JP2011246365A - Polymerizable liquid crystal compound, composition, and polymer thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compound having liquid crystallizability and good miscibility; and to provide a polymerizable liquid crystal composition containing the compound and having suitable optical anisotropy and good coatability.SOLUTION: The compound is represented by formula (1).

Description

  The present invention relates to a compound having a 1,4-dimethylenecyclohexane skeleton, a polymerizable liquid crystal composition containing the compound, a polymer film obtained from the polymerizable liquid crystal composition, an anisotropic polymer, and uses thereof.

In recent years, polymerizable liquid crystal compounds have been used in molded articles exhibiting optical anisotropy (birefringence) such as reflective polarizing plates and retardation plates. This compound exhibits optical anisotropy in a liquid crystal state, and its orientation is fixed by polymerization.
Examples of the fixed alignment state of the polymer include homogeneous (horizontal alignment), tilt (tilt alignment), homeotropic (vertical alignment), and twist (twist alignment).

  A polymer having homogeneous orientation can be used as a composite retardation plate or a circularly polarizing plate by combining with a half-wave plate, a quarter-wave plate, or a film having other optical functions, for example ( Patent Document 1).

Polymers having homeotropic alignment are classified as positive C-plates in the refractive index ellipsoid because the direction of the optical axis is in the _nz direction and the refractive index in the optical axis direction is greater than the refractive index in the orthogonal direction. Is done. This positive C-plate can be applied to optical compensation such as a horizontally aligned liquid crystal mode, so-called IPS (In-Plane Switching) mode, for example, improvement of viewing angle characteristics of a polarizing plate by combining with a film having other optical functions. (See Non-Patent Documents 1 to 3 and Patent Documents 2 to 3).

  In order to improve the function of such a polymer, various polymerizable compounds have been developed. However, one polymerizable compound often does not satisfy a sufficient function. Therefore, attempts have been made to prepare a composition by mixing several polymerizable compounds and polymerize the composition (see Patent Documents 4 to 5).

  When manufacturing the molded object which shows optical anisotropy, the liquid crystal composition before superposition | polymerization must maintain a liquid crystal state in the superposition | polymerization process normally performed at room temperature. Therefore, the polymerizable compound used in the liquid crystal composition must have good compatibility with other liquid crystal compounds. However, in general, a compound having a polymerizable group has a narrow liquid crystal temperature range due to the bulk of the polymerizable group, and has low compatibility with other liquid crystal compounds.

  Further, the optical anisotropy value (Δn) of the liquid crystalline compound does not show a constant value with respect to the wavelength of transmitted light (wavelength dispersion), and shows a larger value on the short wavelength side. This characteristic is not preferable when the molded body is used for an optical compensation plate such as a reflective polarizing plate or a retardation plate.

  Therefore, the optical anisotropy is small, the liquid crystal temperature range is wide, the compatibility with other liquid crystalline compounds is good, the polymerization rate, the degree of polymerization, the transparency of the polymer, the mechanical strength, the coatability, the solubility, the crystal A compound satisfying a degree of conversion, shrinkage, water permeability, water absorption, gas permeability, melting point, glass transition point, clearing point, heat resistance, chemical resistance and the like is desired.

  So far, the present inventors have found a polymerizable liquid crystal composition that can stably maintain a liquid crystal phase even at room temperature and exhibits uniform alignment (see Patent Document 6). However, in these compositions, when it is necessary to reduce optical characteristics, particularly optical anisotropy, the liquid crystal phase may not be maintained when the composition ratio is changed. In addition, in order to control optical anisotropy, it has been proposed to use a compound having an aromatic ring in the minor axis direction of the mesogen (compound having a triptycene ring), but a large amount of the compound is added to the composition. In such a case, crystallization may proceed, and there is a problem in controlling optical anisotropy (see Patent Document 7).

JP 2002-372623 A WO05 / 38517A1 brochure US2006 / 182900 JP 2006-307150 A JP 2004-231638 A JP 2007-16213 A JP 2006-111571 A

M.S.Park et al, IDW '04 FMC8-4 M.Nakata et al, SID '06 P-58 K.J.Kim et al, SID '06 Digest p.1158-1161

  The present invention has a liquid crystallinity, a compound having a good miscibility with other liquid crystal compounds and an organic solvent, and an appropriate optical anisotropy and a good coating property containing this compound. It is an object to provide a polymerizable liquid crystal composition having the following. Polymers excellent in optical anisotropy, transparency, chemical stability, heat resistance, hardness, dimensional stability, adhesion, adhesion, mechanical strength, and the like by polymerization of the polymerizable liquid crystal composition and its characteristics It is also an issue to provide an application using the. Furthermore, another object of the present invention is to provide a retardation film, an optical compensation film, and a reflective film containing this polymer, and to provide a liquid crystal display device containing these films.

  The present inventors have found that a polymerizable liquid crystal compound having a 1,4-dimethylenecyclohexane skeleton has a wide liquid crystal phase expression temperature range centering on room temperature, and has an excellent phase with other polymerizable liquid crystal compounds. It exhibits solubility, good solubility in organic solvents, and when used as a component of a polymerizable liquid crystal composition, it can ensure alignment uniformity of the optical anisotropic body and is effective in controlling optical anisotropy. While maintaining the liquid crystallinity, the optical anisotropy can be arbitrarily adjusted, and the polymer obtained from this polymerizable liquid crystal composition has a mechanical surface treatment such as rubbing, photo-alignment treatment, or chemical It has been found that an anisotropic polymer whose orientation is uniformly controlled can be formed when applied onto a support substrate subjected to a surface treatment.

The compound of the present invention is shown in the following [1].
[1] A compound represented by formula (1).

[式（２−１）〜（２−６）中、Ｒ^aは独立して水素、ハロゲン、炭素数１〜５のアルキルまたは炭素数１〜５のハロゲン化アルキルである。] (In formula (1), R ¹ is a polymerizable group represented by any ^one of formulas (2-1) to (2-6), hydrogen, chlorine, fluorine, —CN, alkyl having 1 to 10 carbons, Alkoxy having 1 to 10 carbons, —CF ₃ or —OCF ₃ ;
A ¹ is independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2,7- Diyl or bicyclo [2.2.2] octane-1,4-diyl, one or two non-adjacent —CH ₂ — in 1,4-cyclohexylene may be replaced by —O— One or two —CH═ in 1,4-phenylene may be replaced by —N═, and any hydrogen in 1,4-phenylene is halogen, —CN, alkyl having 1 to 5 carbons, or carbon 1 May be substituted with ˜5 alkoxy or C 1-5 alkyl halide;
Z ¹ is —CO—, —COCH ₂ —, —CO (CH ₂ ) ₂ — or —COCH═CH—;
Z ² is independently a single bond or alkylene having 1 to 20 carbon atoms, and any —CH ₂ — in the alkylene is —O—, —CO—, —COO—, —OCO—, —CH═CH—. , -CF = CF- or -C≡C-, and any hydrogen may be replaced by halogen;
Q ¹ is a single bond or alkylene having 1 to 20 carbon atoms, and any —CH ₂ — in the alkylene is —O—, —CO—, —COO—, —OCO—, —OCOO— or —CH═CH. -Any hydrogen may be replaced with halogen;
m is an integer from 1 to 5;
R ^a is hydrogen, halogen, alkyl having 1 to 5 carbons or alkyl halide having 1 to 5 carbons. )

[In formulas (2-1) to (2-6), R ^a is independently hydrogen, halogen, alkyl having 1 to 5 carbons or alkyl halide having 1 to 5 carbons. ]

  The compound of the present invention has a polymerizable group and a 1,4-dimethylenecyclohexane skeleton, has a liquid crystal phase, and has good miscibility with other liquid crystal compounds and organic solvents. In addition, the polymerizable liquid crystal composition containing the compound of the present invention can easily control optical anisotropy, has an appropriate optical anisotropy value, and has good coating properties. The anisotropic polymer and polymer film obtained by polymerization of the composition of the present invention have optical anisotropy, transparency, chemical stability, heat resistance, hardness, dimensional stability, adhesiveness, adhesion and mechanical strength. Excellent characteristics. Therefore, the polymer of the present invention is suitable for applications such as retardation films, polarizing elements, circularly polarizing elements, elliptically polarizing elements, antireflection films, selective reflection films, color compensation films, viewing angle compensation films, and liquid crystal alignment films. Yes.

Retardation measurement result of anisotropic polymer of Example 5 Retardation measurement result of anisotropic polymer of Example 6

  Hereinafter, the polymerizable liquid crystal compound according to the present invention, the polymerizable liquid crystal composition containing the compound, the polymer obtained from the composition, and the use thereof will be described in detail. The terminology used in this specification is as follows.

  “Liquid crystal compound” is a general term for compounds having a liquid crystal phase such as a nematic phase and a smectic phase, and compounds having no liquid crystal phase but useful as components of a liquid crystal composition. A compound having a liquid crystal phase such as a nematic phase or a smectic phase is particularly referred to as a “compound having liquid crystallinity”, and a compound having no liquid crystal phase is referred to as a “compound having no liquid crystallinity”.

  “Compound (1)” means a compound represented by the formula (1). Moreover, it may mean at least one of the compounds represented by the formula (1). “Composition (1)” means a composition containing at least one compound (1). “Polymer (1)” means a polymer obtained by polymerizing compound (1) or composition (1).

The term “arbitrary” used in describing a chemical structural formula means that not only the position but also the number is arbitrary. And for example, the expression “any A may be replaced by B, C or D” means that any A is replaced by B, any A is replaced by C, and any A is D In addition to the case where any A is replaced by at least two of B to D. However, it does not include that a plurality of consecutive —CH ₂ — are replaced by the same group.

The present invention includes the above [1] and the following [2] to [31].
[2] The compound according to [1], wherein in the formula (1) according to [1], m is an integer of 1 to 3.
[3] In the formula (1) according to [1], A ¹ is independently 1,4-cyclohexylene, 1,4-phenylene or 1,3-dioxane-2,5-diyl; Any hydrogen in 4-phenylene may be replaced by chlorine, fluorine, -CN, alkyl having 1 to 3 carbons, alkoxy having 1 to 3 carbons or fluoroalkyl having 1 to 3 carbons, [1] or The compound according to [2].

[4] In the formula (1) according to [1], A ¹ is independently 1,4-cyclohexylene or 1,4-phenylene, and any hydrogen in 1,4-phenylene is chlorine, fluorine, The compound according to any one of [1] to [3], which may be replaced by —CN, —CH ₃ , —OCH ₃ or —CF ₃ .

[5] In the formula (1) according to [1], Z ² is independently a single bond, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, —COOCH ₂ —, —CH. ₂ COOCH ₂ —, —CH═CH—, — (CH ₂ ) ₂ COO—, —OCO (CH ₂ ) ₂ —, —CH═CH—COO—, —OCO—CH═CH— or —C≡C— The compound according to any one of [1] to [4], wherein

[6] In the formula (1) according to [1], Z ² is independently a single bond, —COO—, —OCO—, —COOCH ₂ — or —CH ₂ COOCH ₂ —. [5] The compound according to any one of [5].

[7] In the formula (1) according to [1], R ¹ is located with a polymerizable group represented by any one of formulas (2-1) ~ (2-6); Q ¹ is 1 to the number of carbon atoms Any one of [1] to [6], wherein any of —CH ₂ — in the alkylene may be replaced by —O—, —COO—, —OCO— or —OCOO—. Compound described in 1.

[8] The formula (1) according to [1], wherein R ¹ is a polymerizable group represented by the formula (2-1), according to any one of [1] to [7]. Compound.
[9] In the formula (1) according to [1], R ¹ is hydrogen, chlorine, fluorine, —CN, alkyl having 1 to 10 carbons, alkoxy having 1 to 10 carbons, —CF ₃ or —OCF _3. The compound according to any one of [1] to [6], wherein Q ¹ is a single bond.

[10] The compound according to any one of [1] to [9], wherein m is 2 in the formula (1) according to [1].
[11] A polymerizable liquid crystal composition containing at least one of the compounds according to any one of [1] to [10].

  [12] A polymerizable liquid crystal composition comprising at least one compound represented by formula (1) and at least one polymerizable compound selected from the group of compounds represented by formulas (M1) and (M2) object.

（式（１）中、Ｒ¹は式（２−１）で表される重合性の基、水素、塩素、フッ素、−ＣＮ、炭素数１〜１０のアルキル、炭素数１〜１０のアルコキシ、−ＣＦ₃または−ＯＣＦ₃であり；
Ａ¹は独立して１，４−シクロヘキシレン、１，４−シクロヘキセニレン、１，４−フェニレン、ナフタレン−２，６−ジイル、テトラヒドロナフタレン−２，６−ジイル、フルオレン−２，７−ジイルまたはビシクロ［２．２．２］オクタン−１，４−ジイルであり、１，４−シクロヘキシレンにおける１つまたは隣接しない２つの−ＣＨ₂−は−Ｏ−で置き換えられてもよく、１，４−フェニレンにおける１つまたは２つの−ＣＨ＝は−Ｎ＝で置き換えられてもよく、１，４−フェニレンにおける任意の水素はハロゲン、−ＣＮ、炭素数１〜５のアルキル、炭素数１〜５のアルコキシまたは炭素数１〜５のハロゲン化アルキルで置き換えられてもよく；
Ｚ¹は−ＣＯ−、−ＣＯＣＨ₂−、−ＣＯ（ＣＨ₂）₂−または−ＣＯＣＨ＝ＣＨ−であり；
Ｚ²は独立して単結合または炭素数１〜２０のアルキレンであり、このアルキレンにおける任意の−ＣＨ₂−は−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−または−Ｃ≡Ｃ−で置き換えられてもよく、任意の水素はハロゲンで置き換えられてもよく；
Ｑ¹は単結合または炭素数１〜２０のアルキレンであり、このアルキレンにおける任意の−ＣＨ₂−は−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＯＣＯＯ−または−ＣＨ＝ＣＨ−で置き換えられてもよく、任意の水素はハロゲンで置き換えられてもよく；
ｍは１〜５の整数であり；
Ｒ^aは水素、ハロゲン、炭素数１〜５のアルキルまたは炭素数１〜５のハロゲン化アルキルである。）

(In formula (1), R ¹ is a polymerizable group represented by formula (2-1), hydrogen, chlorine, fluorine, —CN, alkyl having 1 to 10 carbons, alkoxy having 1 to 10 carbons, be -CF ₃ or -OCF _3;
A ¹ is independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2,7- Diyl or bicyclo [2.2.2] octane-1,4-diyl, one or two non-adjacent —CH ₂ — in 1,4-cyclohexylene may be replaced by —O— One or two —CH═ in 1,4-phenylene may be replaced by —N═, and any hydrogen in 1,4-phenylene is halogen, —CN, alkyl having 1 to 5 carbons, or carbon 1 May be substituted with ˜5 alkoxy or C 1-5 alkyl halide;
Z ¹ is —CO—, —COCH ₂ —, —CO (CH ₂ ) ₂ — or —COCH═CH—;
Z ² is independently a single bond or alkylene having 1 to 20 carbon atoms, and any —CH ₂ — in the alkylene is —O—, —CO—, —COO—, —OCO—, —CH═CH—. , -CF = CF- or -C≡C-, and any hydrogen may be replaced by halogen;
Q ¹ is a single bond or alkylene having 1 to 20 carbon atoms, and any —CH ₂ — in the alkylene is —O—, —CO—, —COO—, —OCO—, —OCOO— or —CH═CH. -Any hydrogen may be replaced with halogen;
m is an integer from 1 to 5;
R ^a is hydrogen, halogen, alkyl having 1 to 5 carbons or alkyl halide having 1 to 5 carbons. )

（式（２−１）中、Ｒ^aは水素、ハロゲン、炭素数１〜５のアルキルまたは炭素数１〜５のハロゲン化アルキルである。）

(In the formula (2-1), R ^a is hydrogen, halogen, alkyl having 1 to 5 carbons or alkyl halide having 1 to 5 carbons.)

（式（Ｍ１）および（Ｍ２）中、Ｒ²は独立して式（２−１）〜（２−６）のいずれかで表される重合性の基であり；
Ｒ³は独立して式（２−１）〜（２−６）のいずれかで表される重合性の基、炭素数１〜１０のアルキル、炭素数１〜１０のアルコキシ、水素、塩素、フッ素、−ＣＮ、−ＣＦ₃または−ＯＣＦ₃であり；
Ａ²は独立して１，４−シクロヘキシレン、１，４−フェニレン、ナフタレン−２，６−ジイル、テトラヒドロナフタレン−２，６−ジイル、フルオレン−２，７−ジイル、ビシクロ［２．２．２］オクタン−１，４−ジイル、トリプチセン−１，４−ジイルまたは１，４−フェニレンノルボルネンであり、この１，４−フェニレンおよびフルオレン−２，７−ジイルにおける任意の水素はハロゲン、−ＣＮ、炭素数１〜５のアルキル、炭素数１〜５のアルコキシまたは炭素数１〜５のハロゲン化アルキルで置き換えられてもよく；
Ｚ³は独立して単結合、−ＣＨ₂Ｏ−、−ＯＣＨ₂−、−ＣＯＯ−、−ＯＣＯ−、−Ｃ≡Ｃ−、−ＣＨ＝ＣＨＣＯＯ−、−ＯＣＯＣＨ＝ＣＨ−、−（ＣＨ₂）₂ＣＯＯ−、−ＯＣＯ（ＣＨ₂）₂−、−ＣＯＯ（ＣＨ₂）₂−、−（ＣＨ₂）₂ＯＣＯ−、−（ＣＨ₂）₂−または−Ｏ（ＣＨ₂）₂Ｏ−であり；
Ｑ²は独立して単結合または炭素数１〜２０のアルキレンであり、このアルキレンにおける任意の−ＣＨ₂−は−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＯＣＯＯ−または−ＣＨ＝ＣＨ−で置き換えられてもよく、任意の水素はハロゲンで置き換えられてもよく；
ｎは１〜５の整数であり；
ｘは０または１である。）

(In formulas (M1) and (M2), R ² is a polymerizable group independently represented by any one of formulas (2-1) to (2-6);
R ³ is independently a polymerizable group represented by any one of formulas (2-1) to (2-6), alkyl having 1 to 10 carbons, alkoxy having 1 to 10 carbons, hydrogen, chlorine, Fluorine, —CN, —CF ₃ or —OCF ₃ ;
A ² is independently 1,4-cyclohexylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diyl, bicyclo [2.2. 2] Octane-1,4-diyl, triptycene-1,4-diyl or 1,4-phenylenenorbornene, wherein any hydrogen in 1,4-phenylene and fluorene-2,7-diyl is halogen, —CN , May be replaced by alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons or alkyl halide having 1 to 5 carbons;
Z ³ is independently a single bond, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, —C≡C—, —CH═CHCOO—, —OCOCH═CH—, — (CH ₂ ) ₂ COO—, —OCO (CH ₂ ) ₂ —, —COO (CH ₂ ) ₂ —, — (CH ₂ ) ₂ OCO—, — (CH ₂ ) ₂ — or —O (CH ₂ ) ₂ O— Yes;
Q ² is independently a single bond or alkylene having 1 to 20 carbon atoms, and any —CH ₂ — in the alkylene is —O—, —CO—, —COO—, —OCO—, —OCOO— or — CH = CH— may be replaced and any hydrogen may be replaced with a halogen;
n is an integer from 1 to 5;
x is 0 or 1. )

（式（２−１）〜（２−６）中、Ｒ^aは独立して水素、ハロゲン、炭素数１〜５のアルキルまたは炭素数１〜５のハロゲン化アルキルである。）

(In formulas (2-1) to (2-6), R ^a is independently hydrogen, halogen, alkyl having 1 to 5 carbons or alkyl halide having 1 to 5 carbons.)

[13] In the formula (1) according to [12], A ¹ is independently 1,4-cyclohexylene, 1,4-phenylene or 1,3-dioxane-2,5-diyl; Any hydrogen in 4-phenylene may be replaced by chlorine, fluorine, -CN, alkyl having 1 to 3 carbons, alkoxy having 1 to 3 carbons or fluoroalkyl having 1 to 3 carbons;
Z ² is independently a single bond, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, —COOCH ₂ —, —CH ₂ COOCH ₂ —, —CH═CH—, — (CH ₂ ) ₂ COO—, —OCO (CH ₂ ) ₂ —, —CH═CH—COO—, —OCO—CH═CH— or —C≡C—;
Q ¹ is a single bond or alkylene having 1 to 10 carbons, and any —CH ₂ — in the alkylene may be replaced by —O—, —COO—, —OCO— or —OCOO—;
m is 1-3,
In the formulas (M1) and (M2) described in [12],
R ³ is independently a polymerizable group represented by formula (2-1), alkyl having 1 to 8 carbons, alkoxy having 1 to 8 carbons, chlorine, fluorine, —CN, —CF ₃ or —OCF. ₃ ;
A ² is independently 1,4-cyclohexylene, 1,4-phenylene or 1,4-phenylene norbornene, and any hydrogen in 1,4-phenylene is chlorine, fluorine, —CN, carbon number 1 to 3 alkyl, 1 to 3 carbon alkoxy or 1 to 3 halogenated alkyl may be substituted;
Z ³ is independently a single bond, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, —C≡C—, —CH═CHCOO—, —OCOCH═CH—, — (CH ₂ ) ₂ COO— or —OCO (CH ₂ ) ₂ —;
Q ² is independently a single bond or alkylene having 1 to 10 carbon atoms, and any —CH ₂ — in the alkylene may be replaced by —O—, —COO—, —OCO— or —OCOO—. ;
n is an integer of 2 or 3,
The polymerizable liquid crystal composition according to [12].

[14] In the formula (1) described in [12],
A ¹ is independently 1,4-cyclohexylene or 1,4-phenylene, and any hydrogen in 1,4-phenylene is replaced by chlorine, fluorine, —CH ₃ , —OCH ₃ or —CF ₃ Well;
Z ² is independently a single bond, —COO—, —OCO—, —COOCH ₂ — or —CH ₂ COOCH ₂ —;
Q ¹ is independently alkylene having 1 to 10 carbons, and —CH ₂ — closest to the ring in the alkylene may be replaced by —O—, —COO—, —OCO— or —OCOO—;
m is 2,
In the formulas (M1) and (M2) described in [12],
R ³ is independently a polymerizable group represented by the formula (2-1), alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons, —CN, fluorine, or —OCF ₃ . ;
A ² is independently 1,4-cyclohexylene, 1,4-phenylene, monofluoro-1,4-phenylene or difluoro-1,4-phenylene;
Z ³ is independently a single bond, —COO—, —OCO—, —CH═CHCOO—, —OCOCH═CH—, — (CH ₂ ) ₂ COO— or —OCO (CH ₂ ) ₂ —;
Q ² is independently a single bond or alkylene having 1 to 10 carbon atoms, and —CH ₂ — closest to the ring in the alkylene is replaced by —O—, —COO—, —OCO— or —OCOO—. Well;
n is 2 or 3;
[12] or the polymerizable liquid crystal composition according to [13].

[15] Total of the compound represented by formula (1) according to [12] and a polymerizable compound selected from the group of compounds represented by formulas (M1) and (M2) according to [12] The content of the compound represented by the formula (1) described in [12] is 1 to 90% by weight with respect to 100% by weight,
Any of [12] to [14], wherein the content of the polymerizable compound selected from the group of compounds represented by formula (M1) and formula (M2) according to [12] is 10 to 99% by weight 2. The polymerizable liquid crystal composition according to item 1.

[16] Total of the compound represented by formula (1) according to [12] and a polymerizable compound selected from the group of compounds represented by formulas (M1) and (M2) according to [12] The content of the compound represented by the formula (1) described in [12] is 3 to 85% by weight with respect to 100% by weight,
Any of [12] to [14], wherein the content of the polymerizable compound selected from the group of compounds represented by formula (M1) and formula (M2) according to [12] is 15 to 97% by weight 2. The polymerizable liquid crystal composition according to item 1.

[17] The polymerizability according to any one of [11] to [16], further containing a polymerizable compound having no liquid crystallinity other than the compound represented by the formula (1) according to [12]. Liquid crystal composition.
[18] The polymerizable liquid crystal composition according to any one of [11] to [17], further containing a non-polymerizable liquid crystal compound.

[19] The polymerizable liquid crystal composition according to any one of [11] to [18], further containing a polymerizable optically active compound.
[20] The polymerizable liquid crystal composition according to any one of [11] to [19], further containing a non-polymerizable optically active compound.

[21] A polymer film obtained by polymerizing the polymerizable liquid crystal composition according to any one of [11] to [20].
[22] An anisotropic polymer obtained by polymerizing the polymerizable liquid crystal composition according to any one of [11] to [20].

[23] The anisotropic polymer according to [22], wherein the alignment mode of the polymerizable liquid crystal composition is any one of homogeneous alignment, tilt alignment, twist alignment, and homeotropic alignment.
[24] The anisotropy according to [22] or [23], wherein the alignment form of the polymerizable liquid crystal composition is controlled by any one of rubbing treatment, photo-alignment treatment, ion beam treatment, corona treatment, and plasma treatment. Polymer.

[25] A laminate having a supporting base material made of a glass substrate or a plastic substrate and the anisotropic polymer described in any one of [22] to [24].
[26] An optical compensation film having the anisotropic polymer according to any one of [22] to [24] and / or the laminate according to [25].

[27] A reflective film having the anisotropic polymer according to any one of [22] to [24] and / or the laminate according to [25].
[28] A liquid crystal display device having the optical compensation film according to [26].
[29] A liquid crystal display device having the reflective film according to [27].
[30] A liquid crystal display device having the optical compensation film according to [26].
[31] A liquid crystal display device having the reflective film according to [27].

<< Compound (1) >>
The compound (1) is a polymerizable liquid crystal compound.

R ¹ in the above formula (1) is a polymerizable group represented by any ^one of the above formulas (2-1) to (2-6), hydrogen, chlorine, fluorine, —CN, alkyl having 1 to 10 carbon atoms. , Alkoxy having 1 to 10 carbon atoms, —CF ₃ or —OCF ₃ .
R ¹ is preferably a polymerizable group represented by the formula (2-1).

R ^a in the above formulas (2-1) to (2-6) is independently hydrogen, halogen, alkyl having 1 to 5 carbons or alkyl halide having 1 to 5 carbons, and hydrogen is preferable.

A ¹ in the above formula (1) is independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl. Fluorene-2,7-diyl or bicyclo [2.2.2] octane-1,4-diyl. In this 1,4-cyclohexylene, one or two non-adjacent —CH ₂ — may be replaced by —O—, and one or two —CH═ in 1,4-phenylene is replaced by —N═. And any hydrogen in 1,4-phenylene is replaced by halogen, -CN, alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons or alkyl halide having 1 to 5 carbons. Also good.

Preferred examples of A ¹ are 1,4-cyclohexylene, 1,4-phenylene or 1,3-dioxane-2,5-diyl, and any hydrogen in the 1,4-phenylene is chlorine, fluorine,- CN, alkyl having 1 to 3 carbon atoms, alkoxy having 1 to 3 carbon atoms, or fluoroalkyl having 1 to 3 carbon atoms may be substituted. A more preferred example of A ¹ is 1,4-cyclohexylene, and 1,4-phenylene in which any hydrogen may be replaced by chlorine, fluorine, —CN, —CH ₃ , —OCH ₃ or —CF ₃ It is.

Z ¹ in the formula (1) _{may, -CO -, - COCH 2 -} , - CO (CH 2) 2 - or -COCH = a CH-. A preferred example of Z ¹ is —CO— or —COCH ₂ —.

Z ² in the above formula (1) is independently a single bond or alkylene having 1 to 20 carbon atoms. And any —CH ₂ — in the alkylene may be replaced by —O—, —CO—, —COO—, —OCO—, —CH═CH—, —CF═CF— or —C≡C—. Well, any hydrogen may be replaced with a halogen. Preferred examples of Z ² include a single bond, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, —COOCH ₂ —, —CH ₂ COOCH ₂ —, —CH═CH—, — (CH ₂ ) ₂ COO—, —OCO (CH ₂ ) ₂ —, —CH═CH—COO—, —OCO—CH═CH— and —C≡C—, more preferred examples being a single bond, —COO—, — OCO -, - COOCH ₂ - and -CH ₂ COOCH ₂ - are.

Q ¹ in the above formula (1) is independently a single bond or alkylene having 1 to 20 carbon atoms. Any —CH ₂ — in the alkylene may be replaced with —O—, —CO—, —COO—, —OCO—, —OCOO— or —CH═CH—, and any hydrogen is replaced with a halogen. May be. A preferred example of Q ¹ is that when R ¹ is a polymerizable group, any —CH ₂ — may be replaced by —O—, —COO—, —OCO— or —OCOO—. In the case of alkylene having 1 to 10 carbons and R ¹ is hydrogen, chlorine, fluorine, —CN, alkyl having 1 to 10 carbons, alkoxy having 1 to 10 carbons, —CF ₃ or —OCF ₃ Is a single bond.

  M in the above formula (1) is independently an integer of 1 to 5. m is preferably an integer of 1 to 3, and m is more preferably 2.

  The compound (1) of the present invention has high polymerization reactivity. Since compound (1) has a 1,4-dimethylenecyclohexane skeleton, it tends to be a compound having small optical anisotropy and excellent solubility. Since compound (1) has a liquid crystal skeleton, it is easily compatible with other liquid crystalline compounds, polymerizable compounds and the like to be uniform, and the liquid crystal phase is easily maintained. Compound (1) has optical activity when it has an asymmetric carbon.

By appropriately selecting the terminal group, ring and bonding group of compound (1), it is possible to arbitrarily adjust physical properties such as optical anisotropy and solubility in a solvent. The effects of the terminal group R ¹ , ring A ¹ and the types of the linking groups Z ¹ and Z ^{2 on} the physical properties of the compound (1) will be described below.

When the terminal group R ¹ is alkyl having 1 to 10 carbons or alkoxy having 1 to 10 carbons, the melting point and the solubility in a solvent are affected, and chlorine, fluorine, —CN, —CF ₃ or —OCF _When it is ₃ , it seems to affect the characteristics such as the melting point, the solubility in a solvent, and the compatibility with other compounds.

Ring A ¹ is 1,4-phenylene, 1,4-phenylene in which any hydrogen is replaced by fluorine, pyridine-2,5-diyl, pyrimidine-2,5-diyl or pyridazine-3,6-diyl In some cases, it tends to be a compound with large optical anisotropy. When the ring A ¹ is 1,4-cyclohexylene, 1,4-cyclohexenylene, or 1,3-dioxane-2,5-diyl, the compound tends to be a compound having small optical anisotropy. When at least two of the plurality of rings A ¹ are 1,4-cyclohexylene, the clearing point tends to be high, the optical anisotropy is small, and the viscosity is low. When at least one ring is 1,4-phenylene, it tends to be a compound having a relatively large optical anisotropy and a large orientational order parameter. When at least two rings are 1,4-phenylene, there is a tendency that the optical anisotropy is large, the temperature range of the liquid crystal phase is wide, and the clearing point is high.

When the bonding group Z ¹ is —CO—, it tends to be a compound having a low clearing point. When the bonding group Z ¹ is —COCH ₂ —, the optical anisotropy is small and the temperature range of the liquid crystal phase tends to be widened.

When the bonding group Z ² is —CH ₂ O—, —OCH ₂ —, or —CF═CF—, it tends to be a compound having a low viscosity. When the linking group Z ² is a single bond, — (CH ₂ ) ₂ —, —OCF ₂ —, —CF ₂ O—, —CH═CH— or — (CH ₂ ) ₄ —, Tend to be. When the bonding group Z ² is —CH═CH— or —CF═CF—, there is a tendency that the temperature range of the liquid crystal phase is wide and the compound has a large elastic constant ratio. When the bonding group Z ² is —C≡C—, it tends to be a compound having a large optical anisotropy.

  When m is 2 or less, the compound tends to be a low viscosity compound, and when m is 2 or more, the compound tends to be a compound with a high clearing point.

  Compound (1) may be optically active or optically inactive. The configuration of the asymmetric carbon when optically active may be R or S. When it has asymmetric carbon, it tends to be a compound with good compatibility.

  As described above, a compound having desired physical properties can be obtained by appropriately selecting the types of terminal groups, rings and bonding groups, and the number of rings.

  Compound (1) can be synthesized by combining organic synthetic chemistry techniques. Methods for introducing the desired end groups, rings and linking groups into the starting material are described by Houben-Wyle, Methods of Organic Chemistry, Georg Thieme Verlag, Stuttgart, Organic Syntheses, John Wily & Sons. , Inc.), Organic Reactions (John Wily & Sons Inc.), Comprehensive Organic Synthesis (Pergamon Press), and New Experimental Chemistry Course (Maruzen) Are listed.

An example of the synthesis method of the compound (1) will be described in the following schemes 1 to 14 according to the synthesis method of the bonding group Z ² . Furthermore, an example of a method for synthesizing the compound (1) will be described in the following scheme 15 by dividing it according to the method for synthesizing the bonding group Z ¹ . In these schemes, MSG ¹ is a monovalent organic group having at least one ring, and MSG ² is a monovalent organic group. A plurality of MSG ¹ (or MSG ² ) may be the same or different. Compounds (1A) to (1P) and (1a) to (1d) correspond to compound (1) of the present invention. These methods can be applied to the optically active compound (1) and the optically inactive compound (1). These methods can also be applied when Q ¹ is synthesized.
In the scheme below, Hal represents a halogen atom.

<Scheme 1> Compound in which Z ² is a single bond As shown below, a compound (S1) and a compound (S2) synthesized by a known method are mixed with tetrakis (triphenylphosphine) palladium, etc. in an aqueous carbonate solution. Compound (1A) can be synthesized by reacting in the presence of the catalyst. This compound (1A) is obtained by reacting a compound (S3) synthesized by a known method with n-butyllithium and then reacting with zinc chloride, and then in the presence of a catalyst such as dichlorobis (triphenylphosphine) palladium. And can be synthesized by further reacting with the compound (S2).

<Scheme 2> Compound in which Z ² is —CH═CH— As shown below, phosphorus ylide synthesized by adding a base such as potassium t-butoxide to a phosphonium salt (S5) synthesized by a known method; Compound (1B) can be synthesized by reacting with aldehyde (S4). Since a cis isomer is generated depending on reaction conditions and substrates, the cis isomer is isomerized to a trans isomer by a known method as necessary.

<Scheme 3> Compound in which Z ² is — (CH ₂ ) ₂ — As shown below, compound (1C) can be synthesized by hydrogenating compound (1B) in the presence of a catalyst such as palladium carbon. .

<Scheme 4> Compound in which Z ² is — (CF ₂ ) ₂ — As shown below, according to the method described in J. Am. Chem. Soc., 2001, 123, 5414, A compound (1D) having — (CF ₂ ) ₂ — can be synthesized by fluorinating the diketone (S6) in the presence of a fluorination catalyst.

<Scheme 5> Compound in which Z ² is — (CH ₂ ) ₄ — As shown below, in accordance with the method of Scheme 2, using phosphonium salt (S7) instead of phosphonium salt (S5), — (CH ₂ ) Compound (1E) can be synthesized by synthesizing a compound having ₂ -CH═CH— and catalytically hydrogenating the compound.

<Scheme 6> Compound in which Z ² is —CH ₂ O— or —OCH ₂ — As shown below, first, compound (S4) is reduced with a reducing agent such as sodium borohydride to obtain compound (S8). obtain. This is halogenated with hydrobromic acid or the like to obtain compound (S9). Next, compound (1F) can be synthesized by reacting compound (S9) with compound (S10) in the presence of potassium carbonate or the like. A compound having —CH ₂ O— can also be synthesized by this method.

<Scheme 7> Compound in which Z ² is —COO— or —OCO— As shown below, compound (S3) and n-butyllithium are reacted, and then carbon dioxide is reacted to produce carboxylic acid (S11). obtain. Compound (1G) having —COO— can be synthesized by dehydrating compound (S11) and compound (S10) in the presence of DCC (1,3-dicyclohexylcarbodiimide) and DMAP (4-dimethylaminopyridine). . A compound having —OCO— can also be synthesized by this method.
Further, by reacting (S11) with thionyl chloride or oxalyl chloride to obtain an acid chloride compound, compound (1G) is synthesized by reacting with compound (S10) in the presence of a base such as pyridine or triethylamine. You can also

<Scheme 8> Compound in which Z ² is —CF═CF— As shown below, first, compound (S3) and n-butyllithium are reacted, and then tetrafluoroethylene is reacted to give compound (S12). Get. Next, after reacting compound (S2) and n-butyllithium, compound (1H) can be synthesized by reacting the obtained compound with compound (S12). A cis compound (1H) can also be synthesized by selecting the synthesis conditions.

<Scheme 9> Compound in which Z ² is —C≡C— As shown below, compound (S13) is reacted with compound (S2) in the presence of a catalyst of dichloropalladium and copper halide to give a compound ( 1J) can be synthesized.

<Scheme 10> Compound in which Z ² is —C≡C—COO— As shown below, first, compound (S13) is lithiated with n-butyllithium and then reacted with carbon dioxide to react with carboxylic acid (S14 ) Next, by dehydrating the carboxylic acid (S14) and the compound (S10) in the presence of DCC and DMAP, a compound (1K) having —C≡C—COO— can be synthesized. A compound having —OCO—C≡C— can also be synthesized by this method.
Further, as (1G) was synthesized from (S11) in Scheme 7, it is possible to first synthesize an acid chloride compound and further synthesize a compound (1K) from the acid chloride compound.

<Scheme 11> Compound in which Z ² is —C≡C—CH═CH— or —CH═CH—C≡C— As shown below, cross coupling of compound (S13) and vinyl bromide (S15) A compound (1L) having —C≡C—CH═CH— can be synthesized by the reaction. When the cis-isomer compound (S15) is used, a cis-isomer (1L) can be produced. By this method, a compound having —CH═CH—C≡C— can also be synthesized.

<Scheme 12> Compound in which Z ² is —CF ₂ O— or —OCF ₂ — As shown below, first, compound (1G) is treated with a sulfurizing agent such as Lawesson's reagent to obtain compound (S16). . Next, the compound (1M) having —CF ₂ O— can be synthesized by fluorinating the compound (S16) using a hydrogen fluoride pyridine complex and NBS (N-bromosuccinimide). The compound (1M) can also be synthesized by fluorinating the compound (S16) with (diethylamino) sulfur trifluoride (DAST). A compound having —OCF ₂ — can also be synthesized by this method. It is also possible to synthesize compounds having these bonding groups by the method described in P. Kirsch et al., Angew. Chem. Int. Ed. 2001, 40, 1480.

<Scheme 13> Compound in which Z ² is —CH═CHCOO— or —OCOCH═CH— As shown below, compound (S4) is first synthesized into compound (S17) by Wittig reaction. Next, the compound (S17) and the compound (S10) are dehydrated in the presence of DCC (1,3-dicyclohexylcarbodiimide) and DMAP (4-dimethylaminopyridine), whereby the compound (1N having —CH═CHCOO— is obtained. ) Can be synthesized. A compound having -OCOCH = CH- can also be synthesized by this method.

<Scheme 14> Compound in which Z ² is — (CH ₂ ) ₂ COO— or —OCO (CH ₂ ) ₂ — As shown below, compound (1N) is hydrogenated in the presence of a catalyst such as palladium carbon. Thus, the compound (1P) having — (CH ₂ ) ₂ COO— can be synthesized. A compound having —OCO (CH ₂ ) ₂ — can also be synthesized by this method.

<Scheme 15>
As shown below, by dehydrating 1,4-cyclohexanedimethanol monoacrylate and compound (S11) in the presence of DCC (1,3-dicyclohexylcarbodiimide) and DMAP (4-dimethylaminopyridine), Z ^A compound (1a) in which ¹ is —CO— can be synthesized.

  Further, as (1G) was synthesized from (S11) in Scheme 7, it is also possible to first synthesize an acid chloride compound and further synthesize compound (1a) from the acid chloride compound.

Further, 1,4-cyclohexanedimethanol monoacrylate and compound (S18), compound (S17) or compound (S19) are dehydrated in the presence of DCC and DMAP, respectively, so that Z ¹ is —COCH ₂ —. A compound (1b), a compound (1c) in which —COCH═CH—, or a compound (1d) having —CO (CH ₂ ) ₂ — can be synthesized.

  The compound (1) of the present invention can be synthesized by appropriately combining the above methods, but is not necessarily limited to the above method. Examples of compounds synthesized by the above method are shown below. The structure of the compound synthesized as described above can be confirmed by, for example, a proton NMR spectrum.

≪Polymerizable liquid crystal composition≫
The polymerizable liquid crystal composition of the present invention has the following first to third embodiments.
The 1st aspect of the polymeric liquid crystal composition of this invention contains the compound (1) which has one polymeric liquid crystallinity. The second embodiment contains at least two compounds (1). The third aspect is a polymerizable compound other than the compound (1) (hereinafter also referred to as other polymerizable compound), a non-polymerizable liquid crystal compound, and / or an optically active compound, and at least one compound. (1). The polymerizable liquid crystal composition of these three embodiments is also referred to as a composition (1). That is, the composition (1) contains at least one compound (1). The polymerizable liquid crystal composition of the present invention has characteristics such as good coatability.

  Further, the composition (1) of the present invention may further contain a polymerization initiator, a solvent, a surfactant, an organosilicon compound, a chain transfer agent, and other additives as long as the effects of the present invention are not impaired. Good.

  The other polymerizable compound is preferably a compound that does not lower the film-forming property of the composition (1) and the mechanical strength of the polymer obtained from the composition (1). This compound is classified into a compound having liquid crystallinity and a compound having no liquid crystallinity.

  In order to obtain a polymerizable liquid crystal composition with easy control of optical anisotropy and good coatability, and to remarkably express the effects of the polymer of the present invention as described above, the composition (1) The content of the other polymerizable compound having liquid crystallinity is preferably 10 to 99% by weight, more preferably 15 to 100% by weight based on the total amount of the compound (1) and the other polymerizable compound. 97% by weight. The amount ratio of the other polymerizable compound having liquid crystallinity and the other polymerizable compound not having liquid crystallinity can be freely changed as long as the total amount thereof is within the above range. May contain only.

(Other polymerizable compounds having liquid crystallinity)
Other polymerizable compounds having liquid crystallinity can adjust the temperature range of the liquid crystal phase of the composition, optical anisotropy, coatability, and the like. Examples of such compounds include compounds having liquid crystallinity having an acryloyloxy group, a methacryloyloxy group, a fumaroyloxy group, a maleimidyl group, an oxirane ring and an oxetane ring, and compounds other than the above compound (1). it can. Other polymerizable compounds having liquid crystallinity may or may not be optically active.

  Preferable examples of the other polymerizable compound having liquid crystallinity are compounds represented by the above formulas (M1) and (M2).

  In the polymerizable liquid crystal composition, the content of the compound represented by the formula (1) is preferably 1 to 100% by weight with respect to the total amount of the compound (1) and the polymerizable compound having liquid crystallinity. 90% by weight, more preferably 3 to 85% by weight, and the content of the polymerizable compound selected from the group of compounds represented by the above formulas (M1) and (M2) is preferably 10 to 10%. It is 99 weight%, More preferably, it is 15 to 97 weight%. When the content of each component in the polymerizable liquid crystal composition is in the above range, the optical anisotropy can be easily controlled, a polymerizable liquid crystal composition having good coating properties can be obtained, and the above Thus, the effects of the polymer of the present invention can be remarkably exhibited.

In the above formulas (M1) and (M2), R ² is independently a polymerizable group represented by any one of the above formulas (2-1) to (2-6).

In the above formulas (2-1) to (2-6), R ^a is independently hydrogen, halogen, alkyl having 1 to 5 carbons or halogenated alkyl having 1 to 5 carbons. Preferred examples of R ^a are hydrogen, methyl and ethyl.

R ³ in the above formulas (M1) and (M2) is independently a polymerizable group represented by any one of the above formulas (2-1) to (2-6), an alkyl having 1 to 10 carbon atoms, alkoxy having 1 to 10 carbon atoms, hydrogen, chlorine, fluorine, -CN, a -CF ₃ or -OCF _3. Preferred examples of R ³ include a polymerizable group represented by the formula (2-1), alkyl having 1 to 8 carbons, alkoxy having 1 to 8 carbons, chlorine, fluorine, —CN, —CF ₃ and —OCF. ₃ .

A ² in the above formulas (M1) and (M2) is independently 1,4-cyclohexylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2 , 7-diyl, bicyclo [2.2.2] octane-1,4-diyl, triptycene-1,4-diyl or 1,4-phenylenenorbornene, which is 1,4-phenylene and fluorene-2,7. Arbitrary hydrogen in -diyl may be replaced by halogen, -CN, alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons or halogenated alkyl having 1 to 5 carbons. Preferred examples of A ² are 1,4-cyclohexylene and 1,4-phenylene, and any hydrogen in 1,4-phenylene is chlorine, fluorine, —CN, alkyl having 1 to 3 carbons, 1 carbon. It may be replaced by ˜3 alkoxy or C 1-3 alkyl halide.

Z ³ in the above formulas (M1) and (M2) is independently a single bond, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, —C≡C—, —CH═CHCOO—. , -OCOCH = CH -, - ( CH 2) 2 COO -, - OCO (CH 2) 2 -, - COO (CH 2) 2 -, - (CH 2) 2 OCO -, - (CH 2) 2 - or -O (CH _{2) 2} is O-. Preferred examples of Z ³ include a single bond, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, —C≡C—, —CH═CHCOO—, —OCOCH═CH—, — (CH ₂ ) ₂ COO— and —OCO (CH ₂ ) ₂ —. More preferred examples of Z ³ are a single bond, —COO—, —OCO—, —CH═CHCOO—, —OCOCH═CH—, — (CH ₂ ) ₂ COO— and —OCO (CH ₂ ) ₂ —. is there.

Q ² in the above formulas (M1) and (M2) is independently a single bond or alkylene having 1 to 20 carbon atoms, and any —CH ₂ — in the alkylene is —O—, —CO—, —COO. -, -OCO-, -OCOO-, or -CH = CH- may be substituted. A preferable example of Q ² is a single bond or alkylene having 1 to 10 carbon atoms, and any —CH ₂ — in the alkylene may be replaced by —O—, —COO—, —OCO— or —OCOO—. . A more preferred example of Q ² is a single bond or alkylene having 1 to 10 carbon atoms. In this alkylene, —CH ₂ — closest to the ring is —O—, —COO—, —OCO— or —OCOO—. It may be replaced.

In the above formulas (M1) and (M2), n is an integer of 1 to 5. n is preferably an integer of 2 or 3.
In the above formulas (M1) and (M2), x is 0 or 1.

The compound (M1) and the compound (M2) exhibit a liquid crystal phase in a wide temperature range.
When R ³ is a polymerizable group, since the compounds (M1) and (M2) have two or more polymerizable groups in the structure, the polymerizable liquid crystal composition containing this compound is polymerized. The polymer can form a three-dimensional network structure, and a polymer having high mechanical strength can be formed. When R ³ is not a polymerizable group in the compound (M1), it becomes a monofunctional compound, and a substituent such as a polar group can be introduced on the opposite side of the polymerizable group in the molecular long axis direction. The alignment control can be adjusted. In both the compound (M1) and the compound (M2), when the ring structure A ² is 1,4-phenylene, a composition having a large optical anisotropy value (Δn) can be obtained. In the case of silene, a composition having a low Δn can be obtained.

In the composition (1) of the present invention, in the above formula (1), A ¹ is independently 1,4-cyclohexylene, 1,4-phenylene or 1,3-dioxane-2,5-diyl. And any hydrogen in 1,4-phenylene may be replaced by chlorine, fluorine, -CN, alkyl having 1 to 3 carbons, alkoxy having 1 to 3 carbons or fluoroalkyl having 1 to 3 carbons; Z ² is independently a single bond, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, —COOCH ₂ —, —CH ₂ COOCH ₂ —, —CH═CH—, — (CH ₂ ) ₂ COO—, —OCO (CH ₂ ) ₂ —, —CH═CH—COO—, —OCO—CH═CH— or —C≡C—; Q ¹ is a single bond or 1 to 10 carbon atoms alkylene, arbitrary -CH ₂ - in this alkylene O -, - COO -, - OCO- or -OCOO- may be replaced by; m is 1 to 3, the compound (1),
In the above formulas (M1) and (M2), R ³ is independently a polymerizable group represented by the above formula (2-1), alkyl having 1 to 8 carbons, alkoxy having 1 to 8 carbons, chlorine , Fluorine, —CN, —CF ₃ or —OCF ₃ ; A ² is independently 1,4-cyclohexylene, 1,4-phenylene or 1,4-phenylenenorbornene, and this 1,4-phenylene Any hydrogen in can be replaced by chlorine, fluorine, -CN, alkyl having 1 to 3 carbons, alkoxy having 1 to 3 carbons or halogenated alkyl having 1 to 3 carbons; Z ³ is independently Single bond, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, —C≡C—, —CH═CHCOO—, —OCOCH═CH—, — (CH ₂ ) ₂ COO— or — OCO (CH _{2) 2} - a and; Q ² is independently A single bond or alkylene having 1 to 10 carbon atoms, arbitrary -CH ₂ - in this alkylene -O -, - COO -, - OCO- or -OCOO- may be replaced by; n is 2 or 3 It is preferable to contain the compound (M1) and / or (M2) which are the integers.
This polymerizable liquid crystal composition is easy to control optical anisotropy, and tends to have good solubility, liquid crystallinity, and coatability in other liquid crystal compounds and organic solvents.

Further, in the composition (1) of the present invention, in the above formula (1), A ¹ is independently 1,4-cyclohexylene or 1,4-phenylene, and any hydrogen in 1,4-phenylene is May be replaced by chlorine, fluorine, —CH ₃ , —OCH ₃ or —CF ₃ ; Z ² is independently a single bond, —COO—, —OCO—, —COOCH ₂ — or —CH ₂ COOCH ₂ —. Q ¹ is independently an alkylene having 1 to 10 carbon atoms, and —CH ₂ — closest to the ring in the alkylene is replaced by —O—, —COO—, —OCO— or —OCOO—. Compound (1), wherein m is 2,
In the above formulas (M1) and (M2), R ³ is independently and independently a polymerizable group represented by the above formula (2-1), an alkyl having 1 to 5 carbons, or an alkyl having 1 to 5 carbons. Alkoxy, —CN, fluorine or —OCF ₃ ; A ² is independently 1,4-cyclohexylene, 1,4-phenylene, monofluoro-1,4-phenylene or difluoro-1,4-phenylene. Z ³ is independently a single bond, —COO—, —OCO—, —CH═CHCOO—, —OCOCH═CH—, — (CH ₂ ) ₂ COO— or —OCO (CH ₂ ) ₂ —; Q ² is independently a single bond or alkylene having 1 to 10 carbon atoms, and —CH ₂ — closest to the ring in the alkylene is replaced by —O—, —COO—, —OCO— or —OCOO—. N is 2 or 3, It is preferable to contain a compound (M1) and / or a compound (M2).
This polymerizable liquid crystal composition is easier to control optical anisotropy than the above composition (1), and has good solubility, liquid crystallinity and coatability in other liquid crystal compounds and organic solvents. Tend to have.

  In addition, the bond position of fluorine to the phenylene ring in the monofluoro-1,4-phenylene and difluoro-1,4-phenylene may be any.

  Preferred examples of the compound (M1) and the compound (M2) include the following compounds (M1-1-1) to (M1-2-40) and compounds (M2-1-1) to (M2-2-7), respectively. ).

In the following compounds, Q ² has the same meaning as Q ² in the formula (M1) and (M2), R ² is the following independently formula (2-1-1), formula (2-2), It is a group represented by Formula (2-3-1), Formula (2-4), Formula (2-5-1), Formula (2-6-1), or Formula (2-6-2).

In each preferred example of the compound (M1) and the compound (M2), R ² is a group represented by the formula (2-1-1), and Q ² is alkyl or alkoxy having 3 to 6 carbon atoms. Certain compounds are preferred.

(Other polymerizable compounds not having liquid crystallinity)
Other polymerizable compounds having no liquid crystallinity include vinyl derivatives, styrene derivatives, (meth) acrylic acid derivatives, oxirane derivatives, oxetane derivatives, sorbic acid derivatives, fumaric acid derivatives, itaconic acid derivatives, etc. The thing which does not have property is mentioned. “(Meth) acrylic acid derivative” is a general term for acrylic acid derivatives or methacrylic acid derivatives. These compounds are suitable for adjusting the viscosity and orientation of the polymerizable liquid crystal composition, and have a great effect of making the thickness of the coating film uniform when the composition is applied. Other polymerizable compounds having no liquid crystallinity include a compound having one polymerizable group, a compound having two polymerizable groups, and a polyfunctional compound having three or more polymerizable groups. A compound having one polymerizable group is suitable for adjusting the viscosity, the melting point and the like. A compound having two or more polymerizable groups is suitable for controlling the mechanical strength of the polymer. Other polymerizable compounds having no liquid crystallinity may be optically active or non-optically active, but optically active compounds are preferred.

  Specific examples of these compounds include compounds described in paragraphs 0097 to 0101 of JP2008-266632A.

  Moreover, you may use the polymeric compound which has the following bisphenol structures. These compounds are suitable for assisting film forming ability and alignment uniformity of the polymerizable liquid crystal composition.

  Compound (N-10) to compound (N-15) are described in Japanese Patent Application Laid-Open No. 2007-16213 and Japanese Patent Application Laid-Open No. 2008-133344. The amount of compound (N-1) to (N-15) added is 0.1% to 25% by weight, preferably 1% to 15%, based on the entire composition (excluding the solvent). % By weight. A plurality of types of compounds may be used.

(Non-polymerizable liquid crystal compound)
The composition (1) may contain a non-polymerizable liquid crystal compound having no polymerizable group. Examples of such non-polymerizable liquid crystal compounds are described in Licris, a database of liquid crystal compounds (LiqCryst, LCI Publisher GmbH, Hamburg, Germany). The compound (1) has good compatibility with other components other than the compound (1) in the composition (1). Therefore, the composition (1) can be used as a liquid crystal composition sealed in a liquid crystal display element. Such a composition (1) may further contain additives such as a dichroic dye. In order to obtain a polymerizable liquid crystal composition with easy control of optical anisotropy and good coatability, and to remarkably express the effects of the polymer of the present invention as described above, the composition (1) The content of the non-polymerizable liquid crystal compound is preferably 50% by weight or less, more preferably 30% by weight or less with respect to 100% by weight of the total amount of the compound (1) and other polymerizable compounds. .

［式（Ａ）中、Ｑ²、Ａ²およびｎはそれぞれ前記式（Ｍ１）中のＱ²、Ａ²およびｎと同義であり、Ｚ^Aは独立して単結合または炭素数１〜１０のアルキレンであり、このアルキレンにおける任意の−ＣＨ₂−は−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−または−Ｃ≡Ｃ−で置き換えられてもよく、任意の水素はハロゲンで置き換えられてもよく、Ｒ^Aは炭素数１〜１０のアルキル、炭素数１〜１０のアルケニル、炭素数１〜１０のアルコキシ、水素、塩素、フッ素、−ＣＮ、−ＣＦ₃または−ＯＣＦ₃である。］
以下に、具体例を示す。 Examples of non-polymerizable liquid crystal compounds include compounds represented by the following formula (A).

Wherein ^{(A), Q 2, A} 2 and n have the same meanings as Q ^2, A ² and n in the formula (M1) in, Z ^A is independently a single bond or 1 to 10 carbon atoms alkylene, arbitrary -CH ₂ - in this alkylene -O -, - CO -, - COO -, - OCO -, - CH = CH -, - replaced by CF = CF- or -C≡C- Any hydrogen may be replaced by halogen, and R ^A is alkyl having 1 to 10 carbons, alkenyl having 1 to 10 carbons, alkoxy having 1 to 10 carbons, hydrogen, chlorine, fluorine,- CN, —CF ₃ or —OCF ₃ . ]
A specific example is shown below.

(Optically active compound)
The composition (1) may contain an optically active compound. A composition containing an appropriate amount of the optically active compound (1) or a composition obtained by adding an appropriate amount of an optically active compound to the non-optically active compound (1) exhibits a helical structure (twisted structure) A retardation film having a fixed helical structure can be obtained by coating and polymerizing on an oriented substrate. The properties of the resulting polymer depend on the helical pitch of the resulting helical structure. The helical pitch length can be adjusted by the type and amount of the optically active compound. One optically active compound may be added, but a plurality of optically active compounds may be used for the purpose of offsetting the temperature dependence of the helical pitch.

  Any optically active compound may be used as long as it induces a helical structure and can be appropriately mixed with the polymerizable liquid crystal composition as a base. Moreover, either a polymerizable compound or a non-polymerizable compound may be used, and an optimum compound can be added to the composition (1) according to the purpose. In consideration of heat resistance and solvent resistance, a polymerizable compound is more preferable. Examples of the skeleton that exhibits optical activity include alkylene having one or more asymmetric carbons, alkenylene, and those having the following structures. The addition amount of the optically active compound is usually 0.01 to 50% by weight, preferably 1 to 30% by weight, based on the entire composition (excluding the solvent).

  In the above formula, Me is methyl, and the carbon to which * is attached is an asymmetric carbon. )

  Further, among the optically active compounds, those having a large twisting force (HTP: helical twisting power) are suitable for shortening the helical pitch. Representative examples of compounds having a large torsional force are disclosed in GB2298202 and DE10221751.

  Specific examples of the polymerizable optically active compound are shown below. In these specific examples, n and m are each an integer of 2 to 12.

In the above formula, R ⁴ is methyl, and R ⁵ and R ⁶ are independently phenyl, alkyl having 1 to 6 carbons or trifluoromethyl.

  In the above formula, -COO-Chol means the following cholesterol ester group.

In the above formula, ^t Bu represents tertiary butyl.

Specific examples of non-polymerizable optically active compounds are shown below. In these specific examples, R ⁷ is independently hydrogen, fluorine, —CN, alkyl having 1 to 6 carbons, alkoxy having 1 to 6 carbons, —CF ₃ or —OCF ₃ .

  In the above formula, -COO-Chol means the following cholesterol ester group.

(Polymerization initiator)
The composition (1) may contain a polymerization initiator. The polymerization initiator can be selected depending on the type of polymerization. A polymerization initiator may be used by 1 type, or may mix and use 2 or more types. Preferred polymerization initiators are shown below.

  Examples of radical photopolymerization initiators include 2-hydroxy-2-methyl-1-phenylpropan-1-one (Darocur 1173), 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane 1-one (Irgacure 651), 1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184), Irgacure 127, Irgacure 500 (mixture of Irgacure 184 and benzophenone), Irgacure 2959, Irgacure 907, Irgacure 907 Cure 369, Irgacure 379, Irgacure 754, Irgacure 1300, Irgacure 819, Irgacure 1700, Irgacure 1800, Irgacure 1850, Irgacure 1870, Daroki Ah 4265, Darocure MBF, Darocure TPO, Irgacure 784, Irgacure 754, Irgacure OXE01, and Irgacure OXE02 can be mentioned. Both Darocur and Irgacure are names of products sold by Ciba Japan Co., Ltd. Known sensitizers (such as isopropylthioxanthone, diethylthioxanthone, ethyl-4dimethylaminobenzoate (Darocur EDB) and 2-ethylhexyl-4-dimethylaminobenzoate (Darocur EHA)) may be added thereto.

  Other examples of photo radical polymerization initiators include p-methoxyphenyl-2,4-bis (trichloromethyl) triazine, 2- (p-butoxystyryl) -5-trichloromethyl-1,3,4-oxadiazole 9-phenylacridine, 9,10-benzphenazine, 4,4′-bis (diethylamino) benzophenone, benzophenone / Michler's ketone mixture, hexaarylbiimidazole / mercaptobenzimidazole mixture, 1- (4-isopropylphenyl) -2- Hydroxy-2-methylpropan-1-one, benzyldimethyl ketal, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2,4-diethylxanthone / p-dimethylamino Methyl benzoate mixture and benzopheno / Methyl triethanolamine mixtures thereof, but it can also be used in any known.

  Preferred examples of initiators used for thermal radical polymerization include benzoyl peroxide, diisopropyl peroxydicarbonate, tertiary butyl peroxy-2-ethylhexanoate, tertiary butyl peroxypivalate, ditertiary butyl peroxide. , Tertiary butyl peroxydiisobutyrate, lauroyl peroxide, 3,3′-bismethoxycarbonyl-4,4′-bis-tertiary butyl peroxycarbonylbenzophenone, 3,4′-bismethoxycarbonyl-4,3 ′ -Bis-tertiary butyl peroxycarbonyl benzophenone, 4,4'-bismethoxycarbonyl-3,3'-bis-tertiary butyl peroxycarbonyl benzophenone, dimethyl 2,2'-azobisisobutyrate, azobis Sobuchironitoriru and azobiscyclohexanecarbonitrile including but may be used any of those known.

  Examples of commercially available azo initiators include V-70, V-65, V-60, V-59, V-40, V-30, V-501, V-, manufactured by Wako Pure Chemical Industries, Ltd. 601, VE-073, VA-080, VA-086, VF-096, VAm-110, VAm-111, VA-044, VA-046B, VA-066, VA-061, V-50, VA-057, VA-067, VR-110, VPE-0201, VPE-0401, VPE-0601 and VPS-1001.

Preferred initiators for photocationic polymerization are diaryl iodonium salts (hereinafter abbreviated as “DAS”), triarylsulfonium salts (hereinafter abbreviated as “TAS”), and the like.
Examples of DAS include diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium tetra (pentafluorophenyl) borate, 4-methoxyphenylphenyliodonium tetrafluoroborate, 4-methoxyphenylphenyliodonium Hexafluorophosphonate, 4-methoxyphenylphenyl iodonium hexafluoroarsenate, bis (4-tert-butylphenyl) iodonium diphenyliodonium tetrafluoroborate, bis (4-tert-butylphenyl) iodonium diphenyliodonium hexafluoroarsenate and bis ( 4-tert-butylphenyl) iodo Um diphenyliodonium trifluoromethanesulfonate and the like. It is also preferable to combine DAS and a photosensitizer. Examples of such photosensitizers include thioxanthone, phenothiazine, chlorothioxanthone, xanthone, anthracene, diphenylanthracene, and rubrene, and any known one can be used.

  Examples of TAS include triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium tetra (pentafluorophenyl) borate, 4-methoxyphenyldiphenylsulfonium tetrafluoroborate, 4-methoxyphenyldiphenylsulfonium hexafluorophosphonate 4-methoxyphenyldiphenylsulfonium hexafluoroarsenate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylsulfonium triphenylsulfonium tetra (pentafluorophenyl) borate, 4-phenylthiophenyldiphenylsulfonium tetrafluoroborate 4-phenylthiofe Le diphenyl sulfonium hexafluorophosphonate and 4 phenylthiophenyldiphenylsulfonium hexafluoroarsenate and the like, but can also be used in any known.

  Examples of commercially available initiators used for photocationic polymerization include “DTS-102” manufactured by Midori Chemical Co., Ltd., “Syracure UVI-6990”, “Syracure UVI-6974”, “Syracure UVI-” manufactured by UCC. 6992 "," Adekaoptomer SP-150, SP-152, SP-170, SP-172 "manufactured by Asahi Denka Co., Ltd.," PHOTOINITITOR 2074 "manufactured by Rhodia," Irgacure 250 "manufactured by Ciba Japan Co., Ltd. “UV-9380C” manufactured by GE Silicones, Inc. can be mentioned, but any known one can be used. In addition, amine-based curing agents described in the review epoxy resin (edited by the Epoxy Resin Technical Association) can be added according to the required properties.

  As an example of a specific trade name of the cationic polymerization initiator by heat, Sun Shin (main agent) of products of Sanshin Chemical Industry Co., Ltd. SI-60, SI-80, SI-100, SI-110, SI-145, SI-150, SI-160, SI-180 and sun aid (auxiliary agent) SI are mentioned. These may be used in combination with a photo radical initiator and a photo cationic polymerization initiator, or in combination with a photo radical initiator.

(solvent)
The composition (1) may be applied to the substrate surface as it is. However, usually, in order to facilitate the coating, the polymerizable liquid crystal composition is diluted with a solvent, or each component of the polymerizable liquid crystal composition is dissolved in the solvent to obtain a polymerizable liquid crystal composition and a solvent. A solution of a polymerizable liquid crystal composition comprising the above is prepared, and this solution is used. This solvent can be used alone or in combination of two or more. Examples of solvents include ester solvents, amide solvents, alcohol solvents, ether solvents, glycol monoalkyl ether solvents, aromatic hydrocarbon solvents, halogenated aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents. , Halogenated aliphatic hydrocarbon solvents and alicyclic hydrocarbon solvents, ketone solvents and acetate solvents.

  Preferred examples of ester solvents include alkyl acetates (eg, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, 3-methoxybutyl acetate, isobutyl acetate, pentyl acetate and isopentyl acetate), ethyl trifluoroacetate, propion Alkyl (eg, methyl propionate, methyl 3-methoxypropionate, ethyl propionate, propyl propionate and butyl propionate), alkyl butyrate (eg: methyl butyrate, ethyl butyrate, butyl butyrate, isobutyl butyrate and propyl butyrate), Dialkyl malonates (eg diethyl malonate), alkyl glycolates (eg methyl glycolate and ethyl glycolate), alkyl lactates (eg methyl lactate, ethyl lactate, isopropyl lactate, n-propyl lactate, butyl lactate and Ethylhexyl), monoacetin, include γ- butyrolactone and γ- valerolactone.

  Preferred examples of the amide solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N-methylpropionamide, N, N-dimethylformamide, N, N-diethylformamide, N, N-diethylacetamide, N, N-dimethylacetamide dimethyl acetal, N-methylcaprolactam and dimethylimidazolidinone.

  Preferred examples of the alcohol solvent include methanol, ethanol, 1-propanol, 2-propanol, 1-methoxy-2-propanol, t-butyl alcohol, sec-butyl alcohol, butanol, 2-ethylbutanol, n-hexanol, n -Heptanol, n-octanol, 1-dodecanol, ethylhexanol, 3,5,5-trimethylhexanol, n-amyl alcohol, hexafluoro-2-propanol, glycerin, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, Propylene glycol, dipropylene glycol, tripropylene glycol, hexylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1 5-pentanediol, 2,4-pentanediol, 2,5-hexanediol, 3-methyl-3-methoxybutanol, cyclohexanol, and methylcyclohexanol.

  Preferred examples of ether solvents include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, bis (2-propyl) ether, 1,4-dioxane, cyclopentyl methyl ether, terpinyl methyl ether, dihydroterpinyl methyl ether, 1,8- Cineol, 1,4-cineole and tetrahydrofuran (THF) are mentioned.

  Preferred examples of glycol monoalkyl ether solvents include ethylene glycol monoalkyl ether (eg, ethylene glycol monomethyl ether and ethylene glycol monobutyl ether), diethylene glycol monoalkyl ether (eg, diethylene glycol monoethyl ether), triethylene glycol monoalkyl ether, Propylene glycol monoalkyl ether (eg: propylene glycol monobutyl ether), dipropylene glycol monoalkyl ether (eg: dipropylene glycol monomethyl ether), ethylene glycol monoalkyl ether acetate (eg: ethylene glycol monobutyl ether acetate), diethylene glycol monoalkyl ether Acetate (eg, diethylene glycol) Coal monoethyl ether acetate), triethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate (eg, propylene glycol monobutyl ether acetate), dipropylene glycol monoalkyl ether acetate (eg, dipropylene glycol monomethyl ether acetate), and Examples include diethylene glycol methyl ethyl ether.

Preferred examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, mesitylene, ethylbenzene, diethylbenzene, i-propylbenzene, n-propylbenzene, t-butylbenzene, s-butylbenzene, n-butylbenzene, anisole, p-cymene, limonene, terpinolene and tetralin.
A preferred example of the halogenated aromatic hydrocarbon solvent is chlorobenzene.

Preferred examples of the aliphatic hydrocarbon solvent include hexane and heptane.
Preferable examples of the halogenated aliphatic hydrocarbon solvent include chloroform, dichloromethane, carbon tetrachloride, dichloroethane, trichloroethylene, and tetrachloroethylene.
Preferable examples of the alicyclic hydrocarbon solvent include cyclohexane and decalin.

  Preferable examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, dihydrocarbon, menthone, piperithenone and methylpropyl ketone.

  Preferred examples of the acetate solvent include ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl acetoacetate, α-tapinyl acetate, peryl acetate, 3-octyl acetate, 2- Examples include octyl acetate, myrtenyl acetate, isobornyl acetate, dihydroterpinyl acetate, dihydrocarbyl acetate, carbyl acetate and 1-methoxy-2-propyl acetate.

  From the viewpoint of the solubility of the polymerizable liquid crystal compound, it is preferable to use an amide solvent, an aromatic hydrocarbon solvent, or a ketone solvent. In consideration of the boiling point of the solvent, these solvents and ester solvents, alcohol solvents, ether solvents are used. A combined use with a solvent and a glycol monoalkyl ether solvent is also preferred. Although there is no particular limitation regarding the selection of the solvent, when a plastic substrate is used as the supporting base, it is necessary to lower the drying temperature in order to prevent deformation of the substrate and to prevent the solvent from attacking the substrate. Solvents preferably used in such a case include aromatic hydrocarbon solvents, ketone solvents, ester solvents, ether solvents, alcohol solvents, acetate solvents, and glycol monoalkyl ether solvents.

  The ratio of the solvent in the solution of the polymerizable liquid crystal composition is 50 to 95% based on the total weight of the solution. The lower limit of this range is a numerical value considering the solubility of the polymerizable liquid crystal compound and the optimum viscosity when the solution is applied. And the upper limit is a numerical value considering the economic viewpoint such as the solvent cost and the time and heat amount when the solvent is evaporated. A preferable range of this ratio is 60 to 90%, and a more preferable range is 70 to 85%.

(Surfactant)
The polymerizable liquid crystal composition of the present invention may contain a surfactant. The surfactant has an effect of facilitating application of the composition to a support substrate or the like with a uniform film thickness and controlling the alignment of the liquid crystal phase. Preferred surfactants include, for example, cationic surfactants, anionic surfactants, and nonionic surfactants, but more preferred surfactants are nonionic surfactants. Preferable examples of the nonionic surfactant include silicone-based, fluorine-based and hydrocarbon-based nonionic surfactants. Among these, examples of silicone-based nonionic surfactants include Polyflow ATF-2, Granol 100, Granol 115, Granol 400, Granol 410, Granol 435, manufactured by Kyoeisha Chemical Co., Ltd., whose main component is modified silicone. Granol 440, Granol 450, Granol B-1484, Polyflow KL-250, Polyflow KL-260, Polyflow KL-270, Polyflow KL-280, BYK-300, BYK-302, BYK-306, BYK-307, BYK-310 BYK-315, BYK-320, BYK-322, BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-337, BYK-341, BYK-344, BYK-345, BYK -346, BYK 347, BYK-348, BYK-370, BYK-375, BYK-377, BYK-378, BYK-3500, BYK-3510 and BYK-3570 and the like.

  Examples of fluorine-based nonionic surfactants include BYK-340, FT 251, 221 MH, FT 250, FTX-215M, FTX-218M, FTX-233M, FTX-245M, FTX-290M, FTX -209F, FTX-213F, Aftergent 222F, FTX-233F, FTX-245F, FTX-208G, FTX-218G, FTX-240G, FTX-206D, Aftergent 212D, FTX-218, FTX-220D, FTX-230D , FTX-240D, FTX-720C, FTX-740C, FTX-207S, FTX-211S, FTX-220S, FTX-230S, KB-L82, KB-L85, KB-L97, KB-L109, KB-L110, KB F2L, KB-F2M, KB-F2S, include KB-F3M and KB-FaM.

  As an example of a hydrocarbon-based nonionic surfactant, Polyflow No. 1 mainly composed of an acrylic polymer is used. 3, Polyflow No. 50EHF, Polyflow No. 54N, Polyflow No. 75, Polyflow No. 77, Polyflow No. 85HF, Polyflow No. 90, polyflow no. 95, BYK-350, BYK-352, BYK-354, BYK-355, BYK-358N, BYK-361N, BYK-380N, BYK-381, BYK-392, and BYK-Silclean3700.

  The above-mentioned polyflow and granol are both names of products sold by Kyoeisha Chemical Co., Ltd. BYK is the name of a product sold by Big Chemie Japan. Footent, FTX and KB are names of products sold by Neos Co., Ltd. The amount of the surfactant varies depending on the kind of the surfactant, the composition ratio of the composition, etc., but is preferably 0.01% to 3% by weight with respect to the weight of the entire composition (1) (excluding the solvent). Is in the range of 0.03 to 2% by weight.

(Organic silicon compound)
The composition (1) may contain an organosilicon compound in order to control the orientation. Specific examples include amine-based 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethylethoxysilane, 3-aminopropyldiisopropylethoxysilane, 3-aminopropylmethyldiethoxysilane, 3 -Aminopropylpentamethyldisiloxane, 3-aminopropylmethylbis (trimethylsiloxy) silane, 3-aminopropyltris (trimethylsiloxy) silane, 3-aminobutyltriethoxysilane, N- (2-aminoethyl) -3- Aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (6-aminohexyl) -3-aminopropyltrimethoxysilane, (3-trimethoxysilylpropyl) diethyleneto Amines and ketimines system of 3-triethoxysilyl-N-, (1, 3-dimethyl - butylidene), for example. In order to control the adhesion with the support substrate, an organosilicon compound other than the above may be contained. Specific examples include vinyltrialkoxysilane, 3-isocyanatopropyltriethoxysilane, 3-glycidoxypropyltrialkoxysilane, 3-chlorotrialkoxysilane, 3-acryloxypropyltrimethoxysilane and 3-methacryloxypropyl. A trialkoxysilane is mentioned. Another example is dialkoxymethylsilane in which one of the three alkoxy groups is replaced by methyl in these compounds. The amount of the organosilicon compound varies depending on the kind of the organosilicon compound, the composition ratio of the composition, etc., but is 1 to 30% by weight, preferably 3 to 15%, based on the weight of the entire composition (1) (excluding the solvent). It is in the range of wt%.

(Chain transfer agent)
One or more chain transfer agents can be added to the composition (1) to control the mechanical properties of the polymer. By using a chain transfer agent, the length of the polymer chain can be controlled. These lengths can also be controlled simultaneously. Increasing the amount of chain transfer agent decreases the polymer chain length. A preferred chain transfer agent is a thiol compound. Examples of monofunctional thiols include dodecanethiol and 2-ethylhexyl- (3-mercaptopropionate). Examples of multifunctional thiols include trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), 1,4-bis (3-mercaptobutyryloxy) butane (Karenz MT) BD1), pentaerythritol tetrakis (3-mercaptobutyrate) (Karenz MT PE1), and 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 ( 1H, 3H, 5H) -trione (Karenz MT NR1). “Karenzu” is a trade name of Showa Denko KK

(Other additives)
Examples of other additives include polymerization inhibitors, oxygen inhibitors, ultraviolet absorbers, light stabilizers, antioxidants, and amine-based curing agents.

  A polymerization inhibitor can be added to the composition (1) in order to prevent initiation of polymerization during storage. Known polymerization inhibitors can be used. Preferred examples thereof include 2,5-di (t-butyl) hydroxytoluene (BHT), hydroquinone, methyl blue, diphenylpicric hydrazide (DPPH), benzothiazine, 4-nitrosodimethyl. Aniline (NIDI) and o-hydroxybenzophenone.

  An oxygen inhibitor can be added to the composition (1) in order to improve the storage stability. The radical generated in the composition reacts with oxygen in the storage environment to give a peroxide radical, which promotes an undesirable reaction with the polymerizable compound. In order to prevent this, it is preferable to add an oxygen inhibitor. Examples of oxygen inhibitors are phosphate esters.

  In order to further improve the weather resistance of the polymerizable liquid crystal composition, an ultraviolet absorber, a light stabilizer (radical scavenger), an antioxidant and the like may be added. Examples of UV absorbers are Tinuvin PS, Tinuvin P, Tinuvin 99-2, Tinuvin 109, Tinuvin 213, Tinuvin 234, Tinuvin 326, Tinuvin 328, Tinuvin 329, Tinuvin 384-2, Tinuvin 571, Tinuvin 900, Tinuvin 928, Tinuvin 1130, Tinuvin 400, Tinuvin 405, Tinuvin 460, Tinuvin 479, Tinuvin 5236, Adekastab LA-32, Adekastab LA-34, Adekastab LA-36, Adekastab LA-31, Adekastab 1413 and Adekastab LA-51 are mentioned. “Tinubin” is a trade name of Ciba Japan Co., Ltd., and “Adeka Stub” is a trade name of Asahi Denka Co., Ltd.

  Examples of light stabilizers are Tinuvin 111FDL, Tinuvin 123, Tinuvin 144, Tinuvin 152, Tinuvin 292, Tinuvin 622, Tinuvin 770, Tinuvin 765, Tinuvin 780, Tinuvin 905, Tinuvin 5100, Tinuvin 5050, Tinuvin 5060, Tinuvin 5151, Chimassorb 119FL, Kimasorb 944FL, Kimasorb 944LD, ADK STAB LA-52, ADK STAB LA-57, ADK STAB LA-62, ADK STAB LA-67, ADK STAB LA-63P, ADK STAB LA-68LD, ADK STAB LA-77, ADK STAB LA-82, ADK STAB LA-82 -87, Siasorb UV-3346 manufactured by Cytec, and Goodlight UV-3034 manufactured by Goodrich. “Kimasorb” is a trade name of Ciba Japan Co., Ltd.

  Examples of antioxidants include ADK STAB AO-20, AO-30, AO-40, AO-50, AO-60, AO-80 manufactured by Asahi Denka Co., Ltd., Sumitizer BHT, Sumitizer BBM- manufactured by Sumitomo Chemical Co., Ltd. S, Sumilizer GA-80, and Irganox 1076, Irganox 1010, Irganox 3114, and Irganox 245 manufactured by Ciba Japan.

  Moreover, the amine hardening agent etc. which are described in the review epoxy resin (edited by epoxy resin technical association) etc. can be added to a composition (1) according to the required characteristic.

(Polymer)
In the following description, a polymer obtained by controlling the orientation of the polymerizable liquid crystal composition and polymerizing is referred to as an anisotropic polymer. A polymer obtained by polymerization without controlling the orientation is referred to as a polymer film. The anisotropic polymer can be formed as follows. First, a solution of a polymerizable liquid crystal composition is applied onto a support substrate that has been subjected to an alignment treatment, and dried to form a coating film. Next, the coating film is irradiated with light or heated to polymerize the polymerizable liquid crystal composition, and the nematic alignment formed in the liquid crystal state by the composition in the coating film is fixed.

  As for the alignment form of the polymerizable liquid crystal composition, a polymerizable liquid crystal composition and a polymer having an alignment form suitable for the purpose can be obtained by appropriately changing the type and amount of each component contained in the composition. However, the polymerizable liquid crystal composition of the present invention preferably has any one of homogeneous alignment, tilt alignment, twist alignment, and homeotropic alignment. An anisotropic polymer and a laminate obtained by polymerizing a polymerizable liquid crystal composition having such an alignment form can be suitably used as an optical compensation film or a reflective film used in a liquid crystal display element or a liquid crystal display device. .

  In the present invention, the term “laminate” simply refers to one having the above-mentioned supporting substrate and an anisotropic polymer formed thereon.

  Supporting substrates that can be used include glass substrates and plastic substrates. Examples of plastic substrates include polyimide, polyamideimide, polyamide, polyetherimide, polyetheretherketone, polyetherketone, polyketonesulfide, polyethersulfone, polysulfone, polyphenylenesulfide, polyphenylene oxide, polyethylene terephthalate, polybutylene terephthalate, polyethylene Examples thereof include plastic films composed of naphthalate, polyacetal, polycarbonate, polyarylate, acrylic resin, polyvinyl alcohol, polypropylene, cellulose, triacetyl cellulose and partially saponified products thereof, epoxy resin, phenol resin, and cycloolefin resin.

  Examples of cycloolefin resins include, but are not limited to, norbornene resins and dicyclopentadiene resins. Among these, those having no unsaturated bond or hydrogenated unsaturated bond are preferably used. For example, hydrogenated products of ring-opening (co) polymers of one or more norbornene monomers, addition (co) polymers of one or more norbornene monomers, norbornene monomers and olefin monomers Addition copolymers with (ethylene, α-olefin, etc.), norbornene monomers and cycloolefin monomers (cyclopentene, cyclooctene, 5,6-dihydrodicyclopentadiene, etc.), and these Specific examples include ZEONEX, ZEONOR (manufactured by Nippon Zeon), ARTON (manufactured by JSR), TOPAS (manufactured by Chicona), APEL (manufactured by Mitsui Chemicals), and Essina (manufactured by Sekisui Chemical Co., Ltd.). And OPTOREZ (manufactured by Hitachi Chemical Co., Ltd.).

  These plastic substrates may be uniaxially stretched films or biaxially stretched films. These plastic substrates may have a surface subjected to, for example, a hydrophilic treatment or a hydrophobic treatment. The method for hydrophilization treatment is not particularly limited, but corona treatment, plasma treatment, ion beam treatment and the like are preferable, and a more preferred method is corona treatment or plasma treatment, and a particularly preferred method is plasma treatment. The plasma treatment is not particularly limited, but methods described in JP 2002-226616 A and JP 2002-121648 may be used. These hydrophilic treatments can also be used when the polymerizable liquid crystal composition is controlled to homeotropic alignment.

  Further, in order to improve the adhesion between the obtained anisotropic polymer and the plastic substrate, an anchor coat layer may be formed on the plastic substrate. As long as such an anchor coat layer enhances the adhesion between the anisotropic polymer and the plastic substrate, there is no problem whether it is an inorganic material or an organic material. The plastic substrate may be a laminated film. Instead of these plastic substrates, metal substrates such as aluminum, iron and copper with slit-shaped grooves on the surface, glass substrates such as alkali glass, borosilicate glass and flint glass whose surfaces are etched into a slit shape, etc. It can also be used.

  When a glass substrate is used as the supporting substrate, the surface may be coated with the plastic film, and an anchor coat layer may be used to improve the adhesion between the obtained anisotropic polymer and the glass substrate. May be formed.

  These supporting substrates such as glass substrates and plastic substrates are preferably subjected to physical and mechanical surface treatment such as rubbing prior to the formation of a coating film of the polymerizable liquid crystal composition. For the rubbing treatment, a rubbing cloth made of materials such as rayon, cotton, and polyamide is usually applied to a metal roll and moved while rotating the roll while in contact with the support substrate, plastic film coating or anchor coat layer. A method, a method of moving the support base material side while fixing the roll, and the like are adopted, and any method may be selected. The rubbing treatment may be applied directly to the supporting substrate, or may be applied to the plastic film coating or the anchor coating layer.

  In addition, depending on the kind of support base material, the surface may be subjected to corona treatment or plasma treatment in advance to improve coatability. In that case, it is good to carry out before the rubbing process. Further, a photo-alignment process using polarized UV may be performed instead of the rubbing process, and various photo-alignment film materials can be applied.

  When applying the solution of the polymerizable liquid crystal composition of the present invention, the solvent is removed after the application, and the layer of the polymerizable liquid crystal composition having a uniform film thickness (hereinafter referred to as “polymerizable liquid crystal layer”) on the supporting substrate. Also called).

  Examples of coating methods for obtaining a uniform film thickness when applying a polymerizable liquid crystal composition or a solution thereof include a spin coating method, a micro gravure coating method, a gravure coating method, a wire bar coating method, a dip coating method, Examples thereof include spray coating, meniscus coating, and die coating.

  The conditions for removing the solvent are not particularly limited. What is necessary is just to dry until a solvent is removed substantially and the fluidity | liquidity of the coating film of polymeric liquid crystal composition is lose | eliminated. The solvent can be removed using air drying at room temperature, drying on a hot plate, drying in a drying furnace, blowing warm air or hot air, and the like. Depending on the type and composition ratio of the compound used in the polymerizable liquid crystal composition, nematic alignment of the polymerizable liquid crystal composition in the coating film may be completed in the process of drying the coating film. Therefore, in this case, the coating film that has undergone the drying step can be subjected to the polymerization step without going through a heat treatment step described later.

  The temperature and time when heat-treating the coating, the wavelength of light used for light irradiation, the amount of light irradiated from the light source, etc. are the types and composition ratios of the compounds used in the polymerizable liquid crystal composition, and the addition of a photopolymerization initiator. The preferred range varies depending on the presence or absence and the amount added. Accordingly, the conditions regarding the temperature and time of the heat treatment of the coating film described below, the wavelength of the light used for light irradiation, and the amount of light irradiated from the light source are merely an approximate range.

  The heat treatment of the coating film is preferably carried out under the condition that the solvent is removed and the uniform orientation of the polymerizable liquid crystal is obtained. You may carry out above the liquid crystal phase transition point of a polymeric liquid crystal composition. As an example of the heat treatment method, there is a method in which the polymerizable liquid crystal composition is heated to a temperature at which a nematic liquid crystal phase is exhibited and nematic alignment is formed in the polymerizable liquid crystal composition in the coating film. Moreover, you may form nematic alignment by changing the temperature of a coating film within the temperature range in which a polymeric liquid crystal composition shows a nematic liquid crystal phase. In this method, the nematic orientation is generally completed in the coating film by heating the coating film to a high temperature range of the temperature range, and then the order is further ordered by lowering the temperature.

  The heat treatment temperature in these heat treatment methods is room temperature to 120 ° C. A preferable range of this temperature is room temperature to 100 ° C, a more preferable range is room temperature to 90 ° C, and a further preferable range is room temperature to 85 ° C. The heat treatment time is 5 seconds to 2 hours. A preferable range of this time is 10 seconds to 40 minutes, and a more preferable range is 20 seconds to 20 minutes. In order to raise the temperature of the polymerizable liquid crystal layer to a predetermined temperature, the heat treatment time is preferably 5 seconds or more. In order not to lower the productivity of the anisotropic polymer, it is preferable to set the heat treatment time within 2 hours. Thus, the laminated body of this invention is obtained, and an anisotropic polymer can be obtained by removing a support base material from this laminated body.

The nematic alignment state of the polymerizable liquid crystal compound formed in the polymerizable liquid crystal layer is fixed by polymerizing the polymerizable liquid crystal composition by light irradiation or heating. The method of light irradiation is not particularly limited, and a method according to the composition may be used, and an electron beam, an ultraviolet ray, a visible ray, an infrared ray (heat ray), or the like can be used. Usually, ultraviolet rays or visible rays may be used. The wavelength range is 150 to 500 nm. A preferable range is 250 to 450 nm, and a more preferable range is 300 to 400 nm. Examples of light sources include low-pressure mercury lamps (sterilization lamps, fluorescent chemical lamps, black lights), high-pressure discharge lamps (high-pressure mercury lamps, metal halide lamps), and short arc discharge lamps (super-high pressure mercury lamps, xenon lamps, mercury xenon lamps). Can be mentioned. Preferable examples of the light source include a metal halide lamp, a xenon lamp, an ultrahigh pressure mercury lamp, and a high pressure mercury lamp. The wavelength region of the irradiation light source may be selected by installing a filter or the like between the light source and the polymerizable liquid crystal layer and passing only a specific wavelength region. The amount of light irradiated from the light source is ² to 5000 mJ / cm ² . A preferred range of light intensity is 10~3000mJ / cm ^2, and more preferred range is 100 to 2000 mJ / cm ^2. It is preferable that the temperature condition at the time of light irradiation is set similarly to the above heat treatment temperature. The atmosphere of the polymerization environment may be any of a nitrogen atmosphere, an inert gas atmosphere, and an air atmosphere, but a nitrogen atmosphere or an inert gas atmosphere is preferable from the viewpoint of improving curability.

  In the polymerization by heating, the heating temperature may be adjusted according to the polymerization start temperature of the thermal polymerization initiator. In order to avoid initiation of the thermal polymerization reaction in the drying step, the temperature difference between the half-life temperature of the thermal polymerization initiator and the drying step is preferably as large as possible. Further, when using a thermal polymerization initiator that generates radicals during thermal polymerization, a method of reducing polymerization inhibition by oxygen by heating in a nitrogen atmosphere or an inert gas atmosphere is preferable from the viewpoint of improving curability. .

  When the anisotropic polymer obtained by polymerizing the polymerizable liquid crystal composition of the present invention with light or heat is used for various optical elements, or when it is applied as an optical compensation element for a liquid crystal display device, the tilt in the thickness direction Control of the angular distribution is important.

  One method of controlling the tilt angle is a method of adjusting the type or composition ratio of the compound having liquid crystallinity used in the polymerizable liquid crystal composition. Further, the tilt angle can be controlled by adding a surfactant to the polymerizable liquid crystal compound. The tilt angle of the anisotropic polymer can also be controlled by the type of solvent and solute concentration in the polymerizable liquid crystal composition, the type and amount of surfactant added, and the like. The tilt angle of the anisotropic polymer can also be controlled by the types and rubbing conditions of the supporting substrate, the plastic film coating and the anchor coating layer, the drying conditions and the heat treatment conditions of the coating film of the polymerizable liquid crystal composition. Furthermore, the irradiation atmosphere in the photopolymerization step after the orientation, the temperature at the time of irradiation, and the like also affect the tilt angle of the anisotropic polymer. That is, it can be considered that almost all the conditions in the manufacturing process of the anisotropic polymer affect the tilt angle to some extent. Therefore, by optimizing the polymerizable liquid crystalline composition and appropriately selecting various conditions of the anisotropic polymer production process, the tilt angle according to the purpose can be obtained.

  The preferred haze value of the anisotropic polymer is 1.5% or less, and the preferred transmittance is 80% or more. A more preferable haze value is 1.0% or less, and a more preferable transmittance is 95% or more. The transmittance preferably satisfies these conditions in the visible light region.

  The anisotropic polymer and the laminate are effective as an optical compensation film and a reflective film applied to liquid crystal display elements (particularly, active matrix type and passive matrix type liquid crystal display elements) and liquid crystal display devices. Examples of liquid crystal display element types suitable for using anisotropic polymers and laminates as optical compensation films are IPS type (in-plane switching), displays with switching in optically isotropic phase (For example, described in WO02 / 93244), TN type (twisted nematic), STN type (super twisted nematic), ECB type (electrically controlled birefringence), DAP type (deformation effect of aligned phase), CSH type (color super homeotropic), VA (vertical alignment), VAN / VAC type (vertically aligned nematic / cholesteric), MVA (multi-domain vertical alignment) or PVA (patterned vertical alignment), OCB type (Optically compensated birefringence), R-OCB (reflective OCB), HAN (composite) Direction nematic), include the OMI (optical mode interference) and SBE type (super birefringence effect). Furthermore, this anisotropic polymer can also be used as a phase letter for a display element such as a guest-host type, a ferroelectric type, or an antiferroelectric type. Preferred are TN type, STN type, VA type and IPS type in an active matrix type display. Note that the optimum values of parameters such as the distribution of thickness and thickness of the tilt angle required for anisotropic polymers strongly depend on the type of liquid crystal display element to be compensated and its optical parameters, and therefore differ depending on the type of element.

  The anisotropic polymer can also be used as an optical element integrated with a polarizing plate or the like. In this case, the anisotropic polymer is disposed outside the liquid crystal cell. On the other hand, since the anisotropic polymer as the optical compensation element has little or no elution of impurities into the liquid crystal filled in the cell, it can be arranged inside the liquid crystal cell. For example, when the method disclosed in Japanese Patent Application Laid-Open No. 2006-285014 is applied, the function of the color filter can be further improved by forming the polymerizable liquid crystal layer of the present invention on the color filter.

  When compound (1) has optical activity, the anisotropic polymer has an immobilized helical structure. When the compound (1) is optically inactive, the polymer (1) having an immobilized helical structure can be obtained by adding the optically active compound to the composition (1).

  The polymer (1) in which both the molecular arrangement and the helical structure are fixed includes a retardation film, a polarizing element, a circular polarizing element, an elliptical polarizing element, an antireflection film, a selective reflection film, a color compensation film, and a viewing angle compensation film. Suitable for applications such as liquid crystal alignment films.

  The polymer (1) in which the molecular arrangement is fixed is suitable for use as a retardation film, a circularly polarizing element, an elliptically polarizing element, a selective reflection film, a color compensation film, a viewing angle compensation film, and a liquid crystal alignment film. The polymer (1) in which the helical structure is fixed is suitable for an antireflection film, a color compensation film, and the like. The polymer (1) in which both the molecular arrangement and the helical structure are not fixed is suitable for an antireflection film, a liquid crystal alignment film, and the like. In any case, it can be used as an adhesive, a synthetic polymer having mechanical anisotropy, a cosmetic, a decorative article, a non-linear optical material, an information storage material, and the like. The above-described thermal polymerization and photopolymerization are suitable for fixing the molecular arrangement and the helical structure.

  In the selective reflection of visible light, which is a characteristic of the polymer (1) having optical anisotropy as described above, the helical structure acts on incident light and reflects circularly polarized light and elliptically polarized light. Since the selective reflection characteristic is expressed by λ = n · Pitch (λ is the selective reflection center wavelength, n is the average refractive index, and Pitch is the helical pitch), λ and its band (Δλ) should be adjusted appropriately by n or Pitch Can do. In order to improve color purity, Δλ should be reduced, and Δλ should be increased when broadband reflection is desired. Furthermore, this selective reflection is greatly influenced by the thickness of the polymer. In order to maintain color purity, the thickness must not be too small. In order to maintain the uniformity of orientation, the thickness must not be too large. Further, the appropriate thickness varies depending on the retardation corresponding to the target element and the birefringence of the anisotropic polymer. Therefore, the range cannot be determined strictly, but is preferably 0.05 to 50 μm, more preferably 0.5 to 20 μm, and even more preferably 1 to 10 μm.

  By making the helical pitch shorter than visible light, a negative C plate described in W. H. de Jeu, Physical Properties of Liquid Crystalline Materials, Gordon and Breach, New York (1980) can be prepared. In order to shorten the helical pitch, it can be achieved by using an optically active compound having a large twisting force (HTP: helical twisting power) and further increasing the amount of addition. Specifically, a negative C plate can be prepared by setting λ to 350 nm or less, preferably 200 nm or less. This negative type C plate is an optical compensation film suitable for VAN type, VAC type, OCB type and the like among liquid crystal display elements.

  By making the helical pitch longer than visible light, it can be used for a reflective film in which the reflection wavelength region as described in JP-A-2004-333671 is set to the near infrared (wavelength 800 to 2500 nm). Increasing the helical pitch can be achieved by using an optically active compound with a small twisting force or by reducing the amount of optically active compound added.

  The polymer (1) can be dissolved in a solvent and processed into a film or the like. In this case, two polymers may be mixed and processed. When processing into a film or the like, it may be laminated. Preferred solvents include, for example, N-methyl-2-pyrrolidone, dimethyl sulfoxide, N, N-dimethylacetamide, N, N-dimethylformamide, N, N-dimethylacetamide dimethyl acetal, tetrahydrofuran, chloroform, 1,4-dioxane. Bis (methoxyethyl) ether, γ-butyrolactone, tetramethylurea, trifluoroacetic acid, ethyl trifluoroacetate, hexafluoro-2-propanol, 2-methoxyethyl acetate, methyl ethyl ketone and cyclopentanone, cyclohexanone. These solvents may be used by mixing with common organic solvents such as acetone, benzene, toluene, heptane and methylene chloride.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not restrict | limited by these Examples. The structure of the compound was confirmed by nuclear magnetic resonance spectrum, infrared absorption spectrum, and mass spectrum. The unit of the phase transition temperature is ° C., C represents a crystal, N represents a nematic phase, SB represents a smectic B phase, and I represents an isotropic liquid phase. Below, the measuring method of a physical-property value is shown.

<Polymerization conditions>
In a nitrogen atmosphere or in the air, light having an intensity of 30 mW / cm ² (365 nm) was irradiated for 30 seconds using a 250 W ultrahigh pressure mercury lamp at room temperature.

<Preparation of a rubbing-treated glass substrate with an alignment film>
A glass substrate having a thickness of 1.1 mm is spin-coated with an aligning agent (trade name: Rixon Aligner PIA-5370, manufactured by Chisso Corp.), dried with a solvent, and then baked at 230 ° C. for 30 minutes. Processed.

<Confirmation of liquid crystal alignment>
The substrate with anisotropic polymer was observed with a polarizing microscope, and the presence or absence of alignment defects was confirmed.

<Measurement with ellipsometer>
Using an OPTIPRO ellipsometer manufactured by Shintech Co., Ltd., a substrate with an anisotropic polymer was irradiated with light having a wavelength of 550 nm. Retardation was measured while decreasing the incident angle of this light from 90 degrees with respect to the film surface. Retardation (phase delay) is represented by Δn × d. The symbol Δn is the optical anisotropy value, and the symbol d is the thickness of the polymer film.

<Film thickness measurement>
The anisotropic polymer layer of the substrate with anisotropic polymer was cut out, and the step was measured using a fine shape measuring apparatus (Alphastep IQ, manufactured by KLA TENCOR Co., Ltd.).

<Evaluation of optical anisotropy value (Δn)>
From the retardation and film thickness value obtained for the anisotropic polymer having homogeneous orientation, Δn = retardation / film thickness was calculated.

[Example 1]
The following compound (1-1-10) was synthesized as follows.

  52 mmol of 1,4-cyclohexanedimethanol monoacrylate, 52 mmol of 4′-pentylbicyclohexane-4-carboxylic acid and 10 mmol of 4-dimethylaminopyridine (DMAP) were added to 100 mL of dichloromethane and stirred under a nitrogen atmosphere. Thereto was added dropwise 50 mL of a dichloromethane solution of 57 mmol of 1,3-dicyclohexylcarbodiimide (DCC). After dropping, the mixture was stirred at room temperature for 8 hours. The deposited precipitate was separated by filtration, and the organic layer was washed with water and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography and recrystallized from ethanol to obtain 18 mmol of the compound (1-1-10).

The phase transition temperature and NMR analysis value of the obtained compound (1-1-10) are as follows.
Phase transition temperature: C 61 I

¹ H-NMR (CDCl ₃ ; δ ppm): 6.41 (d, 1H), 6.18-6.09 (m, 1H), 5.83 (d, 1H), 3.99 (d, 2H) , 3.89 (d, 2H), 2.34-2.25 (m, 1H), 2.13-2.01 (m, 2H), 1.91-1.56 (m, 12H), 1 .33-0.77 (m, 26H).

[Example 2]
The following compound (1-1-12) was synthesized as follows.

  52 mmol of 1,4-cyclohexanedimethanol monoacrylate, 52 mmol of 2- (4′-pentylbicyclohexane) -4-ylcarboxylic acid and 10 mmol of 4-dimethylaminopyridine (DMAP) were added to 100 mL of dichloromethane and stirred under a nitrogen atmosphere. . Thereto was added dropwise 50 mL of a dichloromethane solution of 57 mmol of 1,3-dicyclohexylcarbodiimide (DCC). After dropping, the mixture was stirred at room temperature for 8 hours. The deposited precipitate was separated by filtration, and the organic layer was washed with water and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography and recrystallized from ethanol to obtain 15 mmol of the compound (1-1-12).

The phase transition temperature and NMR analysis value of the resulting compound (1-1-12) are as follows.
Phase transition temperature: C 72 (SB 63) I

¹ H-NMR (CDCl ₃ ; δ ppm): 6.41 (d, 1H), 6.17-6.09 (m, 1H), 5.83 (d, 1H), 3.99 (d, 2H) , 3.89 (d, 2H), 2.17 (d, 2H), 1.87-1.56 (m, 15H), 1.33-0.77 (m, 26H).

[Example 3]
The following compound (1-2-6) was synthesized as follows.

  107 mmol of 1,4-cyclohexanedimethanol monoacrylate and 160 mmol of triethylamine were added to 150 mL of toluene and stirred under a nitrogen atmosphere. Thereto, 70 mL of a toluene solution of 52 mmol of terephthalic acid chloride was dropped. After dropping, the mixture was stirred at room temperature for 8 hours. The deposited precipitate was separated by filtration, and the organic layer was washed with water and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography and recrystallized from ethanol to obtain 31 mmol of the compound (1-2-6).

The phase transition temperature and NMR analysis value of the obtained compound (1-2-6) are as follows.
Phase transition temperature: C 156 I

¹ H-NMR (CDCl ₃ ; δ ppm): 7.82 (S, 4H), 6.44 (d, 2H), 6.20-6.09 (m, 2H), 5.83 (d, 2H) 3.98 (d, 4H), 3.90 (d, 4H), 2.08-1.99 (m, 4H), 1.74-1.39 (m, 10H), 1.10-0. 97 (m, 6H).

[Example 4]
The following compound (1-2-12) was synthesized as follows.

  107 mmol of 1,4-cyclohexanedimethanol monoacrylate, 52 mmol of trans-cyclohexane-1,4-dicarboxylic acid and 21 mmol of 4-dimethylaminopyridine (DMAP) were added to 300 mL of dichloromethane and stirred under a nitrogen atmosphere. Thereto, 60 mL of a dichloromethane solution of 118 mmol of 1,3-dicyclohexylcarbodiimide (DCC) was dropped. After dropping, the mixture was stirred at room temperature for 8 hours. The deposited precipitate was separated by filtration, and the organic layer was washed with water and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography and recrystallized from ethanol to obtain 22 mmol of the compound (1-2-12).

The phase transition temperature and NMR analysis value of the obtained compound (1-2-12) are as follows.
Phase transition temperature: C 104 I

¹ H-NMR (CDCl ₃ ; δ ppm): 6.42 (d, 2H), 6.19-6.09 (m, 2H), 5.83 (d, 2H), 3.99 (d, 4H) , 3.90 (d, 4H), 2.34-2.25 (m, 2H), 2.05 (d, 4H), 1.90-1.77 (m, 7H), 1.74-1 .39 (m, 10H), 1.10-0.97 (m, 7H).

  The compounds used in Examples 5 and 6 are shown below.

The compound (M1-1-10-1) was synthesized by the method described in Makromol. Chem., 190, 2255-2268 (1989).
Compound (M1-2-37-1) and compound (M1-2-40-1) were synthesized by the method described in WO97 / 34862 pamphlet.

  Compound (M1-1-25-1) was synthesized as follows.

  Compound (ex-1) 74 mmol, 3 ′, 6′-dihydroxybenzonorbornene 35 mmol and 4-dimethylaminopyridine (DMAP) 21 mmol were added to 200 mL of dichloromethane, followed by stirring under a nitrogen atmosphere. Thereto was added dropwise 100 mL of a dichloromethane solution of 74 mmol of 1,3-dicyclohexylcarbodiimide (DCC). After dropping, the mixture was stirred at room temperature for 8 hours. The deposited precipitate was separated by filtration, and the organic layer was washed with water and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography and recrystallized from ethanol to obtain 15 mmol of the compound (M1-1-25-1).

The phase transition temperature of the obtained compound (M1-1-25-1) is as follows.
Phase transition temperature: C 77 I

[Example 5]
These compounds were mixed at a weight ratio of Compound (1-1-12): Compound (M1-1-10-1): Compound (M1-1-25-1) = 25: 25: 50. This composition is designated as MIX (A). A nonionic fluorosurfactant having a weight ratio of 0.002 (manufactured by Neos Co., Ltd., trade name “Factent FTX-218”) and a weight ratio of 0.06 with respect to the weight 1 of the MIX (A) A polymerization initiator Irgacure 907 (manufactured by Ciba Japan) was added. Cyclopentanone / propylene glycol monomethyl ether acetate (PGMEA) = 7/3 (weight ratio) was added to this composition to obtain a polymerizable liquid crystal composition (1) having a solvent ratio of 70% by weight. The resulting polymerizable liquid crystal composition (1) was uniformly mixed without phase separation or the like.

Next, the polymerizable liquid crystal composition (1) was applied onto a glass substrate with a rubbed alignment film by spin coating. At this time, the coating property was good.
This substrate was heated at 80 ° C. for 3 minutes, cooled at room temperature for 3 minutes, and the polymerizable liquid crystal layer from which the solvent was removed was polymerized with ultraviolet rays in the air to obtain an anisotropic polymer in which the alignment state of the liquid crystal was fixed. . When this anisotropic polymer was observed with a polarizing microscope, it had no orientation defect and had a uniform orientation. When the retardation of this anisotropic polymer was measured, the result was as shown in FIG. 1, and the orientation was homogeneous. Since the measured retardation value at 90 degrees with respect to the film surface was 138 nm and the film thickness was 1260 nm, Δn was calculated to be 0.11.

[Example 6]
These compounds were mixed in a weight ratio of Compound (1-1-12): Compound (M1-2-37-1): Compound (M1-2-40-1) = 33: 33: 34. This composition is designated as MIX (B). A nonionic fluorosurfactant having a weight ratio of 0.002 (manufactured by Neos Co., Ltd., trade name “Factent FTX-218”) and a weight ratio of 0.06 with respect to the weight 1 of the MIX (B) A polymerization initiator Irgacure 907 (manufactured by Ciba Japan) was added. Cyclohexanone / PGMEA = 9/1 (weight ratio) was added to this composition to obtain a polymerizable liquid crystal composition (2) having a solvent ratio of 75% by weight. The resulting polymerizable liquid crystal composition (2) was uniformly mixed without phase separation or the like.

An anisotropic polymer was obtained by the method described in Example 5, except that the supporting substrate was a glass substrate with an alignment film that was not rubbed. At this time, the coating property was good.
When this anisotropic polymer was observed with a polarizing microscope, it had no orientation defect and had a uniform orientation. When the retardation of this anisotropic polymer was measured, the result was as shown in FIG. 2, which was homeotropic alignment.

[Comparative Example 1]
These compounds were mixed in a weight ratio of Compound (M1-2-37-1): Compound (M1-2-40-1) = 50: 50. This composition is designated as MIX (C). An attempt was made to produce an anisotropic polymer in the same manner as in Example 5 except that this MIX (C) was used, but crystallization progressed and evaluation was difficult.

  From the results of the above Examples and Comparative Examples, it is possible to prevent the progress of crystallization at room temperature by introducing a polymerizable compound having a 1,4-dimethylenecyclohexane skeleton into the mixture. It has been found that the anisotropic polymer obtained from the polymerizable liquid crystal composition can control Δn while maintaining the alignment of the liquid crystal.

Claims (31)

The compound represented by Formula (1).

[In formula (1), R ¹ is a polymerizable group represented by any ^one of formulas (2-1) to (2-6), hydrogen, chlorine, fluorine, —CN, alkyl having 1 to 10 carbons, Alkoxy having 1 to 10 carbons, —CF ₃ or —OCF ₃ ;
A ¹ is independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2,7- Diyl or bicyclo [2.2.2] octane-1,4-diyl, one or two non-adjacent —CH ₂ — in 1,4-cyclohexylene may be replaced by —O— One or two —CH═ in 1,4-phenylene may be replaced by —N═, and any hydrogen in 1,4-phenylene is halogen, —CN, alkyl having 1 to 5 carbons, or carbon 1 May be substituted with ˜5 alkoxy or C 1-5 alkyl halide;
Z ¹ is —CO—, —COCH ₂ —, —CO (CH ₂ ) ₂ — or —COCH═CH—;
Z ² is independently a single bond or alkylene having 1 to 20 carbon atoms, and any —CH ₂ — in the alkylene is —O—, —CO—, —COO—, —OCO—, —CH═CH—. , -CF = CF- or -C≡C-, and any hydrogen may be replaced by halogen;
Q ¹ is a single bond or alkylene having 1 to 20 carbon atoms, and any —CH ₂ — in the alkylene is —O—, —CO—, —COO—, —OCO—, —OCOO— or —CH═CH. -Any hydrogen may be replaced with halogen;
m is an integer from 1 to 5;
R ^a is hydrogen, halogen, alkyl having 1 to 5 carbons or alkyl halide having 1 to 5 carbons. ]

[In formulas (2-1) to (2-6), R ^a is independently hydrogen, halogen, alkyl having 1 to 5 carbons or alkyl halide having 1 to 5 carbons. ]   The compound of Claim 1 whose m is an integer of 1-3 in Formula (1) of Claim 1. The formula (1) according to claim 1, wherein A ¹ is independently 1,4-cyclohexylene, 1,4-phenylene or 1,3-dioxane-2,5-diyl; The arbitrary hydrogen in is optionally substituted by chlorine, fluorine, -CN, alkyl having 1 to 3 carbons, alkoxy having 1 to 3 carbons or fluoroalkyl having 1 to 3 carbons. Compound described in 1. In formula (1) according to claim 1, A ¹ is independently 1,4-cyclohexylene or 1,4-phenylene, and any hydrogen in 1,4-phenylene is chlorine, fluorine, -CN, -CH _3, may be replaced by -OCH ₃ or -CF _3, a compound according to any one of claims 1 to 3. In the formula (1) according to claim 1, a single bond Z ² is _{independently, -CH 2 O -, - OCH} 2 -, - COO -, - OCO -, - COOCH 2 -, - CH 2 COOCH 2 -, - CH = CH -, - (CH 2) 2 COO -, - OCO (CH 2) 2 -, - CH = CH-COO -, - is OCO-CH = CH- or -C≡C-, The compound according to any one of claims 1 to 4. In the formula (1) according to claim 1, a single bond Z ² is independently, -COO -, - OCO -, - COOCH 2 - or -CH ₂ COOCH ₂ - are any of claims 1 to 5 2. The compound according to item 1. The formula (1) according to claim 1, wherein R ¹ is a polymerizable group represented by any ^one of formulas (2-1) to (2-6); Q ¹ is an alkylene having 1 to 10 carbon atoms. and a, arbitrary -CH ₂ - in this alkylene -O -, - COO -, - OCO- or may be replaced by -OCOO-, a compound according to any one of claims 1 to 6. The compound according to any one of claims 1 to 7, wherein in the formula (1) according to claim 1, R ¹ is a polymerizable group represented by the formula (2-1). In the formula (1) according to claim 1, R ¹ is hydrogen, chlorine, fluorine, -CN, alkyl having 1 to 10 carbons, alkoxy having 1 to 10 carbons, -CF ₃ or -OCF ₃ ; The compound according to any one of claims 1 to 6, wherein Q ¹ is a single bond.   The compound according to any one of claims 1 to 9, wherein in the formula (1) according to claim 1, m is 2.   A polymerizable liquid crystal composition containing at least one of the compounds according to claim 1. A polymerizable liquid crystal composition comprising at least one compound represented by formula (1) and at least one polymerizable compound selected from the group of compounds represented by formulas (M1) and (M2).

[In Formula (1), R ¹ is a polymerizable group represented by Formula (2-1), hydrogen, chlorine, fluorine, —CN, alkyl having 1 to 10 carbons, alkoxy having 1 to 10 carbons, be -CF ₃ or -OCF _3;
A ¹ is independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2,7- Diyl or bicyclo [2.2.2] octane-1,4-diyl, one or two non-adjacent —CH ₂ — in 1,4-cyclohexylene may be replaced by —O— One or two —CH═ in 1,4-phenylene may be replaced by —N═, and any hydrogen in 1,4-phenylene is halogen, —CN, alkyl having 1 to 5 carbons, or carbon 1 May be substituted with ˜5 alkoxy or C 1-5 alkyl halide;
Z ¹ is —CO—, —COCH ₂ —, —CO (CH ₂ ) ₂ — or —COCH═CH—;
Z ² is independently a single bond or alkylene having 1 to 20 carbon atoms, and any —CH ₂ — in the alkylene is —O—, —CO—, —COO—, —OCO—, —CH═CH—. , -CF = CF- or -C≡C-, and any hydrogen may be replaced by halogen;
Q ¹ is a single bond or alkylene having 1 to 20 carbon atoms, and any —CH ₂ — in the alkylene is —O—, —CO—, —COO—, —OCO—, —OCOO— or —CH═CH. -Any hydrogen may be replaced with halogen;
m is an integer from 1 to 5;
R ^a is hydrogen, halogen, alkyl having 1 to 5 carbons or alkyl halide having 1 to 5 carbons. ]

[In Formula (2-1), R ^a is hydrogen, halogen, alkyl having 1 to 5 carbon atoms or alkyl halide having 1 to 5 carbon atoms. ]

[In formulas (M1) and (M2), R ² is independently a polymerizable group represented by any one of formulas (2-1) to (2-6);
R ³ is independently a polymerizable group represented by any one of formulas (2-1) to (2-6), alkyl having 1 to 10 carbons, alkoxy having 1 to 10 carbons, hydrogen, chlorine, Fluorine, —CN, —CF ₃ or —OCF ₃ ;
A ² is independently 1,4-cyclohexylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diyl, bicyclo [2.2. 2] Octane-1,4-diyl, triptycene-1,4-diyl or 1,4-phenylenenorbornene, wherein any hydrogen in 1,4-phenylene and fluorene-2,7-diyl is halogen, —CN , May be replaced by alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons or alkyl halide having 1 to 5 carbons;
Z ³ is independently a single bond, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, —C≡C—, —CH═CHCOO—, —OCOCH═CH—, — (CH ₂ ) ₂ COO—, —OCO (CH ₂ ) ₂ —, —COO (CH ₂ ) ₂ —, — (CH ₂ ) ₂ OCO—, — (CH ₂ ) ₂ — or —O (CH ₂ ) ₂ O— Yes;
Q ² is independently a single bond or alkylene having 1 to 20 carbon atoms, and any —CH ₂ — in the alkylene is —O—, —CO—, —COO—, —OCO—, —OCOO— or — CH = CH— may be replaced and any hydrogen may be replaced with a halogen;
n is an integer from 1 to 5;
x is 0 or 1. ]

[In formulas (2-1) to (2-6), R ^a is independently hydrogen, halogen, alkyl having 1 to 5 carbons or alkyl halide having 1 to 5 carbons. ] In the formula (1) according to claim 12, A ¹ is independently 1,4-cyclohexylene, 1,4-phenylene or 1,3-dioxane-2,5-diyl, 1,4-phenylene Any hydrogen in may be replaced by chlorine, fluorine, -CN, alkyl having 1 to 3 carbons, alkoxy having 1 to 3 carbons or fluoroalkyl having 1 to 3 carbons;
Z ² is independently a single bond, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, —COOCH ₂ —, —CH ₂ COOCH ₂ —, —CH═CH—, — (CH ₂ ) ₂ COO—, —OCO (CH ₂ ) ₂ —, —CH═CH—COO—, —OCO—CH═CH— or —C≡C—;
Q ¹ is a single bond or alkylene having 1 to 10 carbons, and any —CH ₂ — in the alkylene may be replaced by —O—, —COO—, —OCO— or —OCOO—;
m is 1-3,
In formulas (M1) and (M2) according to claim 12,
R ³ is independently a polymerizable group represented by formula (2-1), alkyl having 1 to 8 carbons, alkoxy having 1 to 8 carbons, chlorine, fluorine, —CN, —CF ₃ or —OCF. ₃ ;
A ² is independently 1,4-cyclohexylene, 1,4-phenylene or 1,4-phenylene norbornene, and any hydrogen in 1,4-phenylene is chlorine, fluorine, —CN, carbon number 1 to 3 alkyl, 1 to 3 carbon alkoxy or 1 to 3 halogenated alkyl may be substituted;
Z ³ is independently a single bond, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, —C≡C—, —CH═CHCOO—, —OCOCH═CH—, — (CH ₂ ) ₂ COO— or —OCO (CH ₂ ) ₂ —;
Q ² is independently a single bond or alkylene having 1 to 10 carbon atoms, and any —CH ₂ — in the alkylene may be replaced by —O—, —COO—, —OCO— or —OCOO—. ;
n is an integer of 2 or 3,
The polymerizable liquid crystal composition according to claim 12. In formula (1) according to claim 12,
A ¹ is independently 1,4-cyclohexylene or 1,4-phenylene, and any hydrogen in 1,4-phenylene is replaced by chlorine, fluorine, —CH ₃ , —OCH ₃ or —CF ₃ Well;
Z ² is independently a single bond, —COO—, —OCO—, —COOCH ₂ — or —CH ₂ COOCH ₂ —;
Q ¹ is independently alkylene having 1 to 10 carbons, and —CH ₂ — closest to the ring in the alkylene may be replaced by —O—, —COO—, —OCO— or —OCOO—;
m is 2,
In formulas (M1) and (M2) according to claim 12,
R ³ is independently a polymerizable group represented by the formula (2-1), alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons, —CN, fluorine, or —OCF ₃ . ;
A ² is independently 1,4-cyclohexylene, 1,4-phenylene, monofluoro-1,4-phenylene or difluoro-1,4-phenylene;
Z ³ is independently a single bond, —COO—, —OCO—, —CH═CHCOO—, —OCOCH═CH—, — (CH ₂ ) ₂ COO— or —OCO (CH ₂ ) ₂ —;
Q ² is independently a single bond or alkylene having 1 to 10 carbon atoms, and —CH ₂ — closest to the ring in the alkylene is replaced by —O—, —COO—, —OCO— or —OCOO—. Well;
n is 2 or 3;
The polymerizable liquid crystal composition according to claim 12 or 13. The total amount of the compound represented by the formula (1) according to claim 12 and the polymerizable compound selected from the group of compounds represented by the formulas (M1) and (M2) according to claim 12 is 100 wt. %, The content of the compound represented by the formula (1) according to claim 12 is 1 to 90% by weight,
The content of a polymerizable compound selected from the group of compounds represented by formula (M1) and formula (M2) according to claim 12 is 10 to 99% by weight. The polymerizable liquid crystal composition according to item. The total amount of the compound represented by the formula (1) according to claim 12 and the polymerizable compound selected from the group of compounds represented by the formulas (M1) and (M2) according to claim 12 is 100 wt. %, The content of the compound represented by the formula (1) according to claim 12 is 3 to 85% by weight,
The content of a polymerizable compound selected from the group of compounds represented by formula (M1) and formula (M2) according to claim 12 is 15 to 97% by weight. The polymerizable liquid crystal composition according to item.   The polymerizable liquid crystal composition according to any one of claims 11 to 16, further comprising a polymerizable compound having no liquid crystallinity other than the compound represented by formula (1) according to claim 12.   The polymerizable liquid crystal composition according to claim 11, further comprising a non-polymerizable liquid crystal compound.   The polymerizable liquid crystal composition according to claim 11, further comprising a polymerizable optically active compound.   The polymerizable liquid crystal composition according to claim 11, further comprising a non-polymerizable optically active compound.   A polymer film obtained by polymerizing the polymerizable liquid crystal composition according to claim 11.   An anisotropic polymer obtained by polymerizing the polymerizable liquid crystal composition according to any one of claims 11 to 20.   The anisotropic polymer according to claim 22, wherein the alignment form of the polymerizable liquid crystal composition is any one of homogeneous alignment, tilt alignment, twist alignment, and homeotropic alignment.   The anisotropic polymer according to claim 22 or 23, wherein the alignment form of the polymerizable liquid crystal composition is controlled by any one of rubbing treatment, photo-alignment treatment, ion beam treatment, corona treatment, and plasma treatment.   The laminated body which has a support base material which consists of a glass substrate or a plastic substrate, and the anisotropic polymer of any one of Claims 22-24.   An optical compensation film comprising the anisotropic polymer according to any one of claims 22 to 24 and / or the laminate according to claim 25.   A reflective film comprising the anisotropic polymer according to any one of claims 22 to 24 and / or the laminate according to claim 25.   A liquid crystal display device comprising the optical compensation film according to claim 26.   A liquid crystal display device having the reflective film according to claim 27.   A liquid crystal display device comprising the optical compensation film according to claim 26.   A liquid crystal display element device comprising the reflective film according to claim 27.

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