JPWO2014142103A1 - Composition and single-layer coated horizontal alignment film - Google Patents

Abstract

(A) Polymer A containing repeating units represented by formulas [1a], [1b] and [1c], (B) Polymer B containing repeating units represented by formula [6], and ( C) A composition containing an organic solvent is provided. [Wherein, X and Y are each independently a group represented by the formula [2] or [3], M1 is a group represented by the formula [4], and M2 is represented by the formula [5]. A is a linear or branched alkyl group, m, n and p are 0 <m <1, 0 <n <1, 0 ≦ p ≦ 0.5, and m + n + p ≦ 1, and q and r are each independently an integer of 2 to 9. (Wherein R4 is a hydrogen atom or a methyl group, R5 is a methyl group, an ethyl group or a propyl group)

Description

  The present invention relates to a composition and a single-layer coating type horizontal alignment film. Specifically, a material having optical properties suitable for applications such as display devices and recording materials, in particular, a composition comprising a liquid crystalline polymer suitable for optical compensation films such as polarizing plates and retardation plates for liquid crystal displays, And a single-layer coated horizontal alignment film obtained from the 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 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), an alignment film using a polymer containing a photocrosslinking site (Patent Documents 5 and 6), etc. Various single-layer coated orientation films have been reported. However, the orientation direction of the film obtained by the film production process has a problem that a shift due to the influence of the surface of the substrate is observed, and it has been desired to solve such a problem.

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

  The present invention has been made in view of the above problems, a composition capable of producing a single-layer coating type horizontal alignment film by a simple process, and capable of solving the problem of misalignment of the alignment direction, and the composition It aims at providing the single layer application type | mold horizontal orientation film obtained from a thing.

  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. Can be used to form a single layer coating type horizontal alignment film having a high refractive index anisotropy (Δn) without using a liquid crystal alignment film. Furthermore, it has been found that by introducing an alkyl chain into the polymer, solubility in an organic solvent is improved, and a single-layer coating type horizontal alignment film having a higher Δn can be produced under low temperature conditions. Furthermore, the present inventor added a poly (meth) acrylic acid ester as an additive to the composition containing the above polymer, so that the control of the orientation direction is more excellent, and the single layer coating type horizontal that exhibits high optical anisotropy. The inventors have found that an oriented film can be easily obtained, and completed the present invention.

［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［３］中、Ｒ¹は水素原子又はメチル基である。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］で表される基であり、

（式［４］及び［５］中、ｓ１、ｓ２、ｓ３及びｓ４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る。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［６］中、Ｒ⁴は水素原子又はメチル基である、Ｒ⁵はメチル基、エチル基、ｎ−プロピル基、イソプロピル基又はシクロプロピル基である。）
２．１の組成物を基板に塗布し、次いで偏光を照射し、硬化させることにより得られる単層塗布型水平配向フィルム。
３．上記偏光が、直線偏光紫外線である２の単層塗布型水平配向フィルム。
４．２又は３の単層塗布型水平配向フィルムを備える光学部材。That is, this invention provides the following composition and a single layer application type | mold horizontal orientation film.
1. (A) Polymer A containing repeating units represented by the following formulas [1a], [1b] and [1c],
(B) Polymer B containing the repeating unit represented by the following formula [6], 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 [3], R ¹ is a hydrogen atom or a methyl group. The 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],

(Wherein [4] and [5], the s1, s2, s3 and s4, are each independently 1 or 2, G ¹ and G ² each independently represent a single bond, -COO- or -OCO- in 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.
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. ]

(In Formula [6], R ⁴ is a hydrogen atom or a methyl group, R ⁵ is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, or a cyclopropyl group.)
A single-layer coating type horizontal alignment film obtained by coating the composition of 2.1 on a substrate, and then irradiating and curing the polarized light.
3. 2. A single-layer coating type horizontal alignment film in which the polarized light is linearly polarized ultraviolet rays.
An optical member provided with the single-layer coating type horizontal alignment film of 4.2 or 3.

The polymer of the present invention contains a γ-butyrolactone skeleton in the main chain. Therefore, it is possible to produce a single-layer coated horizontal alignment film exhibiting high Δn by a process of applying a composition containing this polymer, irradiating linearly polarized light at room temperature, and performing post-baking. Further, by using a polymer containing a unit having an alkyl group side chain, solubility in a solvent can be improved.
In addition, by adding a poly (meth) acrylate that does not exhibit liquid crystallinity to a solution of a liquid crystalline base polymer having a cinnamic acid ester structure, deviation of the orientation angle (horizontal direction) of the resulting oriented film is reduced. A single-layer coated horizontal alignment film can be obtained.

It is a figure which shows the retardation value angle dependence ((alpha) angle) in wavelength 550nm of the pattern of the film obtained in Example 1. FIG. It is a figure which shows the retardation value angle dependence ((alpha) angle) in wavelength 550nm of the pattern of the film obtained by the comparative example 1. FIG.

[(A) Polymer A]
The polymer (hereinafter referred to as polymer A) which is the component (A) of the composition of the present invention contains repeating units represented by the following formulas [1a] and [1b]. It contains a repeating unit represented by [1c].

（式［３］中、Ｒ¹は水素原子又はメチル基である。破線は結合手である（以下同じ）。）
これらのうち、Ｘ、Ｙともに式［３］で表される基が好ましい。In the formulas [1a] and [1c], X and Y are each independently a group represented by the following formula [2] or [3].

(In Formula [3], R ¹ is a hydrogen atom or a methyl group. The broken line is a bond (the same applies hereinafter).)
Of these, a group represented by the formula [3] is preferable for both X and Y.

（式［４］及び［５］中、ｓ１、ｓ２、ｓ３及びｓ４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る。）In formula [1a], M ¹ is a group represented by the following formula [4], and in formula [1b], M ² is a group represented by the following formula [5].

(Wherein [4] and [5], the s1, s2, s3 and s4, are each independently 1 or 2, G ¹ and G ² each independently represent a single bond, -COO- or -OCO- in R ² and R ³ each independently represent 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.)

Here, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. In the present invention, a fluorine atom is preferable.
The alkyl group may be linear, branched or cyclic, and the carbon number thereof is not particularly limited. In the present invention, a linear alkyl group having 1 to 10 carbon atoms is used. preferable. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, cyclobutyl group, n- Examples include a pentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, and an n-decyl group. 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 alkoxy group may be linear, branched or cyclic, and the number of carbon atoms is not particularly limited. In the present invention, a straight-chain alkoxy group having 1 to 10 carbon atoms is used. preferable. Specific examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, s-butoxy group, t-butoxy group, n-pentoxy group, and n-hexyl. An oxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, etc. are mentioned. 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, a methoxy group or the like.

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, t-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 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 -A tridecyl group, n-tetradecyl group, 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. Is preferably a number satisfying 0.2 ≦ m ≦ 0.8, 0.1 ≦ n ≦ 0.5, and 0.1 ≦ p ≦ 0.3.

  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 A preferably has a weight average molecular weight of 3,000 to 200,000, more preferably 4,000 to 150,000, and still more preferably 5,000 to 100,000. If the weight average molecular weight exceeds 200,000, the solubility in a solvent may be reduced and handling properties may be reduced. If the weight average molecular weight is less than 3,000, curing is insufficient at the time of thermosetting, resulting in solvent resistance and heat resistance. May decrease.
In the present invention, the weight average molecular weight is a measured value in terms of polystyrene by gel permeation chromatography (GPC).

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

  As for the content rate of said other repeating unit, 0-10 mol% is preferable in 100 mol% of all the repeating units. When the content rate of said other repeating unit is too large, characteristics, such as liquid crystallinity, of the polymer A may deteriorate.

  The polymer A can be used individually by 1 type or in combination of 2 or more types.

［式中、Ｒ²、Ｒ³、Ｇ¹、Ｇ²、Ａ、ｑ、ｒ、及びｓ１〜ｓ４は、上記と同じ。
Ｘ'及びＹ'は、それぞれ独立に下記式［１０］又は［１１］で表される重合性基である。

（式中、Ｒ¹は上記と同じ。）］[Synthesis of polymerizable compounds]
The polymerizable compound that is a raw material of the polymer A is represented by the following formula [7], [8], or [9].

[Wherein R ² , R ³ , G ¹ , G ² , A, q, r, and s1 to s4 are the same as above.
X ′ and Y ′ are each independently a polymerizable group represented by the following formula [10] or [11].

(Wherein R ¹ is the same as above)]

  The polymerizable compound represented by the above formula [7] is produced, for example, as follows.

（式中、Ｒ²、Ｘ'、ｑ、ｓ１及びｓ２は上記と同じ。ＤＣＣはＮ，Ｎ'−ジシクロヘキシルカルボジイミド、ＤＭＡＰは４−ジメチルアミノピリジンを表す。）When G ¹ is —COO—, as represented by the following scheme, it is produced by condensing a benzoic acid derivative represented by the formula [12] and a phenol derivative in a solvent in the presence of a condensing agent. The

(Wherein R ² , X ′, q, s1 and s2 are the same as above. DCC represents N, N′-dicyclohexylcarbodiimide, and DMAP represents 4-dimethylaminopyridine.)

（式中、Ｒ²、Ｘ'、ｑ、ｓ１及びｓ２は上記と同じ。）When G ¹ is —OCO—, it is produced by condensing a phenol derivative represented by the formula [13] and a benzoic acid derivative in a solvent in the presence of a condensing agent, as represented by the following scheme. The

(Wherein R ² , X ′, q, s1 and s2 are the same as above)

The compounds represented by the above formulas [12] and [13] are commercially available from SYNTHON Chemicals or Midori Chemical Co., when X ′ is a group represented by the formula [10].
In addition, the compounds represented by the above formulas [12] and [13] are, for example, Talaga et al. (P. Talaga, M. Schaeffer, C. Benezra) when X ′ is a group represented by the formula [11]. and JL Stampf, Synthesis, 530 (1990)). This method is a method of reacting 2- (bromomethyl) acrylic acid with an aldehyde or a ketone using SnCl ₂ as represented by the following synthesis scheme (A1). 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'は一価の有機基を表し、Ａｍｂｅｒｌｙｓｔ（登録商標）１５は、ロームアンドハース社製イオン交換樹脂である。ＴＨＦはテトラヒドロフランを表す。Ｅｔはエチル基を表す。）

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

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

（式中、Ｒ'は上記と同じ。）

(In the formula, R ′ is the same as above.)

（式中、ｑ及びｓ１は上記と同じ。Ｍｅはメチル基を表す。ＰＣＣはピリジニウムクロロクロマートを表す。）A compound represented by the formula [12] or [13] can be synthesized by the method of the following synthesis scheme (B) or (C) to which the method of the synthesis scheme (A1) or (A2) is applied.

(In the formula, q and s1 are the same as above. Me represents a methyl group. PCC represents pyridinium chlorochromate.)

（式中、ｑ及びｓ１は上記と同じ。）

(Wherein q and s1 are the same as above)

（式中、Ｒ³、Ｇ²、ｒ、ｓ３及びｓ４は、上記と同じ。）The compound represented by the formula [8] is, for example, condensed with a compound represented by the formula [14] and a cinnamic acid compound in a solvent in the presence of a condensing agent, as represented by the following scheme. It is manufactured by.

(In the formula, R ³ , G ² , r, s3 and s4 are the same as above.)

（式中、Ｇ²、ｒ、ｓ３及びｓ４は、上記と同じ。）The compound represented by the formula [14] can be obtained, for example, by the method shown in the following synthesis scheme (D).

(In the formula, G ² , r, s3 and s4 are the same as above.)

  The compound represented by the formula [9] is available as a commercial product when Y ′ is a group represented by the formula [10].

（式中、Ａは上記と同じ。）Moreover, the compound represented by Formula [9] can also be synthesize | combined by the method shown to the following synthetic scheme (E), when Y 'is group represented by Formula [11].

(In the formula, A is the same as above.)

[(B) Polymer B]
The polymer of the component (B) (hereinafter referred to as polymer B) contains a repeating unit represented by the following formula [6].

In the formula [6], R ⁴ is a hydrogen atom or a methyl group, and R ⁵ is a methyl group, an ethyl group, an n-propyl group, an isopropyl group or a cyclopropyl group. R ⁴ is preferably a methyl group. R ⁵ is preferably a methyl group.

  The polymer B preferably has a weight average molecular weight of 3,000 to 1,000,000, more preferably 5,000 to 600,000, and further preferably 5,000 to 100,000. preferable. When the weight average molecular weight exceeds 1,000,000, the solubility in a solvent may be lowered, and the handling property may be lowered.

  The polymer B may be a homopolymer composed of one type of repeating unit or a copolymer composed of a plurality of repeating units. When the polymer B is a copolymer, it is preferable that all repeating units satisfy the formula [6]. The polymer B is particularly preferably a homopolymer.

  The addition amount of the polymer B is preferably 1 to 15 parts by mass and more preferably 2 to 10 parts by mass with respect to 100 parts by mass of the polymer A.

  The polymer B can be used individually by 1 type or in combination of 2 or more types.

[Synthesis of polymer]
The method for synthesizing the polymers A and B is not particularly limited, and radical polymerization, anionic polymerization, cationic polymerization, and the like can be employed. Of these, radical polymerization is particularly preferred. Specifically, a polymerizable compound capable of giving the above-mentioned repeating unit is heated in the presence of a polymerization initiator in a solvent and polymerized.

  The polymerization initiator can be appropriately selected from conventionally known ones. For example, peroxides such as benzoyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide; persulfates such as sodium persulfate, potassium persulfate, ammonium persulfate; azobisisobutyronitrile (AIBN), azo Examples thereof include azo compounds such as bismethylbutyronitrile and azobisisovaleronitrile. These can be used individually by 1 type or in combination of 2 or more types.

The amount of the polymerization initiator used is preferably about 0.01 to 0.05 mol with respect to 1 mol of the polymerizable compound.
What is necessary is just to set reaction temperature suitably from 0 degreeC to the boiling point of the solvent to be used, but about 20-100 degreeC is preferable. The reaction time is preferably about 0.1 to 30 hours.

  The solvent used in the polymerization reaction is not particularly limited, and may be appropriately selected from various solvents generally used in the polymerization reaction. Specifically, water; methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, t-butanol, 1-pentanol, 2-pentanol, 3-pentanol, iso Alcohols such as pentanol, t-pentanol, 1-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 2-octanol, 2-ethyl-1-hexanol, benzyl alcohol, cyclohexanol; diethyl ether, diisopropyl Ethers such as ether, dibutyl ether, cyclopentyl methyl ether, tetrahydrofuran, and 1,4-dioxane; Halogenated hydrocarbons such as chloroform, dichloromethane, dichloroethane, and carbon tetrachloride; methyl cellosolve and ethyl cellosolve Ether alcohols such as isopropyl cellosolve, butyl cellosolve, diethylene glycol monobutyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; esters such as ethyl acetate, butyl acetate, ethyl propionate, cellosolve acetate; n-pentane, n -Aliphatic or aromatic hydrocarbons such as hexane, n-heptane, n-octane, n-nonane, n-decane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, ethylbenzene, anisole Acetals such as methylal and diethyl acetal; fatty acids such as formic acid, acetic acid and propionic acid; nitropropane, nitrobenzene, dimethylamine, monoethanol Emissions, pyridine, N- methyl-2-pyrrolidone (NMP), N, N- dimethylformamide, dimethyl sulfoxide, acetonitrile and the like. These can be used individually by 1 type or in mixture of 2 or more types.

  In the case where the polymers A and B contain the other repeating units, the synthesis method may be polymerization in the presence of a polymerizable compound that gives the other repeating units in the polymerization.

  The polymers A and B may be any of random copolymers, alternating copolymers, and block copolymers.

[(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; polarities such as N, N-dimethylformamide and N-methyl-2-pyrrolidone Solvent; Esters such as ethyl acetate, butyl acetate, ethyl lactate; methyl 3-methoxypropionate, methyl 2-methoxypropionate, ethyl 3-methoxypropionate, ethyl 2-methoxypropionate, ethyl 3-ethoxypropionate, Alkoxy esters such as 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, diethylene glycol Diglycol dialkyl ethers such as coal 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 and propylene glycol monoethyl ether; diethylene glycol monomethyl ether; Diglycol monoalkyl ethers such as diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether; glycol monoalkyl ether esters such as propylene glycol monomethyl ether acetate, carbitol acetate, ethyl cellosolve acetate; cyclohexanone, Me Ethyl ketone, methyl isobutyl ketone and 2-heptanone. These organic solvents can be used individually by 1 type or in mixture of 2 or more types.

Among these, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, cyclohexanone, a mixed solvent of toluene and 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]
In addition, 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 fluorine-based surfactants, silicone-based surfactants, nonionic surfactants, etc., but fluorine-based surfactants having a high effect of improving affinity with the substrate. Agents are preferred.

  Specific examples of the fluorosurfactant (hereinafter referred to as “trade name”), EFTOP EF301, EF303, EF352 (manufactured by Tochem Products), MegaFuck F171, F173, R-30 (manufactured by DIC Corporation) , FLORARD FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.) and the like. Not. In addition, surfactant can be used individually by 1 type or in combination of 2 or more types, The addition amount is 5 mass parts or less with respect to 100 mass parts of polymers A and B in total.

  Furthermore, an adhesion promoter may be added to the 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, Examples include, but are not limited to, heterocyclic compounds such as mercaptopyrimidine; urea compounds such as 1,1-dimethylurea and 1,3-dimethylurea; and thiourea compounds.

  An adhesion promoter can be used individually by 1 type or in combination of 2 or more types, The addition amount is 1 mass part or less with respect to 100 mass parts of polymers A and B in total.

[Composition]
The composition of the present invention is obtained by mixing (A) at least one polymer A, (B) at least one polymer B, (C) an organic solvent, and other components as necessary. . The method for preparing the composition of the present invention is not particularly limited, and the polymer A, the polymer B, and other components may be added to the organic solvent simultaneously or in any order and mixed.

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

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

The film formed in this manner 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 light to visible light having a wavelength of 150 to 450 nm is usually used, and it is performed by irradiating the 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, and is preferably 0.1 to 3 μm, for example.

  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.
[1] 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).
[2] Average molecular weight measurement The number average molecular weight (Mn) and the weight average molecular weight (Mw) were measured using Shodex GPC-101 (solvent: tetrahydrofuran, calibration curve: standard polystyrene) manufactured by Showa Denko K.K.
[3] Retardation value of film The α angle dependency of the retardation value at a wavelength of 550 nm was measured using a retardation measuring device (RETS-100, manufactured by Otsuka Electronics Co., Ltd.).
[4] Polarization microscope observation Observation was performed using a polarizing microscope E600-Pol manufactured by Nikon Corporation.

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

29.2 g (100 mmol) of 4- (6-acryloyloxy-1-hexyloxy) benzoic acid (manufactured by SYNTHON Chemicals), 17.0 g (100 mmol) of 4-hydroxybiphenyl, 0.6 g of DMAP, and a small amount of dibutylhydroxytoluene ( BHT) was suspended in 200 mL of methylene chloride under stirring at room temperature, and a solution of 24.0 g (116 mmol) of DCC dissolved in 100 mL of methylene chloride was added thereto and stirred overnight. The precipitated DCC urea was filtered off, and the filtrate was washed with 0.5 mol / L hydrochloric acid 150 mL, saturated aqueous sodium hydrogen carbonate solution 150 mL and saturated brine 150 mL successively, dried over magnesium sulfate, and the solvent was removed. 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 (P2)

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 a temperature of 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 (P2). (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 cooling tube, 7.2 g (23 mmol) of the intermediate compound (P2) obtained above, 4.1 g (25 mmol) of 2- (bromomethyl) acrylic acid, 60 mL of THF, tin (II) chloride 4.7 g (25 mmol) and 19 mL of a 10% by mass aqueous HCl solution were added to form a mixture, and the mixture was reacted by stirring at a temperature of 70 ° C. for 5 hours. 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 at room temperature with stirring. 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 50 mol of 0.5 mol / L hydrochloric acid, 50 mL of saturated aqueous sodium hydrogen carbonate solution and 50 mL of saturated brine successively, dried over magnesium sulfate, and the solvent was removed. Distilled off and purified by recrystallization with ethanol to obtain 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 polymer (1)

In a flask equipped with a condenser tube, 0.44 g (1.0 mmol) of the polymerizable compound (M1) obtained in Synthesis Example 1 and 0.30 g (0.6 mmol) of the polymerizable compound (M2) obtained in Synthesis Example 2 ), 0.10 g (0.4 mmol) of n-dodecyl acrylate, 8.0 g of NMP, and 17 mg 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 0.60g of polymers (1) (yield 71%).
Mn of the obtained polymer was 10,828 and Mw was 23,822 (Mw / Mn = 2.2).

[Synthesis Example 4] Synthesis of polymethyl methacrylate (PMMA) In a flask equipped with a cooling tube, 10.0 g (100 mmol) of methyl methacrylate, 100 mL of toluene and 160 mg of AIBN were charged, and the atmosphere in the flask was replaced with nitrogen. The reaction was stirred for 20 hours. The obtained reaction solution was put into 600 mL of hexane to precipitate a white powder. After filtering this white powder, it vacuum-dried at room temperature and obtained 8.1g of PMMA (yield 81%).
Mn of the obtained polymer was 9,045 and Mw was 19,899 (Mw / Mn = 2.2).

[Synthesis Example 5] Synthesis of polydecyl acrylate (PDA) A flask equipped with a cooling tube was charged with 12.0 g (50 mmol) of n-dodecyl acrylate, 100 g of 1,4-dioxane, and 80 mg of AIBN, and the atmosphere in the flask was replaced with nitrogen. Thereafter, the reaction was performed by stirring at a temperature of 60 ° C. for 20 hours, and then the obtained reaction solution was put into 2,000 mL of water / methanol (1/1). Since the obtained product was a viscous liquid, the product was separated by decantation and dried to obtain 7.4 g of PDA (yield 62%).
Mn of the obtained polymer was 14,120 and Mw was 38,124 (Mw / Mn = 2.7).

[Examples and Comparative Examples] Preparation of Composition and Production / Evaluation of Film A composition was prepared using the polymer obtained in the synthesis example, a film was produced, and its characteristics were examined.

[Example 1]
Polymer (1) 300 mg, PMMA (manufactured by ALDRICH, Mw = 120,000) 15 mg, and surfactant R-30 (manufactured by DIC Corporation) 0.6 mg were added to toluene / cyclohexanone (75/25, w / W) Dissolved in 1.700 g to obtain a composition.

[Example 2]
300 mg of polymer (1), 15 mg of PMMA synthesized in Synthesis Example 4, and 0.6 mg of surfactant R-30 (manufactured by DIC), 1.700 g of toluene / cyclohexanone (75/25, w / w) To obtain a composition.

[Example 3]
300 mg of polymer (1), 30 mg of PMMA synthesized in Synthesis Example 4, and 0.6 mg of surfactant R-30 (manufactured by DIC), 1.700 g of toluene / cyclohexanone (75/25, w / w) To obtain a composition.

[Example 4]
300 mg of polymer (1), 15 mg of polyethyl methacrylate (PEMA) (manufactured by ALDRICH, Mw = 515,000), and 0.6 mg of surfactant R-30 (manufactured by DIC), toluene / cyclohexanone (75/25, w / w) Dissolved in 1.700 g to obtain a composition.

[Comparative Example 1]
300 mg of polymer (1) and 0.6 mg of surfactant R-30 (manufactured by DIC Corporation) were dissolved in 1.700 g of toluene / cyclohexanone (75/25, w / w) to obtain a composition. .

[Comparative Example 2]
300 mg of polymer (1), 15 mg of polybutyl methacrylate (PBMA) (manufactured by ALDRICH, Mw = 337,000), and 0.6 mg of surfactant R-30 (manufactured by DIC), toluene / cyclohexanone (75/25, w / w) Dissolved in 1.700 g to obtain a composition.

[Comparative Example 3]
300 mg of polymer (1), 15 mg of poly (t-butyl methacrylate) (PtBMA) (manufactured by ALDRICH, Mw = 170,000), and 0.6 mg of surfactant R-30 (manufactured by DIC Corporation) in toluene / Cyclohexanone (75/25, w / w) was dissolved in 1.700 g to obtain a composition.

[Comparative Example 4]
300 mg of polymer (1), 15 mg of PDA synthesized in Synthesis Example 5, and 0.6 mg of surfactant R-30 (manufactured by DIC), 1.700 g of toluene / cyclohexanone (75/25, w / w) To obtain a composition.

[Preparation of oriented film]
Each composition was applied onto a TAC film by bar coating (bar # 5), prebaked at 60 ° C. for 2 minutes using a hot plate, and then allowed to cool to room temperature. At this time, the film | membrane obtained on the film was transparent.
Next, the coating film formed on the 10 × 10 cm TAC film was exposed by the following process and then post-baked at 110 ° C. for 15 minutes using an oven. The film thickness of the obtained film was about 1 μm, and when observed with a polarizing microscope, it was confirmed that the film was horizontally oriented with respect to the substrate surface.
[Exposure method (patterning process)]
Pattern 1: Irradiation with linearly polarized ultraviolet rays 20 mJ / cm ² was performed without a mask.
Pattern 2: After exposure with Pattern 1, half of the film was masked and further irradiated with linearly polarized ultraviolet rays 60 mJ / cm ² from the vertical direction (angle 90 °). By this method, a patterned film showing a difference of 90 ° in the orientation direction was obtained. During the exposure, the TAC film was stretched in the stretching direction and irradiated so that the patterns 1 and 2 were symmetrical with respect to the stretching direction.

  The retardation value (Δnd) and Δα of the obtained film are shown in Table 1 below. Note that Δα represents an angle deviation from the orientation angle (90 °).

  As is clear from Table 1, the addition of PMMA and PEMA could reduce the angle deviation in the orientation direction of the patterned film produced on the TAC film.

  1 and 2 show the α angle dependency of the retardation values of the films of Example 1 and Comparative Example 1. Comparing Example 1 (FIG. 1) and Comparative Example 1 (FIG. 2), in Example 1, the retardation value of both patterns is about 0 nm when the α angle is 45 °, whereas in Comparative Example 1, A shift in the retardation value of each pattern was observed.

Claims (4)

(A) Polymer A containing repeating units represented by the following formulas [1a], [1b] and [1c],
(B) Polymer B containing the repeating unit represented by the following formula [6], 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 [3], R ¹ is a hydrogen atom or a methyl group. The 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],

(Wherein [4] and [5], the s1, s2, s3 and s4, are each independently 1 or 2, G ¹ and G ² each independently represent a single bond, -COO- or -OCO- in 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.
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. ]

(In Formula [6], R ⁴ is a hydrogen atom or a methyl group, R ⁵ is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, or a cyclopropyl group.)   A single-layer coating type horizontal alignment film obtained by applying the composition according to claim 1 to a substrate, and then irradiating and curing the polarized light.   The single-layer coated horizontal alignment film according to claim 2, wherein the polarized light is linearly polarized ultraviolet light.   An optical member provided with the single layer application type | mold horizontal orientation film of Claim 2 or 3.

Images