bromo-1-hexanol, 13.8 g (100 mmol) of potassium carbonate, and acetone 70 mL was added to make a mixture, and the mixture was reacted at 64 ° C. (under heating under reflux) 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 & Co., 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 intermediate compound (I3) (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 (F3)

Next, in a 100 mL three-necked flask with a condenser tube, 2.2 g (10.0 mmol) of PCC and 15.0 mL of dichloromethane were stirred and mixed, and 2.5 g of the intermediate compound (I3) obtained above (10 0.0 mmol) in 15.0 mL of dichloromethane 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 (F3) (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 (G3)

Next, 1.25 g (5.0 mmol) of the intermediate compound (F3) obtained above, 0.83 g (5.0 mmol) of 2- (bromomethyl) acrylic acid, Amberlyst (registered) Trademark) 15 (Rohm End Haas Co., Ltd. trade name) 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 kept at 70 ° C. for 5 hours. Stir to react. 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 (G3) (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 (H3)

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 (G3) obtained above, and 5 mL of 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, Amberlyst (registered trademark) 15 (trade name of Rohm End Haas Co., Ltd.) 1.0 g, and 20.0 mL of THF are added to a 50 mL eggplant flask with a condenser tube to obtain a mixture, For 5 hours with stirring. 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 was the target intermediate compound (H3) (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)

13.1 g (138.0 mmol) of 3-bromo-1-propanol was dissolved in 100 mL of THF together with 18.9 mL of triethylamine (TEA) and a small amount of BHT, stirred at room temperature, and dissolved in 50 mL of THF under cooling with a water bath. 2 mL (150 mmol) of acryloyl chloride was added dropwise over 15 minutes and the mixture was stirred for 30 minutes. The water bath was removed, and the mixture was stirred 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 (J3)

In a 500 mL eggplant flask equipped with a cooling officer, 17.6 g (94.3 mmol) of 4-hydroxy-4′-biphenol, 18.2 g (94.3 mmol) of compound (P3), 24.0 g (190 mmol) of potassium carbonate, 250 mL of acetone Was added to make a mixture, and the mixture was reacted at a temperature of 54 ° C. with stirring 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). 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 (J3) (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 (B1)

Intermediate compound (H3) 6.1 g (20.0 mmol), intermediate compound (J3) 6.0 g (20.0 mmol) obtained above, N, N-dimethyl-4-aminopyridine (DMAP) 0. 08 g and a small amount of 2,6-di-tert-butyl-p-cresol (BHT) were suspended in 10 mL of dichloromethane with stirring at room temperature, and 4.7 g of dicyclohexylcarbodiimide (DCC) dissolved in 20 mL of dichloromethane. 23.0 mmol) was added and stirred overnight, and the precipitated DCC urea was filtered off, and the filtrate was washed twice with 60 mL of 0.5 mol / L hydrochloric acid, saturated aqueous sodium hydrogen carbonate solution and saturated brine successively. After washing and drying with magnesium sulfate, the solvent was distilled off, and 8.8 g of a polymerizable liquid crystal compound (B1) was obtained by recrystallization with ethanol (yield). 75%). The result of having measured this solid by NMR is shown below.
¹ H-NMR (CDCl3) 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, 4H), 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 (B1), the phase transition to the smectic X phase at 109 ° C. during the temperature rise, the phase transition to the nematic phase at 144 ° C., and the isotropic liquid state at 168 ° C. It became.

[Examples and Comparative Examples] 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 used in Examples 1 to 8 are shown in Table 1, and the compositions of the compositions used in Comparative Examples 1 to 5 are shown in Table 2.
The following compounds (C1), (C2), (C3), (C5) and (E1) are products of Shin-Nakamura Chemical Co., Ltd., and compound (C4) is a product of Nippon Kayaku Co., Ltd. Yes, compound (E2) is a product of Tokyo Chemical Industry Co., Ltd. Compound (E3) is known.

[Example 1] Polymerizable liquid crystal composition and polymer (film) thereof
150 mg of polymerizable liquid crystal compound (A1), 90 mg of polymerizable liquid crystal compound (A2), 60 mg of polymerizable liquid crystal compound (B1), 9 mg of polyvalent acrylate compound (C1), 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 has a thickness obtained by applying a liquid crystal alignment agent (SE-1410 manufactured by Nissan Chemical Industries, Ltd.) to the ITO surface of a glass substrate with ITO by spin coating and baking at 230 ° C. 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 film thickness of the obtained film was 1.8 μm, and when observed with a polarizing microscope, it was confirmed that the film was hybrid-aligned on the substrate surface (average tilt 40 °). The retardation value was 117 nm and the haze value was 1.44.
When this film was heated on a hot plate at 200 ° C. for 30 minutes, the retardation value was 109 nm and the haze value was 1.30.

[Example 2] Polymerizable liquid crystal composition and polymer (film) thereof
150 mg of polymerizable liquid crystal compound (A1), 90 mg of polymerizable liquid crystal compound (A2), 60 mg of polymerizable liquid crystal compound (B1), 15 mg of polyvalent acrylate compound (C2), 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.

A film was produced in the same manner as in Example 1 except that this polymerizable liquid crystal composition was used. The polymerizable composition on the substrate after pre-baking was in a liquid crystal state.
The film thickness of the obtained film was 1.8 μm, and when observed with a polarizing microscope, it was confirmed that the film was hybrid-aligned on the substrate surface (average tilt 40 °). The retardation value was 121 nm and the haze value was 0.66.
When this film was heated on a hot plate at 200 ° C. for 30 minutes, the retardation value was 109 nm and the haze value was 0.38.

[Example 3] Polymerizable liquid crystal composition and polymer (film) thereof
150 mg of polymerizable liquid crystal compound (A1), 90 mg of polymerizable liquid crystal compound (A2), 60 mg of polymerizable liquid crystal compound (B1), 15 mg of polyvalent acrylate compound (C3), 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.

A film was produced in the same manner as in Example 1 except that this polymerizable liquid crystal composition was used. The polymerizable composition on the substrate after pre-baking was in a liquid crystal state.
The film thickness of the obtained film was 1.8 μm, and when observed with a polarizing microscope, it was confirmed that the film was hybrid-aligned on the substrate surface (average tilt 40 °). The retardation value was 115 nm and the haze value was 0.08.
When this film was heated on a hot plate at 200 ° C. for 30 minutes, the retardation value was 98 nm and the haze value was 0.07.

[Example 4] Polymerizable liquid crystal composition and polymer (film) thereof
150 mg of polymerizable liquid crystal compound (A1), 90 mg of polymerizable liquid crystal compound (A2), 60 mg of polymerizable liquid crystal compound (B1), 9 mg of polyvalent acrylate compound (C4), 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.

A film was produced in the same manner as in Example 1 except that this polymerizable liquid crystal composition was used. The polymerizable composition on the substrate after pre-baking was in a liquid crystal state.
The film thickness of the obtained film was 1.8 μm, and when observed with a polarizing microscope, it was confirmed that the film was hybrid-aligned on the substrate surface (average tilt 40 °). The retardation value was 101 nm, and the haze value was 0.05.
When this film was heated on a hot plate at 200 ° C. for 30 minutes, the retardation value was 92 nm and the haze value was 0.07.

[Example 5] Polymerizable liquid crystal composition and polymer (film) thereof
150 mg of polymerizable liquid crystal compound (A1), 90 mg of polymerizable liquid crystal compound (A2), 60 mg of polymerizable liquid crystal compound (B1), 15 mg of polyvalent acrylate compound (C4), 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.

A film was produced in the same manner as in Example 1 except that this polymerizable liquid crystal composition was used. The polymerizable composition on the substrate after pre-baking was in a liquid crystal state.
The film thickness of the obtained film was 1.8 μm, and when observed with a polarizing microscope, it was confirmed that the film was hybrid-aligned on the substrate surface (average tilt 40 °). The retardation value was 96 nm and haze value was 1.15.
When this film was heated on a hot plate at 200 ° C. for 30 minutes, the retardation value was 95 nm and the haze value was 2.18.

[Example 6] Polymerizable liquid crystal composition and polymer (film) thereof
150 mg of polymerizable liquid crystal compound (A1), 90 mg of polymerizable liquid crystal compound (A2), 60 mg of polymerizable liquid crystal compound (B1), 3 mg of polyvalent acrylate compound (C5), 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.

A film was produced in the same manner as in Example 1 except that this polymerizable liquid crystal composition was used. The polymerizable composition on the substrate after pre-baking was in a liquid crystal state.
The film thickness of the obtained film was 1.8 μm, and when observed with a polarizing microscope, it was confirmed that the film was hybrid-aligned on the substrate surface (average tilt 40 °). The retardation value was 106 nm and the haze value was 0.03.
When this film was heated on a hot plate at 200 ° C. for 30 minutes, the retardation value was 99 nm and the haze value was 0.08.

[Comparative Example 1] Polymerizable liquid crystal composition and polymer (film)
150 mg of polymerizable liquid crystal compound (A1), 90 mg of polymerizable liquid crystal compound (A2), 60 mg of polymerizable liquid crystal compound (B1), 15 mg of compound (E1), 4 mg of Irgacure 369 (trade name) manufactured by Ciba Geigy Co., which is a photopolymerization initiator, In addition, 0.6 mg of surfactant R30 (manufactured by DIC Corporation) was dissolved in 0.7 g of cyclohexanone to obtain a polymerizable liquid crystal composition.

A film was produced in the same manner as in Example 1 except that this polymerizable liquid crystal composition was used. The polymerizable composition on the substrate after pre-baking was in a liquid crystal state.
The film thickness of the obtained film was 1.7 μm, and when observed with a polarizing microscope, it was confirmed that the film was horizontally oriented (tilt <10 °) on the substrate surface. The retardation value was 296 nm and the haze value was 0.08.
When this film was heated on a hot plate at 200 ° C. for 30 minutes, the retardation value was 201 nm and the haze value was 0.08.

[Comparative Example 2] Polymerizable liquid crystal composition and polymer (film)
150 mg of polymerizable liquid crystal compound (A1), 90 mg of polymerizable liquid crystal compound (A2), 60 mg of polymerizable liquid crystal compound (B1), 30 mg of compound (E2), 4 mg of Irgacure 369 (trade name) manufactured by Ciba Geigy Co., which is a photopolymerization initiator, In addition, 0.6 mg of surfactant R30 (manufactured by DIC Corporation) was dissolved in 0.7 g of cyclohexanone to obtain a polymerizable liquid crystal composition.

A film was produced in the same manner as in Example 1 except that this polymerizable liquid crystal composition was used. The polymerizable composition on the substrate after pre-baking was in a liquid crystal state.
The film thickness of the obtained film was 1.9 μm, and when observed with a polarizing microscope, it was confirmed that the film was horizontally oriented (tilt <10 °) on the substrate surface. The retardation value was 261 nm and the haze value was 0.08.
When this film was heated on a hot plate at 200 ° C. for 30 minutes, the retardation value was 144 nm and the haze value was 0.08.

[Comparative Example 3] Polymerizable liquid crystal composition and polymer (film) thereof
150 mg of polymerizable liquid crystal compound (A1), 90 mg of polymerizable liquid crystal compound (A2), 60 mg of polymerizable liquid crystal compound (B1), 30 mg of compound (E3), 4 mg of Irgacure 369 (trade name) manufactured by Ciba Geigy Co., which is a photopolymerization initiator, In addition, 0.6 mg of surfactant R30 (manufactured by DIC Corporation) was dissolved in 0.7 g of cyclohexanone to obtain a polymerizable liquid crystal composition.

A film was produced in the same manner as in Example 1 except that this polymerizable liquid crystal composition was used. The polymerizable composition on the substrate after pre-baking was in a liquid crystal state.
The film thickness of the obtained film was 1.9 μm, and when observed with a polarizing microscope, it was confirmed that the film was horizontally oriented (tilt <10 °) on the substrate surface. The retardation value was 328 nm and haze value was 0.16.
When this film was heated on a hot plate at 200 ° C. for 30 minutes, the retardation value was 265 nm and the haze value was 0.16.

[Comparative Example 4] Polymerizable liquid crystal composition and polymer (film) thereof
Polymerizable liquid crystal compound (A1) 150 mg, polymerizable liquid crystal compound (A2) 90 mg, polymerizable liquid crystal compound (B1) 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.

A film was produced in the same manner as in Example 1 except that this polymerizable liquid crystal composition was used. The polymerizable composition on the substrate after pre-baking was in a liquid crystal state.
The film thickness of the obtained film was 1.8 μm, and when observed with a polarizing microscope, it was confirmed that the film was horizontally oriented (tilt <10 °) on the substrate surface. The retardation value was 289 nm and haze value was 0.16.
When this film was heated on a hot plate at 200 ° C. for 30 minutes, the retardation value was 209 nm and the haze value was 0.16.

[Comparative Example 5] Polymerizable liquid crystal composition and polymer (film) thereof
Polymeric liquid crystal compound (A1) 150 mg, polymerizable liquid crystal compound (A2) 150 mg, polyvalent acrylate compound (C4) 9 mg, Ciba Geigy's Irgacure 369 (trade name) 4 mg, which is 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.

A film was produced in the same manner as in Example 1 except that this polymerizable liquid crystal composition was used. The polymerizable composition on the substrate after pre-baking was in a liquid crystal state.
The film thickness of the obtained film was 1.8 μm, and when observed with a polarizing microscope, it was confirmed that the film was horizontally oriented (tilt <10 °) on the substrate surface. The retardation value was 258 nm and haze value was 1.49.
When this film was heated on a hot plate at 200 ° C. for 30 minutes, the retardation value was 18 nm and the haze value was 0.24.

The summary of Examples 1 to 6 and Comparative Examples 1 to 5 is shown in Table 3 below. In Table 3, Δnd value thermal stability (%) is the ratio of Δnd value after baking to Δnd value before baking.
In addition, the retardation value angle dependency of the films prepared in Examples 1 to 6 at a wavelength of 590 nm is shown in FIG. 1, and the retardation value angle dependency of the films prepared in Comparative Examples 1 to 5 at a wavelength of 590 nm is shown in FIG. Show.

Next, the control of the alignment mode (horizontal or hybrid) by the alignment film manufacturing process will be described with examples.

[Example 7] Polymerizable liquid crystal composition and polymer (film) thereof
Polymerizable liquid crystal compound (A1) 150 mg, polymerizable liquid crystal compound (A2) 90 mg, polymerizable liquid crystal compound (B1) 60 mg, and polyvalent acrylate compound (C4) 4.5 mg, Irgacure 369 manufactured by Ciba Geigy Co., which is a photopolymerization initiator (Product name) 4 mg and surfactant R30 (manufactured by DIC Corporation) 0.6 mg 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 has a thickness obtained by applying a liquid crystal alignment agent (PAOC-120 manufactured by Nissan Chemical Industries, Ltd.) to the ITO surface of a glass substrate with ITO by spin coating and baking at 130 ° C. After forming a 200 nm thin film, it is irradiated with polarized UV light of 500 mJ / cm ² obliquely (40 °).

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 film thickness of the obtained film was 1.8 μm, and when observed with a polarizing microscope, it was confirmed that the film was hybrid-aligned on the substrate surface (average tilt 40 °). The retardation value was 143 nm and the haze value was 0.13.

[Example 8] Polymerizable liquid crystal composition and polymer (film) thereof
The polymerizable liquid crystal composition obtained in Example 7 was 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) and prebaked on a hot plate at 100 ° C. for 60 seconds. Then, it was left to cool to room temperature. 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 has a thickness obtained by applying a liquid crystal alignment agent (PAOC-120 manufactured by Nissan Chemical Industries, Ltd.) to the ITO surface of a glass substrate with ITO by spin coating and baking at 130 ° C. After forming a 200 nm thin film, it was irradiated with polarized UV light of 1,000 mJ / cm ² from directly above.

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 film thickness of the obtained film was 1.8 μm, and when observed with a polarizing microscope, it was confirmed that the film was horizontally aligned on the substrate surface. The retardation value was 306 nm and the haze value was 0.13.

FIG. 3 shows the retardation value angle dependency of the films prepared in Examples 7 and 8 at a wavelength of 590 nm.

The polymer obtained from the composition of the present invention can be suitably used as an optically anisotropic film such as a polarizing plate or a retardation plate.

Claims

(A) at least one selected from polymerizable liquid crystal compounds represented by the following formula [1],
(B) at least one selected from polymerizable liquid crystal compounds represented by the following formula [2], and (C) at least one structure selected from a trimethylolpropane structure, a pentaerythritol structure, and an ethylene glycol structure, or from these Containing at least one selected from polyhydric acrylate compounds obtained from polyhydric alcohols having 3 to 50 oxygen atoms in total and acrylic acid or derivatives thereof, having a structure in which at least one selected is condensed. A polymerizable liquid crystal composition characterized by the above.

[Wherein R 1 , R 3 and R 4 each independently represents the following formula [3] or [4]

(In the formula, X is a hydrogen atom or a methyl group. The broken line is a bond.)
It is an organic group represented by. R 2 is a hydrogen atom, a halogen atom, a cyano group or a methoxy group. n1, n2 and n3 are each independently an integer of 2 to 10. q is 0 or 1. p is 1 when q is 0, and 0 or 1 when q is 1. r is 1 or 2; s is 1 when r is 1 and 0 when r is 2. ]
The polymerizable liquid crystal composition according to claim 1, wherein the polyvalent acrylate compound (C) is represented by the following formula [5] or [6].

(In the formula, R 5 represents a methyl group, or the following formula [7] or [8].

It is an organic group represented by. n4 to n10 are each independently an integer of 0 to 10. n11 is an integer of 4 to 10. A broken line is a bond. )
The polymerizable liquid crystal composition according to claim 1, wherein the polymerizable liquid crystal compound (B) is represented by the following formula [9].

(Wherein n2, n3, r and s are the same as above)
A polymer obtained from the polymerizable liquid crystal composition according to any one of claims 1 to 3.
A film obtained from the polymerizable liquid crystal composition according to any one of claims 1 to 3.
A hybrid alignment film obtained from the polymerizable liquid crystal composition according to any one of claims 1 to 3.
An optical member comprising the oriented film according to claim 6.