JP5870932B2 - Polymerizable compound, polymerizable liquid crystal composition, polymer and alignment film - Google Patents

Description

  The present invention relates to a polymerizable compound having a benzophenone moiety, a polymerizable liquid crystal composition containing the polymerizable compound, and a polymer and an alignment film obtained using the polymerizable liquid crystal composition. Specifically, materials having optical properties such as display devices and recording materials, in particular, polymerizable compounds that can be suitably used for optical compensation films such as polarizing plates and retardation plates for liquid crystal displays, and polymerizable liquid crystal compositions containing the same And a polymer and an alignment film obtained from the polymerizable liquid crystal composition.

  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 of obtaining a polymer by supporting a specific polymerizable liquid crystal compound having an acrylic group between supports and irradiating the compound while maintaining the compound in a liquid crystal state (Patent Document 1: Japanese Patent Laid-Open No. 62-70407). And a method of obtaining a polymer by adding a photopolymerization initiator to a mixture of two kinds of polymerizable liquid crystal compounds having an acrylic group or a composition in which a chiral liquid crystal is mixed with this mixture and irradiating with ultraviolet rays. (Patent Document 2: JP-A-9-208957).

  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. 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.

On the other hand, when compared with an optically anisotropic film obtained from another process (for example, stretching of a polyvinyl alcohol film), the wavelength dependency of the optical anisotropy of the film obtained from the polymerizable liquid crystal compound is low. There is.
An anisotropic polymer obtained from a monomer having a benzophenone skeleton is also known (Patent Document 3: German Patent Application Publication No. 4226994).

JP-A-62-70407 JP-A-9-208957 German Patent Application No. 4226994

  The present invention has been made in view of such circumstances, and has a predetermined polymerizable compound having an α-methylene-γ-butyrolactone moiety and a benzophenone moiety, high optical anisotropy and high chemical resistance. An object of the present invention is to provide a polymerizable liquid crystal composition containing the polymerizable compound, which can give a polymer (film), and a polymer and an alignment film obtained from the polymerizable liquid crystal composition.

  As a result of intensive studies to solve the above problems, the present inventor has found that a predetermined polymerizable compound having an α-methylene-γ-butyrolactone moiety and a benzophenone moiety is excellent in polymerizability and is stable. And the polymer and film obtained from the polymerizable liquid crystal composition have high optical anisotropy and high chemical resistance, and the present invention has been completed.

（式中、ｎ１及びｎ２はそれぞれ独立に３〜１０の整数を表し、ｍは３〜１０の整数を表す。）
２．下記式［１］及び［２］で表される重合性化合物から選ばれる少なくとも１種と、液晶性化合物とを含有することを特徴とする重合性液晶組成物、

（式中、ｎ１及びｎ２はそれぞれ独立に３〜１０の整数を表し、ｍは３〜１０の整数を表す。）
３．上記液晶性化合物が、重合性基を有する液晶性化合物である２の重合性液晶組成物、
４．上記重合性基を有する液晶性化合物が、下記式［３］及び／又は［４］で表される重合性基を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．上記重合性基を有する液晶性化合物が、下記式［５］及び［６］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種の化合物である３又は４の重合性液晶組成物、

（式中、Ｍ¹、Ｍ²及びＭ³はそれぞれ独立に下記式［３］又は［４］

（式中、破線は結合手を表す。）
で表される基である。Ｘはフッ素原子、シアノ基又は炭素数が４〜８の１価炭化水素基である。ｆ１及び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。）
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の重合体又は８の配向フィルムを備える光学部材
を提供する。That is, the present invention
1. A polymerizable compound represented by the following formula [1] or [2]:

(In the formula, n1 and n2 each independently represent an integer of 3 to 10, and m represents an integer of 3 to 10.)
2. A polymerizable liquid crystal composition comprising at least one selected from polymerizable compounds represented by the following formulas [1] and [2], and a liquid crystal compound;

(In the formula, n1 and n2 each independently represent an integer of 3 to 10, and m represents an integer of 3 to 10.)
3. 2. The polymerizable liquid crystal composition, wherein the liquid crystal compound is a liquid crystal compound having a polymerizable group,
4). The polymerizable liquid crystal composition of 3, wherein the liquid crystalline compound having a polymerizable group is a compound having a polymerizable group represented by the following formula [3] and / or [4]:

(In the formula, a broken line represents a bond.)
5. 3 or 4 polymerizable liquid crystal composition, wherein the liquid crystalline compound having a polymerizable group is at least one compound selected from the group consisting of compounds represented by the following formulas [5] and [6]:

(In the formula, M ¹ , M ² and M ³ are each independently represented by the following formula [3] or [4]:

(In the formula, a broken line represents a bond.)
It is group represented by these. X is a fluorine atom, a cyano group, or a monovalent hydrocarbon group having 4 to 8 carbon atoms. f1 and f2 each independently represent an integer of 2 to 9, and g represents an integer of 2 to 9. )
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 is provided.

  The polymerizable liquid crystal composition containing the polymerizable compound of the present invention provides a polymer exhibiting high optical anisotropy and high chemical resistance. The film obtained from the polymerizable liquid crystal composition containing the polymerizable compound of the present invention does not show disorder of alignment and has a low haze value. Furthermore, the polymerizability of the liquid crystal composition is improved by adding the polymerizable compound of the present invention. In addition, in the film obtained from the liquid crystal composition to which the polymerizable compound of the present invention is added, alignment disorder is not observed. Therefore, the polymer obtained from the polymerizable liquid crystal composition containing the polymerizable compound of the present invention can be used as an optically anisotropic film such as a polarizing plate or a retardation plate, and in particular, using photolithography in the air. This is suitable for use in forming a pattern.

It is a graph which shows the angle dependence of the retardation value of the film of Example 3. It is a graph which shows the angle dependence of the retardation value of the film of Example 4. It is a graph which shows the angle dependence of the retardation value of the film of Example 5. It is a graph which shows the angle dependence of the retardation value of the film of Example 6. It is a graph which shows the angle dependence of the retardation value of the film of the comparative example 1. It is a graph which shows the thermal stability of (DELTA) nd of the film by the addition amount of a polymeric compound (Z1).

Hereinafter, the present invention will be described in more detail.
In the present specification, the “polymerizable liquid crystal compound” means a compound having a polymerizable group such as an acryl group or an α-methylene lactone ring in the molecule and exhibiting a liquid crystal phase. “Liquid crystal composition” means a composition having a characteristic of exhibiting a liquid crystal phase. "Liquid crystallinity" means exhibiting a liquid crystal phase.

（式中、ｎ１及びｎ２はそれぞれ独立に３〜１０の整数を表し、ｍは３〜１０の整数を表す。）[Polymerizable compound]
The polymerizable compound of the present invention is represented by the following formula [1] or [2].

(In the formula, n1 and n2 each independently represent an integer of 3 to 10, and m represents an integer of 3 to 10.)

The polymerizable compound represented by the formula [1] or [2] is a compound having a benzophenone moiety and an α-methylene-γ-butyrolactone moiety.
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 a high glass transition point (Tg) and heat resistance to the polymer obtained using this compound.

  The benzophenone part of the polymerizable compound represented by the formula [1] or [2] is a sensitization part of photopolymerization, and undergoes a dimerization reaction with light to obtain a crosslinked polymer. Therefore, the sensitivity of the material can be improved by using the polymerizable compound of the present invention.

  In formula [1] or [2], the repeating part of the methylene group is a so-called spacer part. Here, n1, n2 and m represent the number of repeating methylene groups and are each independently an integer of 3 to 10, preferably an integer of 4 to 6.

Examples of the polymerizable compound include compounds represented by the following formulas (1) to (29), but are not limited thereto.

[Synthesis of polymerizable compounds]
The polymerizable 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, pp. 56- 59 (1983)).

（式中、Ｒは１価の有機基を表す。ＴＨＦはテトラヒドロフランを表す。Ａｍｂｅｒｌｙｓｔ（登録商標）１５は、ロームエンドハース社製イオン交換樹脂である。）

(In the formula, R represents a monovalent organic group. THF represents tetrahydrofuran. Amberlyst (registered trademark) 15 is an ion exchange resin manufactured by Rohm End Haas).

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 in the case of using acetal or ketal is shown in the following scheme (A2).

（式中、Ｒは上記と同じ。破線は結合手を表す。）

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

  An intermediate of the compound represented by the formula [1] or [2] can be synthesized by the method of the following synthesis scheme (B) applying the method of the above synthesis scheme (A1) or (A2).

（式中、ｎは上記と同じ。ＰＣＣはピリジニウムクロロクロマートを表す。）

(In the formula, n is the same as above. PCC represents pyridinium chlorochromate.)

  The polymerizable compound represented by the formula [1] can be synthesized according to the following synthesis scheme (C).

（式中、ｎは上記と同じ。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 is the same as above. DCC represents dicyclohexylcarbodiimide, and DMAP represents N, N-dimethyl-4-aminopyridine.)

  When n = m in the formula [2], the compound represented by the formula [2] can be synthesized according to the following synthesis scheme (D).

（式中、ｎは上記と同じ。）

(Wherein n is the same as above)

  In the case of n ≠ m in the formula [2], the compound represented by the formula [2] can be synthesized according to the following synthesis scheme (E).

（式中、ｎ及びｍは上記と同じ。）

(In the formula, n and m are the same as above.)

[Polymerizable liquid crystal composition]
The polymerizable liquid crystal composition according to the present invention includes at least one selected from the polymerizable compounds represented by the above formulas [1] and [2] and a compound having a liquid crystal structure site (hereinafter referred to as a specific compound). Is obtained by mixing. The specific compound to mix can also be used individually by 1 type or in combination of multiple types.
The said specific compound needs to be a compound (liquid crystalline compound) which exhibits liquid crystallinity. The said specific compound may have polymeric groups, such as an acryl group and a lactone ring, and does not need to have it. In the case of having a polymerizable group, the specific compound may be monofunctional or polyfunctional.

（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 [3] or [4].

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

（式中、Ｍ¹、Ｍ²及びＭ³はそれぞれ独立に上記式［３］又は［４］で表される基である。Ｘはフッ素原子、シアノ基又は炭素数が４〜８の１価炭化水素基である。ｆ１及び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 [5] or [6] is particularly preferable.

(In the formula, M ¹ , M ² and M ³ are each independently a group represented by the above formula [3] or [4]. 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 compounding ratio of the specific compound is not particularly limited, but is preferably 900 to 200 parts by mass, more preferably 100 parts by mass with respect to 100 parts by mass of the polymerizable compound represented by the formula [1] and / or [2]. It is 400-200 mass parts.

  Specific examples of the specific compound include compounds represented by the following formulas (30) to (120), nematic liquid crystals, ferroelectric liquid crystals, commercially available liquid crystal compositions, and the like, but are not limited thereto. is not.

  In the polymerizable liquid crystal composition of the present invention, a photopolymerization initiator, a thermal polymerization initiator, a sensitizer and the like 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, 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 5 parts by mass or less with respect to 100 parts by mass of the total amount of the polymerizable compound represented by the formula [1] and / or [2] and the specific compound having a polymerizable group. Is more preferable, and 0.5 to 2.0 parts by mass is more preferable.

  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 a polymerizable compound represented by the formula [1] and / or [2] and a specific compound having a polymerizable group. 5 parts by mass or less is preferable with respect to a total of 100 parts by mass, and more preferably 0.5 to 2.0 parts by mass.

  The photopolymerization initiator can be used in combination with at least one of thermal polymerization initiators.

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 amount added is the sum of the polymerizable compound represented by the formula [1] and / or [2] and the specific compound having a polymerizable group. 0.1 mass part or less is preferable with respect to 100 mass parts.

  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.

  Adhesion promoters include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, chloromethyldimethylchlorosilane; trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylvinylethoxysilane, diphenyldimethoxysilane, phenyltri Alkoxysilanes such as ethoxysilane; silazanes such as hexamethyldisilazane, N, N′-bis (trimethylsilyl) urea, dimethyltrimethylsilylamine, trimethylsilylimidazole; vinyltrichlorosilane, γ-chloropropyltrimethoxysilane, γ-amino Propyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, Silanes such as-(N-piperidinyl) propyltrimethoxysilane; benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazole, thiouracil, mercaptoimidazole, Heterocyclic compounds such as mercaptopyrimidine; urea compounds such as 1,1-dimethylurea and 1,3-dimethylurea, and thiourea compounds.

  The adhesion promoter can be used singly or in combination of two or more, and the amount of the adhesion promoter is determined between the polymerizable compound represented by the formula [1] and / or [2] and the specific compound having a polymerizable group. 1 mass part or less is preferable with respect to a total of 100 mass parts.

  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 methyl Diglycol dialkyl ethers such as ethyl 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 mono Diglycol monoalkyl ethers such as ethyl 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 Emissions, 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 working environment.

  These organic solvents can be used alone or in combination of two or more. 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, and a fluorine-based surfactant having a high effect of improving affinity with a substrate is preferable.

  Specific examples of the fluorosurfactant (hereinafter referred to as “trade name”), F-top EF301, EF303, EF352 (manufactured by Tochem Products), MegaFuck F171, F173, R-30 (Dainippon Ink Chemical Industries, Ltd.) ), Florard FC430, FC431 (Sumitomo 3M), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.) However, it is not limited to these. In addition, surfactant can also be used individually by 1 type or in combination of multiple types.

  As a suitable example of the polymerizable liquid crystal composition of the present invention, at least one selected from the polymerizable compounds represented by the formulas [1] and [2] is 100 parts by mass, the specific compound is 400 to 200 parts by mass, and photoinitiation. And a liquid crystal composition composed of 5 parts by mass or less of the agent.

  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 as 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 to exhibit a stable liquid crystal phase at room temperature (20 to 40 ° C., the same applies hereinafter). When the polymerizable liquid crystal composition contains an organic solvent, it is preferable that a stable 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 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 spin coating or casting method. It is done.

  As the substrate, glass, quartz, a plastic sheet, a color filter, a plastic film such as triacetyl cellulose (TAC), or the like can be used. Of the two substrates, one substrate is a belt or drum on which a functional thin film such as ITO is formed, a plastic sheet, a plastic film, and a metal such as stainless steel, chrome, or aluminum. It is also possible to use it.

  The substrate to be used is preferably subjected to orientation treatment for the purpose of improving the orientation of the resulting film. As a method of alignment treatment, a method of applying an alignment material containing a polyimide precursor, polyimide, polyvinyl cinnamate, etc. and irradiating with rubbing or polarized ultraviolet rays, a method of forming an oblique deposition film of silicon dioxide , Can be appropriately selected from known methods such as a method of 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 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 multi-domaining in the polymerization step is to form a polymerized domain by exposing the polymerizable liquid crystal composition in a liquid crystal state to ultraviolet rays through a mask, and the remaining domains are polymerized in an isotropic liquid state. Methods and the like.

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. According to these methods, it is possible to obtain a multi-domained substrate in which the rubbed domain and the domain irradiated with ultraviolet rays are the alignment-treated portions 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.

  Since the film obtained from the polymerizable liquid crystal composition of the present invention has optical anisotropy, it can be suitably used for a polarizing plate, a retardation plate and the like.

  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 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 was identified by heating the sample on a hot stage (MATS-2002S, manufactured by Tokai Hit) and using a polarizing microscope (manufactured by Nikon). The phase transition temperature was measured using a differential scanning calorimeter (DSC3100SR) manufactured by Bruker AXS, Inc. under 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 of wavelength 590nm was measured using the retardation measuring apparatus (RETS-100, Otsuka Electronics Co., Ltd. product).

[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 a temperature of 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 to obtain 8.7 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 white solid was 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 2,6-di-tert-butyl-p-cresol (BHT) 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. 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 0.5N 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 (E1) was obtained.
The measurement result of ¹ H-NMR was as follows.
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 50 mL of acetone 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). The solvent was distilled off from the resulting solution to obtain 6.9 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 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, intermediate compound obtained above in a state where 2.2 g (10.0 mmol) of pyridinium chlorochromate (PCC) and 30.0 mL of CH ₂ Cl ₂ were added to a 200 mL three-necked flask with a cooling tube and mixed by stirring. A solution prepared by dissolving 2.95 g (10.0 mmol) of (A2) in CH ₂ Cl ₂ (50.0 mL) 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 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 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). The solvent of the obtained solution was distilled off to obtain 2.8 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 (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 & Co., eluent: hexane / ethyl acetate = 2/1). The solvent of the obtained solution was distilled off to obtain 1.5 g of a white solid. From the result of measurement by NMR, it was confirmed that this white solid was the target polymerizable liquid crystal compound (E2) (yield 41%).
The measurement result of ¹ H-NMR was as follows.
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)
Further, 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 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 (E3) [1] Synthesis of intermediate compound (A3)

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 a temperature of 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 & Co., eluent: hexane / ethyl acetate = 1/1). The solvent was distilled off from the resulting solution to obtain 11.3 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 (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, intermediate compound (A3) obtained in the same manner as described above in a state where PCC 2.2 g (10.0 mmol) and CH ₂ Cl ₂ 15.0 mL were placed in a 100 mL three-neck flask with a cooling tube and stirred and mixed. A solution prepared by dissolving 2.5 g (10.0 mmol) in CH ₂ Cl ₂ (15.0 mL) 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). 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 at 70 ° C. for 5 hours with stirring. . 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.
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 1.5 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 (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 10% 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, stirred for 30 minutes at room temperature, 5 mL of 10% hydrochloric acid was added dropwise, and filtered 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 tetrahydrofuran were added to a 50 mL eggplant flask equipped with a cooling tube to form a mixture, and the mixture was stirred at a temperature of 70 ° C. for 5 hours. And reacted. After completion of the reaction, the solvent was distilled off from the solution after the reaction solution was filtered under reduced pressure to obtain a yellow solid. The yellow solid was purified by recrystallization (hexane / ethyl acetate = 1/1) to obtain 0.9 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 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 washed successively with each 80 mL saturated aqueous sodium hydrogen carbonate solution, 0.5N hydrochloric acid and saturated brine. After drying over 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)

In a 500 mL eggplant flask 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 (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)

Intermediate compound (D3) 6.1 g (20.0 mmol), intermediate compound (G3) 6.0 g (20.0 mmol), N, N-dimethyl-4-aminopyridine (DMAP) 0.08 g and a small amount of BHT The suspension was suspended in 10 mL of methylene chloride with stirring at room temperature, and 4.7 g (23.0 mmol) of dicyclohexylcarbodiimide (DCC) dissolved in 20 mL of methylene chloride was added thereto and stirred overnight, and the precipitated DCC urea was filtered off. The filtrate was successively washed twice with 60 mL each of 0.5N hydrochloric acid, saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over magnesium sulfate, the solvent was distilled off, and recrystallization with ethanol, 8.8 g of a polymerizable liquid crystal compound (E3) was obtained (yield 75%).
The measurement result of ¹ H-NMR was as follows.
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, 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 (E3), at the time of temperature rise, the phase transitioned to a smectic X phase at a temperature of 109 ° C., a phase transition to a nematic phase at a temperature of 144 ° C., and an isotropic liquid at a temperature of 168 ° C. It became a state.

[Example 1] Synthesis of polymerizable compound (Z1)

Intermediate compound (D3) 6.1 g (20.0 mmol), 4-hydroxybenzophenone 4.0 g (20.0 mmol), DMAP 0.1 g, and a small amount of BHT were suspended in 80 mL of methylene chloride at room temperature with stirring. Then, DCC 5.2g (25.0mmol) was added thereto and stirred overnight. The precipitated DCC urea was filtered off, and the filtrate was washed twice with 50 mL of 0.5N hydrochloric acid, 50 mL of saturated aqueous sodium hydrogen carbonate solution and 100 mL of saturated brine successively, dried over magnesium sulfate, and then the solvent under reduced pressure. Was distilled off to obtain a yellow solid. This solid was purified by recrystallization (ethanol) to obtain 7.2 g of the target polymerizable compound (Z1) (yield 74%).
The measurement result of ¹ H-NMR was as follows.
¹ H-NMR (CDCl ₃ ) δ: 1.40-1.95 (m, 8H), 2.58 (m, 1H), 3.07 (m, 1H), 4.07 (t, 2H), 4.55 (m, 1H), 5.64 (s , 1H), 6.25 (s, 1H), 6.99 (d, 2H), 7.35 (d, 2H), 7.48 (m, 2H), 7.61 (m, 1H), 7.82 (d, 2H), 7.92 (d, 2H), 8.17 (d, 2H)

[Example 2] Synthesis of polymerizable compound (Z2)

Intermediate compound (D3) 6.1 g (20.0 mmol), 4,4′-dihydroxybenzophenone 2.1 g (10.0 mmol), DMAP 0.1 g, and a small amount of BHT were stirred at room temperature in 80 mL of methylene chloride. To the suspension, 5.2 g (24.0 mmol) of DCC was added and stirred overnight. The precipitated DCC urea was filtered off, and the filtrate was washed twice with 50 mL of 0.5N hydrochloric acid, 50 mL of saturated aqueous sodium hydrogen carbonate solution and 100 mL of saturated brine successively, dried over magnesium sulfate, and then the solvent under reduced pressure. Was distilled off to obtain a yellow solid. This solid was purified by recrystallization using ethanol to obtain 6.2 g of a white solid. The result of having measured this solid by NMR is shown below. From the result of measurement by NMR, it was confirmed that this white solid was a polymerizable compound (Z2) (yield 79%).
The measurement result of ¹ H-NMR was as follows.
¹ H-NMR (CDCl ₃ ) δ: 1.45-1.95 (m, 16H), 2.58 (m, 2H), 3.07 (m, 2H), 4.05 (t, 4H), 4.54 (m, 2H), 5.64 (s , 2H), 6.24 (s, 2H), 6.98 (d, 4H), 7.32 (d, 4H), 7.91 (d, 4H), 8.18 (d, 4H)

[Examples 3 to 6, Comparative Example 1] Preparation of polymerizable liquid crystal composition and evaluation of polymer (film) The compounds used in the following Examples and Comparative Examples are as follows. Table 1 summarizes the compositions of the compositions prepared in Examples 3 to 6 and Comparative Example 1.

[Example 3]
Polymerizable liquid crystal compound (E1) 120 mg, polymerizable liquid crystal compound (E2) 90 mg, polymerizable liquid crystal compound (E3) 60 mg, polymerizable compound (Z1) 30 mg, Irgacure 369 (trade name) manufactured by Ciba Geigy Co., which is a photopolymerization initiator 4 mg and 0.6 mg of surfactant R-30 (Dainippon Ink Chemical Co., Ltd.) were dissolved in 0.70 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), prebaked on a hot plate at a temperature of 100 ° C. for 60 seconds, and then released to room temperature. Chilled. 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 applied to the ITO surface of the glass substrate with ITO by spin coating with a liquid crystal alignment agent (SE-1410 manufactured by Nissan Chemical Industries, Ltd.), baked at a temperature of 230 ° C., and a thickness of 100 nm. After the thin film was formed, rubbing treatment was performed.

Next, the polymerizable liquid crystal composition was polymerized by irradiating the coating film formed on the substrate with a liquid crystal alignment film in the air with light having a strength of 2,000 mJ / cm ² using a metal halide lamp.
The obtained film had a thickness of 1.9 μm, and when observed with a polarizing microscope, it was confirmed that the film was horizontally (tilted) oriented on the substrate surface. And the retardation value was 288 nm ((DELTA) nd1) and haze value was 0.16.
When this film was heated on a hot plate at 160 ° C. for 30 minutes, the retardation value was 240 nm (Δnd 2), 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 retardation value was 207 nm (Δnd 3) and the haze value was 0.09.

[Example 4]
Polymerizable liquid crystal compound (E1) 90 mg, polymerizable liquid crystal compound (E2) 90 mg, polymerizable liquid crystal compound (E3) 60 mg, polymerizable compound (Z1) 60 mg, Irgacure 369 (trade name) manufactured by Ciba Geigy Co., which is a photopolymerization initiator 4 mg and 0.6 mg of surfactant R-30 (Dainippon Ink Chemical Co., Ltd.) were dissolved in 0.70 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), prebaked on a hot plate at a temperature of 100 ° C. for 60 seconds, and then released to room temperature. Chilled. 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 applied to the ITO surface of the glass substrate with ITO by spin coating with a liquid crystal alignment agent (SE-1410 manufactured by Nissan Chemical Industries, Ltd.), baked at a temperature of 230 ° C., and a thickness of 100 nm. After the thin film was formed, rubbing treatment was performed.

Next, the polymerizable liquid crystal composition was polymerized by irradiating the coating film formed on the substrate with a liquid crystal alignment film in the air with light having a strength of 2,000 mJ / cm ² using a metal halide lamp.
The obtained film had a thickness of 1.9 μm, and when observed with a polarizing microscope, it was confirmed that the film was horizontally (tilted) oriented on the substrate surface. And the retardation value ((DELTA) nd1) was 267 nm, and haze value was 0.08.
When this film was heated on a hot plate at 160 ° C. for 30 minutes, the retardation value (Δnd 2) was 233 nm and the haze value was 0.16.
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 retardation value (Δnd 3) was 203 nm and the haze value was 0.09.

[Example 5]
Polymerizable liquid crystal compound (E1) 90 mg, polymerizable liquid crystal compound (E2) 60 mg, polymerizable liquid crystal compound (E3) 60 mg, polymerizable compound (Z1) 90 mg, Irgacure 369 (trade name) manufactured by Ciba Geigy Co., which is a photopolymerization initiator 4 mg and 0.6 mg of surfactant R-30 (Dainippon Ink Chemical Co., Ltd.) were dissolved in 0.70 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), prebaked on a hot plate at a temperature of 100 ° C. for 60 seconds, and then released to room temperature. Chilled. 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 applied to the ITO surface of the glass substrate with ITO by spin coating with a liquid crystal alignment agent (SE-1410 manufactured by Nissan Chemical Industries, Ltd.), baked at a temperature of 230 ° C., and a thickness of 100 nm. After the thin film was formed, rubbing treatment was performed.

Next, the polymerizable liquid crystal composition was polymerized by irradiating the coating film formed on the substrate with a liquid crystal alignment film in the air with light having a strength of 2,000 mJ / cm ² using a metal halide lamp.
The obtained film had a thickness of 1.9 μm, and when observed with a polarizing microscope, it was confirmed that the film was horizontally (tilted) oriented on the substrate surface. And the retardation value ((DELTA) nd1) was 255 nm, and the haze value was 0.08.
When this film was heated on a hot plate at 160 ° C. for 30 minutes, the retardation value (Δnd2) was 228 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 retardation value (Δnd 3) was 204 nm and the haze value was 0.08.

[Example 6]
Polymerizable liquid crystal compound (E1) 90 mg, polymerizable liquid crystal compound (E2) 90 mg, polymerizable liquid crystal compound (E3) 60 mg, polymerizable compound (Z2) 60 mg, Irgacure 369 (trade name) manufactured by Ciba Geigy Co., which is a photopolymerization initiator 4 mg and 0.6 mg of surfactant R-30 (Dainippon Ink Chemical Co., Ltd.) were dissolved in 0.70 g of cyclohexanone to obtain a polymerizable liquid crystal composition.
This polymerizable liquid crystal composition was applied to the liquid crystal alignment film surface of the substrate with a liquid crystal alignment film by spin coating (1000 rpm, 20 seconds), pre-baked on a hot plate at a temperature of 100 ° C. for 60 seconds, and then allowed 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 was applied to the ITO surface of the glass substrate with ITO by spin coating with a liquid crystal alignment agent (SE-1410 manufactured by Nissan Chemical Industries, Ltd.), baked at a temperature of 230 ° C., and a thickness of 100 nm. After the thin film was formed, rubbing treatment was performed.

Next, the polymerizable liquid crystal composition was polymerized by irradiating the coating film formed on the substrate with a liquid crystal alignment film in the air with light having a strength of 2,000 mJ / cm ² using a metal halide lamp.
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 (tilted) oriented on the substrate surface. And the retardation value was 267 nm ((DELTA) nd1) and haze value was 0.08.
When this film was heated on a hot plate at 160 ° C. for 30 minutes, the retardation value was 245 nm (Δnd 2), 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 retardation value was 218 nm (Δnd 3) and the haze value was 0.08.

[Comparative Example 1]
Polymeric liquid crystal compound (E1) 150 mg, polymerizable liquid crystal compound (E2) 90 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 R-30 (Dainippon Ink Chemical Co., Ltd.) was dissolved in 0.70 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), prebaked on a hot plate at a temperature of 100 ° C. for 60 seconds, and then released to room temperature. Chilled. 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 applied to the ITO surface of the glass substrate with ITO by spin coating with a liquid crystal alignment agent (SE-1410 manufactured by Nissan Chemical Industries, Ltd.), baked at a temperature of 230 ° C., and a thickness of 100 nm. After the thin film was formed, rubbing treatment was performed.

Next, the polymerizable liquid crystal composition was polymerized by irradiating the coating film formed on the substrate with a liquid crystal alignment film in the air with light having a strength of 2,000 mJ / cm ² using a metal halide lamp.
The obtained film had a thickness of 1.9 μm, and when observed with a polarizing microscope, it was confirmed that the film was horizontally (tilted) oriented on the substrate surface. And the retardation value was 299 nm ((DELTA) nd1), and haze value was 0.09.
When this film was heated on a hot plate at 160 ° C. for 30 minutes, the retardation value was 234 nm (Δnd 2), 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 retardation value (Δnd 3) was 205 nm and the haze value was 0.08.

1 to 5 show the angle dependency of the retardation value of the film. In the figure, Angle is incident angle, No Bake is processed only by exposure, Ageing is baked for 30 minutes at 160 ° C., Bake is baked for 60 minutes at 200 ° C. after aging, Represent each.
Comparing Examples 1 to 4 (FIGS. 1 to 4) and Comparative Example 1 (FIG. 5), it can be seen that the lines of No Bake and Ageing are closer in FIGS. 1 to 4, thereby improving the polymerizability. I found out that

FIG. 6 is a graph showing the thermal stability of Δnd of the film depending on the amount of the polymerizable compound (Z1) added.
In FIG. 6, Stability is stability, BPGBL Addition is the addition amount of the polymerizable compound (Z1), Ageing is baking at 160 ° C. for 30 minutes, and Bake is baking at 200 ° C. for 60 minutes after Ageing. Respectively.
In the case of Ageing, Δnd Stability (%) is
Δnd Stability (%) = (Δnd2 / Δnd1) × 100
In the case of Bake,
Δnd Stability (%) = (Δnd3 / Δnd2) × 100
It was calculated according to
Δnd1, Δnd2, and Δnd3 are respectively Comparative Example 1 (Compound Z1, 0% addition amount), Example 3 (Compound Z1, 10% addition amount), Example 4 (Compound Z1, 20% addition amount), Example The value obtained in 5 (Compound Z1, 30% addition amount) was used.
From FIG. 6, it was found that as the amount of the compound (Z1) added was increased, retardation similar to that of Bake was obtained only with Ageing, and it was found that the polymerizability was improved.

The above results are summarized in Table 2.

[Example 7, Comparative Example 2] Evaluation of film reduction [Example 7]
The polymerizable liquid crystal composition prepared in Example 4 was applied to the liquid crystal alignment film surface of the substrate with the liquid crystal alignment film by spin coating (1,000 rpm, 20 seconds) and prebaked on a hot plate at a temperature of 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 was applied to the ITO surface of the glass substrate with ITO by spin coating with a liquid crystal alignment agent (SE-1410 manufactured by Nissan Chemical Industries, Ltd.), baked at a temperature of 230 ° C., and a thickness of 100 nm. After the thin film was formed, rubbing treatment was performed.

Next, the coating film formed on the substrate with the liquid crystal alignment film is masked half, and half is exposed to light having an intensity of 2,000 mJ / cm ² using a metal halide lamp in the air. After the composition was polymerized, development was performed using propylene glycol monomethyl ether acetate (PGMEA) for 20 seconds at room temperature, and rinsing was performed using PGMEA for 10 seconds at room temperature. Thereafter, it was confirmed that there were no unexposed portions.
The film thickness of the exposed area after development was 1.9 μm, and when compared with the film thickness of the film of Example 4, no decrease in film thickness was observed. That is, it was shown that the film of an example has high chemical resistance.
Moreover, when the film after image development was observed with the polarization microscope, it confirmed that the film was horizontally aligned on the substrate surface. And the retardation value was 250 nm and haze value was 0.16.

[Comparative Example 2]
The polymerizable liquid crystal composition prepared in Comparative Example 1 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 a temperature of 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 was applied to the ITO surface of the glass substrate with ITO by spin coating with a liquid crystal alignment agent (SE-1410 manufactured by Nissan Chemical Industries, Ltd.), baked at a temperature of 230 ° C., and a thickness of 100 nm. After the thin film was formed, rubbing treatment was performed.

Next, the coating film formed on the substrate with the liquid crystal alignment film is masked half, and half is exposed to light having an intensity of 2,000 mJ / cm ² using a metal halide lamp in the air. After polymerizing the composition, development was performed using PGMEA for 20 seconds at room temperature, and rinsing was performed using PGMEA for 10 seconds at room temperature. Thereafter, it was confirmed that there were no unexposed portions.
The film thickness of the exposed area after development was 1.5 μm. When compared with the film thickness of the film of Comparative Example 1, the film thickness was reduced to 79%. That is, it was shown that the film of the comparative example was inferior in chemical resistance as compared with the film of the example.
Moreover, when the film after image development was observed with the polarization microscope, it confirmed that the film was horizontally aligned on the substrate surface. And the retardation value was 221 nm and haze value was 3.6.

  Table 3 summarizes the results of pattern film reduction evaluation.

  The polymer obtained from the polymerizable liquid crystal composition containing the polymerizable compound of the present invention can be used as an optically anisotropic film such as a polarizing plate or a retardation plate, and is particularly patterned in the air using photolithography. It is suitable for use for forming.

Claims (9)

A polymerizable compound represented by the following formula [1] or [2].

(In the formula, n1 and n2 each independently represent an integer of 3 to 10, and m represents an integer of 3 to 10.) A polymerizable liquid crystal composition comprising at least one selected from polymerizable compounds represented by the following formulas [1] and [2] and a liquid crystal compound.

(In the formula, n1 and n2 each independently represent an integer of 3 to 10, and m represents an integer of 3 to 10.)   The polymerizable liquid crystal composition according to claim 2, wherein the liquid crystal compound is a liquid crystal compound having a polymerizable group. The polymerizable liquid crystal composition according to claim 3, wherein the liquid crystalline compound having a polymerizable group is a compound having a polymerizable group represented by the following formula [3] and / or [4].

(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 having a polymerizable group is at least one compound selected from the group consisting of compounds represented by the following formulas [5] and [6]. object.

(In the formula, M ¹ , M ² and M ³ are each independently represented by the following formula [3] or [4]:

(In the formula, a broken line represents a bond.)
It is group represented by these. X is a fluorine atom, a cyano group, or a monovalent hydrocarbon group having 4 to 8 carbon atoms. f1 and f2 each independently represent an integer of 2 to 9, and g represents an integer of 2 to 9. )   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.

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