JPWO2017138509A1 - Liquid crystal composition and single layer coating type horizontal alignment film - Google Patents

Abstract

(A) a polymer containing a repeating unit represented by the following formula [1a], [1b] and [1c], (B) a liquid crystal property represented by the following formula [7a], [7b] or [7c]. Provided is a liquid crystal composition comprising a compound not shown and (C) an organic solvent.

Description

  The present invention relates to a liquid crystal composition and a single-layer coating type horizontal alignment film. Specifically, a liquid crystal composition having optical characteristics suitable for applications such as a display device and a recording material, and particularly suitable for producing optical compensation films such as polarizing plates and retardation plates for liquid crystal displays, and the composition The present invention relates to a single-layer coating type horizontal alignment film obtained from a product.

  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).

  In addition, an alignment film using a polymerizable liquid crystal compound or polymer that does not require a liquid crystal alignment film (Patent Documents 3 and 4), or an alignment film using a polymer containing a photocrosslinking site (Patent Documents 5 and 6). A variety of single-layer coated orientation films have been reported.

  The present inventors have reported a material for enabling production of a single-layer coating type horizontal alignment film having a high refractive index anisotropy (Δn) by a simple process (Patent Document 7). However, a film having a higher refractive index anisotropy (Δn) is required.

JP-A-62-70407 JP-A-9-208957 European Patent Application No. 1093025 International Publication No. 2008/031243 JP 2008-164925 A JP 11-189665 A International Publication No. 2013/133078

  The present invention has been made in view of the above problems, and is obtained from a liquid crystal composition capable of producing a single-layer coating type horizontal alignment film having a higher refractive index anisotropy (Δn), and the liquid crystal composition. An object is to provide a single-layer coating type horizontal alignment film.

  As a result of intensive studies to solve the above problems, the present inventor has a polymer having a cinnamate structure on a side chain containing a γ-butyrolactone skeleton in the main chain and extending from the γ position of the lactone ring. In addition, a film obtained from a composition containing a compound that does not exhibit a predetermined liquid crystallinity and an organic solvent can be subjected to low-temperature treatment, whereby a horizontal alignment film having a higher refractive index anisotropy (Δn) is obtained. As a result, the present invention has been completed.

［式中、Ｘ及びＹは、それぞれ独立に、下記式［２］又は［３］で表される基であり、

（式中、Ｒ¹は、水素原子又はメチル基であり、破線は、結合手である。）
Ｍ¹は、下記式［４］で表される基であり、Ｍ²は、下記式［５］又は［６］で表される基であり、

（式中、ｓ１、ｓ２、ｓ３、ｓ４、ｓ５及びｓ６は、それぞれ独立に、１又は２であり、Ｇ¹及びＧ²は、それぞれ独立に、単結合、−ＣＯＯ−又は−ＯＣＯ−であり、Ｒ²及びＲ³は、それぞれ独立に、水素原子、ハロゲン原子、シアノ基、炭素数１〜１０のアルキル基、又は炭素数１〜１０のアルコキシ基であり、Ｒ⁴は、炭素数１〜３のアルキル基であり、破線は結合手である。）
Ａは、炭素数２〜１５の直鎖状又は分岐状のアルキル基であり、
ｍ、ｎ及びｐは、それぞれ０＜ｍ＜１、０＜ｎ＜１、０≦ｐ≦０.５、かつ、ｍ＋ｎ＋ｐ≦１を満たす数であり、
ｑ及びｒは、それぞれ独立に、２〜９の整数である。］

（式中、Ｒ⁵及びＲ⁶は、それぞれ独立に、−ＯＨ、−ＯＣＨ₃、−Ｃ(＝Ｏ)ＯＨ、−Ｃ(＝Ｏ)ＯＣＨ₃、−Ｃ(＝Ｏ)ＯＣＨ₂ＣＨ₃又は−ＯＣ(＝Ｏ)ＣＨ₃であり、Ｒ⁷及びＲ⁸は、それぞれ独立に、水素原子、−ＯＨ、−ＯＣＨ₃、−Ｃ(＝Ｏ)ＯＨ、−Ｃ(＝Ｏ)ＯＣＨ₃、−Ｃ(＝Ｏ)ＯＣＨ₂ＣＨ₃又は−ＯＣ(＝Ｏ)ＣＨ₃であり、Ｇ³は、単結合、−Ｃ(＝Ｏ)−Ｏ−又は−Ｏ−Ｃ(＝Ｏ)−であり、Ｇ⁴は、単結合、−ＣＨ＝ＣＨ−又は−ＣＨ₂ＣＨ₂−である。）
２．１の液晶組成物を用いて作製された単層塗布型水平配向フィルム。
３．２の単層塗布型水平配向フィルムを備える光学部材。
４．１の液晶組成物を基板に塗布する工程、偏光を照射する工程、及びポストベークをする工程を含む、単層塗布型水平配向フィルムの製造方法。
５．前記偏光が、直線偏光紫外線である４の単層塗布型水平配向フィルムの製造方法。That is, the present invention provides the following liquid crystal composition and single-layer coating type horizontal alignment film.
1. (A) a polymer containing repeating units represented by the following formulas [1a], [1b] and [1c],
(B) A liquid crystal composition comprising a compound having no liquid crystallinity represented by the following formula [7a], [7b] or [7c], and (C) an organic solvent.

[Wherein, X and Y are each independently a group represented by the following formula [2] or [3],

(In the formula, R ¹ is a hydrogen atom or a methyl group, and a broken line is a bond.)
M ¹ is a group represented by the following formula [4], M ² is a group represented by the following formula [5] or [6],

(In the formula, s1, s2, s3, s4, s5 and s6 are each independently 1 or 2, and G ¹ and G ² are each independently a single bond, —COO— or —OCO—. , R ² and R ³ are each independently a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and R ⁴ is an alkyl group having 1 to 1 carbon atoms. 3 is an alkyl group, and the broken line is a bond.)
A is a linear or branched alkyl group having 2 to 15 carbon atoms,
m, n and p are numbers satisfying 0 <m <1, 0 <n <1, 0 ≦ p ≦ 0.5 and m + n + p ≦ 1, respectively.
q and r are each independently an integer of 2 to 9. ]

(Wherein R ⁵ and R ⁶ are each independently —OH, —OCH ₃ , —C (═O) OH, —C (═O) OCH ₃ , —C (═O) OCH ₂ CH ₃ or —OC (═O) CH ₃ , and R ⁷ and R ⁸ are each independently a hydrogen atom, —OH, —OCH ₃ , —C (═O) OH, —C (═O) OCH ₃ , — C (═O) OCH ₂ CH ₃ or —OC (═O) CH ₃ , G ³ is a single bond, —C (═O) —O— or —O—C (═O) —, G ⁴ is a single bond, —CH═CH— or —CH ₂ CH ₂ —.
A single-layer coating type horizontal alignment film produced using the liquid crystal composition of 2.1.
An optical member provided with the single-layer coating type horizontal alignment film of 3.2.
The manufacturing method of the single-layer coating type horizontal alignment film including the process of apply | coating the liquid crystal composition of 4.1 to a board | substrate, the process of irradiating polarized light, and the process of post-baking.
5. 4. A method for producing a single-layer coating type horizontal alignment film, wherein the polarized light is linearly polarized ultraviolet rays.

  By applying the liquid crystal composition of the present invention, irradiating linearly polarized light at room temperature, and performing post-baking at a low temperature, it is possible to produce a single-layer coating type horizontal alignment film exhibiting high Δn.

It is a figure which shows the retardation value angle dependence of each film obtained by the comparative example 1 and Examples 1-5. It is a figure which shows the retardation value angle dependence of each film obtained by the comparative example 1 and Examples 6-9. It is a figure which shows the retardation value angle dependence of each film obtained by Comparative Examples 2-3 and Examples 10-11.

[Liquid crystal composition]
The liquid crystal composition of the present invention comprises (A) a predetermined polymer, (B) a compound that does not exhibit predetermined liquid crystallinity, and (C) an organic solvent.

[(A) Polymer]
The polymer of the component (A) contains repeating units represented by the following formulas [1a] and [1b], and further contains a repeating unit represented by the following formula [1c] as necessary.

In the formulas [1a] and [1c], X and Y are each independently a group represented by the following formula [2] or [3].

In the formula [3], R ¹ is a hydrogen atom or a methyl group. A broken line is a bond (hereinafter the same). Of these, X and Y are preferably groups represented by the formula [3].

In the formula [1a], M ¹ is a group represented by the following formula [4]. In the formula [1b], M ² is a group represented by the following formula [5] or [6].

Wherein [4] ~ [6], s1, s2, s3, s4, s5 and s6 are each independently 1 or 2, G ¹ and G ² each independently represent a single bond, -COO- Or -OCO-. R ² and R ³ are each independently a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. R ⁴ is an alkyl group having 1 to 3 carbon atoms.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. In the present invention, a fluorine atom is preferable.

The alkyl group represented by R ² and R ³ may be linear, branched or cyclic, but in the present invention, a linear alkyl group having 1 to 10 carbon atoms is preferred. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, s-butyl group, tert-butyl group, cyclobutyl group, n- Examples include a pentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, and an n-decyl group. Of these, an alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group, an ethyl group, and the like are particularly preferable. The alkyl group represented by R ⁴ may be either linear or branched, but in the present invention, a linear alkyl group having 1 to 3 carbon atoms is preferable.

  The alkoxy group may be linear, branched or cyclic, but in the present invention, a linear alkoxy group having 1 to 10 carbon atoms is preferred. Specific examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, s-butoxy group, tert-butoxy group, n-pentoxy group, and n-hexyl. An oxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, etc. are mentioned. Among these, a C1-C3 alkoxy group is still more preferable, and especially a methoxy group, an ethoxy group, etc. are preferable. In the alkyl group and alkoxy group, part or all of the hydrogen atoms may be substituted with a halogen atom such as a fluorine atom.

R ² or R ³ is more preferably a hydrogen atom, a fluorine atom, a cyano group, a methyl group, or a methoxy group. R ⁴ is preferably a methyl group or an ethyl group, and more preferably a methyl group.

G ¹ is preferably —COO— or —OCO—, and G ² is preferably a single bond.

  In the formula [1c], A is a linear or branched alkyl group having 2 to 15 carbon atoms. Specific examples of the alkyl group include ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, tert-butyl, n-pentyl, 1-methyl-n-butyl. Group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n- Propyl group, 1-ethyl-n-propyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n- Pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2,3 -Dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1- Methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, n-heptyl group, 1-methyl-n-hexyl group, 2-methyl-n-hexyl group, 3-methyl-n-hexyl Group, 1,1-dimethyl-n-pentyl group, 1,2-dimethyl-n-pentyl group, 1,3-dimethyl-n-pentyl group, 2,2-dimethyl-n-pentyl group, 2,3- Dimethyl-n-pentyl group, 3,3-dimethyl-n-pentyl group, 1-ethyl-n-pentyl group, 2-ethyl-n-pentyl group, 3-ethyl-n-pentyl group, 1-methyl-1 -Ethyl-n-butyl group, 1-methyl-2-ethyl-n-butyl group, 1 Ethyl-2-methyl-n-butyl group, 2-methyl-2-ethyl-n-butyl group, 2-ethyl-3-methyl-n-butyl group, n-octyl group, 1-methyl-n-heptyl group 2-methyl-n-heptyl group, 3-methyl-n-heptyl group, 1,1-dimethyl-n-hexyl group, 1,2-dimethyl-n-hexyl group, 1,3-dimethyl-n-hexyl Group, 2,2-dimethyl-n-hexyl group, 2,3-dimethyl-n-hexyl group, 3,3-dimethyl-n-hexyl group, 1-ethyl-n-hexyl group, 2-ethyl-n- Hexyl group, 3-ethyl-n-hexyl group, 1-methyl-1-ethyl-n-pentyl group, 1-methyl-2-ethyl-n-pentyl group, 1-methyl-3-ethyl-n-pentyl group 2-methyl-2-ethyl-n-pentyl group, 2-methyl-3 Ethyl-n-pentyl group, 3-methyl-3-ethyl-n-pentyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, An n-pentadecyl group etc. are mentioned.

  Among these, in view of solubility of the resulting polymer in an organic solvent, an alkyl group having 4 to 15 carbon atoms, particularly 4 to 12 carbon atoms is preferable, and n-butyl group, 2-ethyl-n-hexyl group, n -A dodecyl group etc. are more preferable.

In the formulas [1a] to [1c], m, n, and p are numbers satisfying 0 <m <1, 0 <n <1, 0 ≦ p ≦ 0.5, and m + n + p ≦ 1, respectively. From the viewpoint of improving Δn and improving the solubility of the polymer, m, n, and p are 0.2 ≦ m ≦ 0.9, 0.1 ≦ n ≦ 0.8, and 0 ≦ p ≦ 0.0, respectively. 4 is preferable, and 0.2 ≦ m ≦ 0.8, 0.1 ≦ n ≦ 0.5, and 0.1 ≦ p ≦ 0.3 are more preferable. However, when M ² is a group represented by the formula [6], it is preferable that p = 0, 0 <m <1, 0 <n <1, and m + n ≦ 1, and 0.2 More preferably, ≦ m ≦ 0.9 and 0.1 ≦ n ≦ 0.8 are satisfied, and more preferably 0.5 ≦ m ≦ 0.8 and 0.2 ≦ n ≦ 0.5.

  In the formulas [1a] and [1b], q and r are each independently an integer of 2 to 9, preferably 3 to 6, and more preferably 5 or 6 as q.

  The polymer of component (A) preferably has a weight average molecular weight (Mw) of 3,000 to 200,000, more preferably 4,000 to 150,000, and 5,000 to 100,000. More preferably. If Mw exceeds 200,000, solubility in the solvent may be reduced and handling properties may be reduced. If Mw is less than 3,000, curing is insufficient during heat curing, and solvent resistance and heat resistance are reduced. There is a case. In addition, Mw is a polystyrene conversion measured value by gel permeation chromatography (GPC).

  Moreover, the polymer of (A) component may also contain other repeating units other than Formula [1a]-[1c], unless the effect of this invention is impaired. Examples of the polymerizable compound that gives the other repeating unit include acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylamide compounds, acrylonitrile, maleic anhydride, and styrene compounds.

  The content of other repeating units is preferably 0 to 10 mol% in 100 mol% of all repeating units. If the content of other repeating units is too large, the properties of the polymer, such as liquid crystal properties, may deteriorate.

  When the polymer of the component (A) contains the other repeating unit, as a synthesis method thereof, polymerization may be performed in the presence of a polymerizable compound that gives the other repeating unit.

  In addition, the polymer of the component (A) may be any of a random copolymer, an alternating copolymer, and a block copolymer. Moreover, the said polymer may be used individually by 1 type or in combination of 2 or more types.

  Examples of the method for synthesizing the polymer of component (A) include, but are not limited to, the methods described in International Publication Nos. 2013/133078 and 2015/025794.

[(B) Compound not showing liquid crystallinity]
The compound (B) that does not exhibit liquid crystallinity is represented by the following formula [7a], [7b] or [7c].

In formula [7a], R ⁵ and R ⁶ are each independently —OH, —OCH ₃ , —C (═O) OH, —C (═O) OCH ₃ , —C (═O) OCH ₂ CH. ₃ or —OC (═O) CH ₃ . Of these, —C (═O) OCH ₃ or —C (═O) OCH ₂ CH ₃ is preferred, and —C (═O) OCH ₂ CH ₃ is more preferred.

In formula [7b], R ⁷ and R ⁸ each independently represent a hydrogen atom, —OH, —OCH ₃ , —C (═O) OH, —C (═O) OCH ₃ , —C (═O). OCH ₂ CH ₃ or —OC (═O) CH ₃ . Of these, —C (═O) OCH ₃ or —C (═O) OCH ₂ CH ₃ is preferred, and —C (═O) OCH ₂ CH ₃ is more preferred.

In formula [7b], G ³ represents a single bond, —C (═O) —O— or —O—C (═O) —. Among these, a single bond or —C (═O) —O— is preferable, and a single bond is more preferable.

In formula [7c], G ⁴ is a single bond, —CH═CH— or —CH ₂ CH ₂ —. Among these, a single bond or —CH═CH— is preferable, and a single bond is more preferable.

Examples of the compound represented by the formula [7a] include, but are not limited to, those shown below.

Examples of the compound represented by the formula [7b] include, but are not limited to, those shown below.

Examples of the compound represented by the formula [7c] include, but are not limited to, those shown below.

  The compounds represented by the formulas [7a] to [7c] can be synthesized using a known method (for example, esterification reaction), or can be obtained as a commercial product.

  As for content of (B) component, 1-10 mass parts is preferable with respect to 100 mass parts of polymers of (A) component, and 1-5 mass parts is more preferable. If content of (B) component is the said range, the effect of a retardation improvement will be shown. (B) The compound of a component may be used individually by 1 type or in combination of 2 or more types.

[(C) Organic solvent]
Examples of the organic solvent of component (C) include ethers such as tetrahydrofuran and dioxane; aromatic hydrocarbons such as benzene, toluene and xylene; N, N-dimethylformamide, N-methyl-2-pyrrolidone (NMP) Polar solvents such as ethyl acetate, butyl acetate, ethyl lactate, etc .; methyl 3-methoxypropionate, methyl 2-methoxypropionate, ethyl 3-methoxypropionate, ethyl 2-methoxypropionate, 3-ethoxypropion Alkoxy esters such as ethyl acetate and ethyl 2-ethoxypropionate; glycol dialkyl ethers such as ethylene glycol dimethyl ether and propylene glycol dimethyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and die Diglycol dialkyl ethers such as ethylene glycol methyl ethyl ether and dipropylene glycol dimethyl ether; Glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether; diethylene glycol monomethyl ether Diglycol monoalkyl ethers such as diethylene glycol 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; cyclohexa Emissions, methyl ethyl ketone, methyl isobutyl ketone and 2-heptanone. These organic solvents may be used alone or in combination of two or more.

  Among these, toluene, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, cyclohexanone and the like are preferable. The amount of the organic solvent used is preferably about 60 to 95% by mass in the composition.

[Other ingredients]
A surfactant may be added to the 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, and a nonionic surfactant. 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), EFTOP (registered trademark) EF301, EF303, EF352 (manufactured by Tochem Products), MegaFac (registered trademark) F171, F173, R- 30, R-30N (manufactured by DIC Corporation), Florard (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Corporation), Asahi Guard (registered trademark) AG710, Surflon (registered trademark) S-382, SC101, SC102 , SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.) and the like. In addition, surfactant can also be used individually by 1 type or in combination of multiple types, The addition amount is 5 mass parts or less with respect to 100 mass parts of polymers.

  Furthermore, an adhesion promoter may be added to the 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; 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, γ- ( Silanes such as -piperidinyl) propyltrimethoxysilane; benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazole, thiouracil, mercaptoimidazole, mercaptopyrimidine, etc. Heterocyclic compounds of the above; urea compounds such as 1,1-dimethylurea, 1,3-dimethylurea; and thiourea compounds.

  The adhesion promoter can be used alone or in combination of two or more, and the addition amount is preferably 1 part by mass or less with respect to 100 parts by mass of the polymer.

[Single-layer coating type horizontal alignment film]
A substrate (for example, a silicon / silicon dioxide coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum, or chromium, a glass substrate, a quartz substrate, an ITO substrate) or a film (For example, resin film such as triacetyl cellulose (TAC) film, cycloolefin polymer film, polyethylene terephthalate film, acrylic film, etc.) etc., bar coat, spin coat, flow coat, roll coat, slit coat, slit coat A film can be formed by applying by a subsequent method such as spin coating, ink jet method, printing method or the like to form a coating film, followed by heat drying with a hot plate or oven.

  As conditions for heat drying, for example, a heating temperature and a heating time appropriately selected from the range of 50 to 100 ° C. and 0.1 to 60 minutes are employed. The heating temperature and heating time are preferably 50 to 80 ° C. and 0.1 to 2 minutes.

  The film thus formed is irradiated with linearly polarized light and post-baked to obtain a single-layer coating type horizontal alignment film. As a method of irradiating linearly polarized light, ultraviolet rays or visible rays having a wavelength of 150 to 450 nm are usually used, and the irradiation is performed by irradiating linearly polarized light at room temperature or in a heated state.

  Moreover, what is necessary is just to heat a post-baking with a hotplate or oven etc., The temperature and time become like this. Preferably it is 90-150 degreeC and 2 to 20 minutes, More preferably, it is 95 to 120 degreeC and 5 to 20 minutes. is there.

  The film thickness of the single-layer coating type horizontal alignment film of the present invention can be appropriately selected in consideration of the level difference of the substrate to be used and the optical and electrical properties. For example, 0.1 to 3 μm is preferable.

  The thus obtained single-layer coating type horizontal alignment film of the present invention is a material having optical characteristics suitable for applications such as display devices and recording materials, and in particular, polarizing plates and retardation plates for liquid crystal displays. It is suitable as an optical compensation film.

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 measuring method and measuring conditions of each physical property in an Example are as follows.
[NMR]
The compound was dissolved in deuterated chloroform (CDCl ₃ ), and ¹ H-NMR was measured using a nuclear magnetic resonance apparatus (300 MHz, manufactured by Diol).
[Average molecular weight measurement]
Number average molecular weight (Mn) and weight average molecular weight (Mw) were measured using Shodex GPC-101 (solvent: tetrahydrofuran (THF), calibration curve: standard polystyrene) manufactured by Showa Denko K.K.
[Retardation value of film]
The retardation value angle dependency at a wavelength of 550 nm was measured using a retardation measuring device (RETS-100, manufactured by Otsuka Electronics Co., Ltd.).

[1] Synthesis of Compound [Synthesis Example 1] Synthesis of polymerizable compound (M1)

4- (6-acryloyloxy-1-hexyloxy) benzoic acid (manufactured by SYNTHON Chemicals) 29.2 g (100 mmol), 4-hydroxybiphenyl 17.0 g (100 mmol), 4-dimethylaminopyridine (DMAP) 0.6 g A small amount of dibutylhydroxytoluene (BHT) was suspended in 200 mL of methylene chloride with stirring at room temperature, and 24.0 g (116 mmol) of N, N′-dicyclohexylcarbodiimide (DCC) was dissolved in 100 mL of methylene chloride. The solution was added and stirred overnight. The precipitated DCC urea was filtered off, and the filtrate was washed twice with 0.5 mol / L hydrochloric acid (150 mL), saturated aqueous sodium hydrogen carbonate solution (150 mL) and saturated brine (150 mL), and dried over magnesium sulfate. Distilled off and purified by recrystallization with ethanol to obtain 39.6 g of the target polymerizable compound (M1) (yield 89%). The measurement results of NMR are shown below.
¹ H-NMR (CDCl ₃ ) δ: 1.57 (m, 4H), 1.70 (m, 2H), 1.86 (m, 2H), 4.00 (m, 2H), 4.19 (m, 2H), 5.82 (m, 1H ), 6.12 (m, 1H), 6.39 (m, 1H), 6.97 (d, 2H), 7.29 (m, 2H), 7.36 (m, 1H), 7.47 (m, 2H), 7.62 (m, 4H) , 8.18 (m, 2H)

[Synthesis Example 2] Synthesis of polymerizable compound (M2) (1) Synthesis of intermediate compound (Q2)

In a 500 mL eggplant flask with a condenser tube, 18.6 g (100 mmol) of biphenol, 10.0 g (48 mmol) of 2- (4-bromo-1-butyl) -1,3-dioxolane, 13.8 g (100 mmol) of potassium carbonate, and 200 mL of acetone was added to form a mixture, which was reacted at 64 ° C. with stirring for 24 hours. After completion of the reaction, the reaction solution was poured into 500 mL of pure water to obtain a white solid. This solid was mixed with methanol, filtered, and the solvent was distilled off to obtain a white solid. Next, this solid was mixed with chloroform, filtered, and the solvent was distilled off to obtain 7.2 g of a white solid. The result of having measured this solid by NMR is shown below. From this result, it was confirmed that this white solid was an intermediate compound (Q2) (yield 48%).
¹ H-NMR (CDCl ₃ ) δ: 1.62 (m, 2H), 1.76 (m, 2H), 1.87 (m, 2H), 3.85 (m, 2H), 4.00 (m, 4H), 4.90 (m, 1H ), 6.87 (m, 4H), 7.42 (m, 4H)

(2) Synthesis of intermediate compound (Z2)

Next, in a 300 mL eggplant flask equipped with a condenser tube, 7.2 g (23 mmol) of the intermediate compound (Q2), 4.1 g (25 mmol) of 2- (bromomethyl) acrylic acid, 60 mL of THF, and 4.7 g (25 mmol) of tin (II) chloride. ) And 19 mL of 10% by mass hydrochloric acid to make a mixture, and the mixture was reacted at 70 ° C. for 5 hours with stirring. After completion of the reaction, the reaction solution was poured into 200 mL of pure water to obtain 6.1 g of a white solid. The result of having measured this solid by NMR is shown below. From this result, it was confirmed that this white solid was an intermediate compound (Z2) (yield 78%).
¹ H-NMR (CDCl ₃ ) δ: 1.60-1.95 (m, 6H), 2.64 (m, 1H), 3.11 (s, 1H), 4.02 (t, 2H), 4.60 (m, 1H), 4.82 (s , 1H), 5.64 (s, 1H), 6.24 (s, 1H), 6.88 (d, 2H), 6.94 (d, 2H), 7.44 (m, 4H)

(3) Synthesis of polymerizable compound (M2)

Intermediate compound (Z2) 3.4 g (10 mmol), 4-methoxycinnamic acid 1.8 g (10 mmol), DMAP 0.08 g, and a small amount of BHT were suspended in 30 mL of methylene chloride under stirring at room temperature. A solution prepared by dissolving 2.6 g (13 mmol) of DCC in 15 mL of methylene chloride was added and stirred overnight. The precipitated DCC urea was filtered off, and the filtrate was washed twice with 0.5 mol / L hydrochloric acid 50 mL, saturated aqueous sodium hydrogen carbonate solution 50 mL and saturated brine 50 mL successively, dried over magnesium sulfate, and the solvent was removed. Distilled off and purified by recrystallization with ethanol to obtain 4.3 g of the target polymerizable compound (M2) (yield 86%). The measurement results of NMR are shown below.
¹ H-NMR (CDCl ₃ ) δ: 1.60-1.90 (m, 6H), 2.63 (m, 1H), 3.09 (m, 1H), 3.87 (s, 3H), 4.03 (m, 2H), 4.57 (m , 1H), 5.64 (m, 1H), 6.24 (d, 1H), 6.54 (d, 1H), 6.95 (m, 4H), 7.26 (m, 2H), 7.44 (m, 2H), 7.57 (m, 4H), 7.86 (d, 1H)

[Synthesis Example 3] Synthesis of polymerizable compound (M3) (1) Synthesis of intermediate compound (A3)

In a 200 mL eggplant flask equipped with a condenser tube, methyl 4-hydroxybenzoate (7.61 g, 50.0 mmol), 6-bromo-1-hexanol (9.1 g, 50.0 mmol), potassium carbonate (13.8 g, 100 mmol), and acetone 70 mL was added to make a mixture, and the mixture was reacted at 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 to 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, in a 100 mL three-necked flask with a condenser tube, 2.2 g (10.0 mmol) of pyridinium chlorochromate and 15.0 mL of methylene chloride were added and stirred and mixed, and 2.5 g (10 of the intermediate compound (A3)) (0.0 mmol) in methylene chloride (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 to 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), 0.83 g (5.0 mmol) of 2- (bromomethyl) acrylic acid, Amberlyst (registered trademark) 15 (ROHM) were placed in a 50 mL eggplant flask equipped with a condenser. (Endhas Co., Ltd.) 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 stirred at a temperature of 70 ° C. for 5 hours to be reacted. It was. 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 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), and 5 mL of 10% by mass sodium hydroxide aqueous solution were added to form a mixture, and the mixture was stirred at a temperature of 85 ° C. for 3 hours. Reacted. 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 mass% 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, Amberlyst (registered trademark) 15 (Rohm End Haas) 1.0 g, and 20.0 mL of THF were added to a 50 mL eggplant flask equipped with a cooling tube to obtain a mixture, and the temperature was 70 ° C. The reaction was stirred for 5 hours. 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 is an intermediate compound (D3) (yield 71%).
¹ H-NMR (DMSO-d6) δ: 1.2-1.8 (m, 8H), 2.60 (m, 1H), 3.09 (m, 1H), 4.04 (m, 2H), 4.55 (m, 1H), 5.69 ( s, 1H), 6.02 (s, 1H), 6.99 (d, 2H), 7.88 (d, 2H), 12.5 (s, broad, 1H).

(5) Synthesis of polymerizable compound (M3)

Intermediate compound (D3) 3.0 g (10.0 mmol), methyl 4-hydroxycinnamate 1.8 g (10.0 mmol), DMAP 0.05 g, and a small amount of BHT were stirred at room temperature in 60 mL of methylene chloride. A solution in which 2.7 g (13.0 mmol) of DCC was dissolved was added thereto, followed by stirring overnight. The precipitated DCC urea was filtered off, and the filtrate was washed twice with 50 mol / L hydrochloric acid 50 mL, saturated aqueous sodium hydrogen carbonate solution 50 mL and saturated brine 100 mL successively, dried over magnesium sulfate, and then under reduced pressure. The solvent was distilled off to obtain a yellow solid. This solid was purified by recrystallization (ethanol). 2.6 g of the target polymerizable compound (M3) was obtained (yield 56%).
¹ H-NMR (CDCl ₃ ) δ: 1.40-1.90 (m, 8H), 2.58 (m, 1H), 3.08 (m, 1H), 3.80 (s, 3H), 4.05 (t, 2H), 4.55 (m , 1H), 5.64 (s, 1H), 6.22 (s, 1H), 6.42 (d, 1H), 6.97 (d, 2H), 7.22 (d, 2H), 7.60 (d, 2H), 7.70 (d, 1H), 8.15 (d, 2H).

[Synthesis Example 4] Synthesis of polymer (P1)

  In a flask equipped with a condenser, 2.16 g (4.8 mmol) of polymerizable compound (M1), 1.80 g (3.6 mmol) of polymerizable compound (M2), 0.84 g (3.6 mmol) of n-dodecyl acrylate , 48.0 g of NMP and 0.10 g of azobisisobutyronitrile (AIBN) were charged, and the atmosphere in the flask was replaced with nitrogen, followed by stirring at 60 ° C. for 20 hours for reaction. The obtained reaction solution was put into 400 mL of methanol to precipitate a white powder. After filtering this white powder, it vacuum-dried at room temperature and obtained 3.60g of polymers (P1) (yield 75%). Mn of the polymer (P1) was 13,258 (Mw / Mn = 2.0).

[Synthesis Example 5] Synthesis of polymer (P2)

  In a flask equipped with a condenser tube, 0.36 g (0.8 mmol) of the polymerizable compound (M1), 0.60 g (1.2 mmol) of the polymerizable compound (M2), 0.48 g (2.0 mmol) of n-dodecyl acrylate. , 16.0 g of NMP and 0.034 g of AIBN were charged, and the inside of the flask was purged with nitrogen, followed by stirring at 60 ° C. for 20 hours for reaction. The obtained reaction solution was put into 200 mL of methanol to precipitate a white powder. After filtering this white powder, it vacuum-dried at room temperature and obtained 0.95g of polymers (P3) (yield 66%). Mn of the polymer (P2) was 13,647 (Mw / Mn = 2.0).

[Synthesis Example 6] Synthesis of polymer (P3)

  In a flask equipped with a condenser, 0.20 g (0.4 mmol) of the polymerizable compound (M1) obtained in Synthesis Example 1 and 0.44 g (1.0 mmol) of the polymerizable compound (M3) obtained in Synthesis Example 3 were used. ), NMP (5.8 g) and AIBN (12 mg) were charged, the inside of the flask was purged with nitrogen, and the mixture was reacted by stirring at a temperature of 60 ° C. for 20 hours. The obtained reaction solution was put into 200 mL of methanol to precipitate a white powder. After filtering this white powder, it vacuum-dried at room temperature and obtained 0.5g of polymers (P3) (yield 78%). Mn of the obtained polymer (P3) was 15,877 (Mw / Mn = 3.26).

[2] Preparation of liquid crystal composition and film production / evaluation The structures of the compounds (1) to (9) used in the following examples are shown below.

Compound (2) was synthesized by an esterification reaction using 4- (4-hydroxyphenyl) benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and sulfuric acid with ethanol.

Compound (6) was synthesized by an esterification reaction using p-anisic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and compound (1) using DMAP.

[Example 1]
Toluene / cyclohexanone containing 150 mg of polymer (P1) and 7.5 mg of compound (1) (manufactured by Tokyo Chemical Industry Co., Ltd.) and R-30N (manufactured by DIC Corporation) as a surfactant. (75/25, w / w) dissolved in 0.850 g to prepare a liquid crystal composition.
The obtained composition was applied to a glass substrate by spin coating (300 rpm / 5 seconds, 500 rpm / 20 seconds), pre-baked on a hot plate at a temperature of 55 ° C. for 30 seconds, and then allowed to cool to room temperature.
Next, the coating film formed on the glass substrate was irradiated with linearly polarized ultraviolet light at 100 mJ / cm ² (illuminance measurement at a wavelength of 313 nm) vertically, and then post-baked on a hot plate at 100 ° C. for 15 minutes to obtain a film. It was. The obtained film had a thickness of 1.8 μm, a retardation value (Δnd) of 212 nm, and Δn of 0.118.

[Example 2]
A liquid crystal composition and a film were obtained in the same manner as in Example 1 except that the compound (2) was used instead of the compound (1). The obtained film had a film thickness of 1.9 μm, a retardation value of 275 nm, and Δn of 0.145.

[Example 3]
A liquid crystal composition and a film were obtained in the same manner as in Example 1, except that compound (3) (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of compound (1). The obtained film had a film thickness of 1.8 μm, a retardation value of 235 nm, and Δn of 0.127.

[Example 4]
A liquid crystal composition and a film were obtained in the same manner as in Example 1 except that 3.0 mg of compound (4) (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 7.5 mg of compound (1). The obtained film had a thickness of 1.9 μm, a retardation value of 211 nm, and Δn of 0.111.

[Example 5]
A liquid crystal composition and a film were obtained in the same manner as in Example 1 except that compound (5) (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of compound (1). The obtained film had a thickness of 2.0 μm, a retardation value of 242 nm, and Δn of 0.120.

[Example 6]
A liquid crystal composition and a film were obtained in the same manner as in Example 1 except that the compound (6) was used instead of the compound (1). The obtained film had a film thickness of 1.8 μm, a retardation value of 255 nm, and Δn of 0.142.

[Example 7]
A liquid crystal composition and a film were obtained in the same manner as in Example 1, except that compound (7) (manufactured by ALDRICH) was used instead of compound (1). The obtained film had a thickness of 1.8 μm, a retardation value of 240 nm, and Δn of 0.133.

[Example 8]
A liquid crystal composition and a film were obtained in the same manner as in Example 1 except that compound (8) (manufactured by ALDRICH) was used instead of compound (1). The obtained film had a thickness of 2.0 μm, a retardation value of 207 nm, and Δn of 0.103.

[Example 9]
A liquid crystal composition and a film were obtained in the same manner as in Example 1 except that compound (9) (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of compound (1). The obtained film had a thickness of 1.7 μm, a retardation value of 182 nm, and Δn of 0.107.

[Example 10]
Toluene / cyclohexanone (75/25, w / w) containing 150 mg of polymer (P2) and 7.5 mg of compound (2) with 0.02% by mass of surfactant R-30 (manufactured by DIC Corporation) A liquid crystal composition was prepared by dissolving in 0.850 g.
The obtained composition was applied to a glass substrate by spin coating (300 rpm / 5 seconds, 900 rpm / 20 seconds), pre-baked on a hot plate at a temperature of 55 ° C. for 30 seconds, and then allowed to cool to room temperature.
Next, the coating film formed on the glass substrate was irradiated with linearly polarized ultraviolet light at 100 mJ / cm ² (illuminance measurement at a wavelength of 313 nm) vertically, and then post-baked on a hot plate at 100 ° C. for 15 minutes to obtain a film. It was. The obtained film had a thickness of 1.7 μm, a retardation value (Δnd) of 110 nm, and Δn of 0.065.

[Example 11]
150 mg of the polymer (P3) and 7.5 mg of the compound (2) were dissolved in 0.850 g of cyclohexanone containing 0.02% by mass of R-30 (DIC Corporation) as a surfactant, and a liquid crystal composition was obtained. Prepared.
The obtained composition was applied to a glass substrate by spin coating (300 rpm / 5 seconds, 500 rpm / 20 seconds), pre-baked on a hot plate at a temperature of 55 ° C. for 30 seconds, and then allowed to cool to room temperature.
Next, the coating film formed on the glass substrate was irradiated with linearly polarized ultraviolet light at 100 mJ / cm ² (illuminance measurement at a wavelength of 313 nm) vertically, and then post-baked on a hot plate at 100 ° C. for 15 minutes to obtain a film. It was. The obtained film had a thickness of 1.5 μm, a retardation value (Δnd) of 35 nm, and Δn of 0.023.

[Comparative Example 1]
A liquid crystal composition and a film were obtained in the same manner as in Example 1 except that the compound (1) was not used. The obtained film had a film thickness of 1.8 μm, a retardation value of 175 nm, and Δn of 0.099.

[Comparative Example 2]
A liquid crystal composition and a film were obtained in the same manner as in Example 10 except that the compound (2) was not used. The obtained film had a thickness of 1.6 μm, a retardation value of 87 nm, and Δn of 0.054.

[Comparative Example 3]
A liquid crystal composition and a film were obtained in the same manner as in Example 11 except that the compound (2) was not used. The obtained film had a thickness of 1.5 μm, a retardation value of 26 nm, and Δn of 0.018.

  The above results are summarized in Table 1.

  1-3 shows the angle dependence of the retardation values of the films of Examples 1-11 and Comparative Examples 1-3. Thereby, it turned out that a horizontal alignment film is obtained.

Claims (5)

(A) a polymer containing repeating units represented by the following formulas [1a], [1b] and [1c],
(B) A liquid crystal composition comprising a compound having no liquid crystallinity represented by the following formula [7a], [7b] or [7c], and (C) an organic solvent.

[Wherein, X and Y are each independently a group represented by the following formula [2] or [3],

(In the formula, R ¹ is a hydrogen atom or a methyl group, and a broken line is a bond.)
M ¹ is a group represented by the following formula [4], M ² is a group represented by the following formula [5] or [6],

(In the formula, s1, s2, s3, s4, s5 and s6 are each independently 1 or 2, and G ¹ and G ² are each independently a single bond, —COO— or —OCO—. , R ² and R ³ are each independently a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and R ⁴ is an alkyl group having 1 to 1 carbon atoms. 3 is an alkyl group, and the broken line is a bond.)
A is a linear or branched alkyl group having 2 to 15 carbon atoms,
m, n and p are numbers satisfying 0 <m <1, 0 <n <1, 0 ≦ p ≦ 0.5 and m + n + p ≦ 1, respectively.
q and r are each independently an integer of 2 to 9. ]

(Wherein R ⁵ and R ⁶ are each independently —OH, —OCH ₃ , —C (═O) OH, —C (═O) OCH ₃ , —C (═O) OCH ₂ CH ₃ or —OC (═O) CH ₃ , and R ⁷ and R ⁸ are each independently a hydrogen atom, —OH, —OCH ₃ , —C (═O) OH, —C (═O) OCH ₃ , — C (═O) OCH ₂ CH ₃ or —OC (═O) CH ₃ , G ³ is a single bond, —C (═O) —O— or —O—C (═O) —, G ⁴ is a single bond, —CH═CH— or —CH ₂ CH ₂ —.   A single-layer coating type horizontal alignment film produced using the liquid crystal composition according to claim 1.   An optical member comprising the single-layer coating type horizontal alignment film according to claim 2.   A method for producing a single-layer coating type horizontal alignment film, comprising a step of applying the liquid crystal composition according to claim 1 to a substrate, a step of irradiating polarized light, and a step of post-baking.   The method for producing a single-layer coated horizontal alignment film according to claim 4, wherein the polarized light is linearly polarized ultraviolet light.

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