JP2006342332A - Cyclic ether polymerizable liquid crystal composition, homeotropically aligned liquid crystal film and method for producing homeotropically aligned liquid crystal film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optimum polymerizable liquid crystal composition uniformly coating the top surface of a norbornene-based resin substrate with a polymerizable liquid crystal composition and uniformly forming homeotropic alignment, to provide a liquid crystal film obtained from the same, to provide a homeotropically aligned liquid crystal film prepared by polymerizing a polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition, to provide an optical compensation film using the film and to provide an image display device such as a liquid crystal display device, an organic EL (electroluminescent) display device or a PDP (plasma display panel) having the optical compensation film. <P>SOLUTION: The homeotropically aligned liquid crystal film is obtained by coating the top surface of the norbornene-based resin substrate subjected to a hydrophilization treatment with the polymerizable liquid crystal composition containing the polymerizable liquid crystal compound having a polymerizable group with an epoxy and a non-polymerizable polar group using a polar solvent and polymerizing the polymerizable liquid crystal compound. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a homeotropic alignment liquid crystal film. Furthermore, the present invention relates to an optical film made of this film and a liquid crystal display device on which the optical film is mounted.

  In recent years, applications to optical elements such as polarizing plates and retardation plates using photopolymerizable liquid crystals have been proposed. These optical elements are obtained by polymerizing a polymerizable liquid crystal having optical anisotropy in a liquid crystal state and fixing the alignment of the liquid crystal. The polymerizable liquid crystal can be polymerized while maintaining the alignment state after appropriate alignment control in the liquid crystal state. Therefore, by fixing the alignment vector of the liquid crystal skeleton in an alignment state such as homogeneous alignment (horizontal alignment), tilt alignment (tilt alignment), homeotropic alignment (vertical alignment) or twist alignment (twist alignment) A polymer having anisotropy can be obtained. In the following, the above-described alignment state may be simplified and described as “having homogeneous alignment”, “having tilt alignment”, “having homeotropic alignment”, or “having twist alignment”.

Polymers having homeotropic orientation are classified as positive C-plates in the refractive index ellipsoid because the optical axis direction 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 is used for optical compensation of horizontally aligned liquid crystal mode, so-called IPS (In-Plane Switching) mode, for example, for improving the viewing angle characteristics of the polarizing plate by combining with a film having other optical functions. it can. (For example, see Non-Patent Document 1)

As a method for forming a polymer having homeotropic alignment on a plastic film, for example, Patent Document 1 (Japanese Patent Laid-Open No. 10-319408) includes a surfactant in a matrix of an alignment film formed on a support substrate. Alternatively, there is a method of obtaining homeotropic alignment using an inorganic film. Patent Document 2 (Japanese Patent Laid-Open No. 2003-121852) uses a side chain type liquid crystal polymer, and Patent Document 3 (Japanese Patent Laid-Open No. 2005-266802) uses a method using a side chain polymer film. However, in any of the above methods, a film having an orientation control action must be formed on the surface of the holding substrate, which causes a problem of an increase in manufacturing process.
MSPark et al, IDW '04 FMC8-4 Japanese Patent Laid-Open No. 10-319408 JP 2003-121852 A JP 2005-266802 A

  In the past, the present inventors have formed a specific polymerizable liquid crystal composition having an alignment control film made of polyamic acid baked at a temperature of 180 ° C. or less on a support substrate and having a polar group as an epoxy group and a terminal group. It has been found that a polymerizable liquid crystal film having homeotropic alignment can be obtained by curing by UV irradiation. In this case, the alignment control film is an essential component, but the present invention does not require an alignment control film. In the present invention, the alignment form of the polymerizable liquid crystal is controlled to homeotropic alignment without forming an alignment control film on the norbornene resin film. That is, the polymerizable liquid crystal composition can be directly applied onto the norbornene-based resin film that is the support substrate. Specifically, it is characterized in that a homeotropic alignment liquid crystal film can be easily obtained by directly coating a polymerizable liquid crystal composition on a hydrophilized norbornene resin film.

The first object of the present invention is to uniformly coat a polymerizable liquid crystal composition on an optical plastic film made of a norbornene-based resin without using an alignment control film to form a uniform homeotropic alignment. It is an object to provide an optimal polymerizable liquid crystal composition that can be made, and a method for producing the same. The second object of the present invention is to provide a homeotropic alignment liquid crystal film obtained by polymerizing a polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition, and an optical compensation film using the film. . A third object of the present invention is to provide an image display device such as a liquid crystal display device, an organic EL display device, and a PDP having the optical compensation film.

  The present inventors diligently studied to solve the above problems, and completed the present invention. The present invention has the following configuration.

［式（１−１）および式（１−２）中、Ｚ^１およびＺ^３は互いに独立して−ＣＨ_２−または−Ｏ−であり；
Ｚ^２およびＺ^４は互いに独立して単結合、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−ＣＯＯ−または−ＯＣＯ−ＣＨ＝ＣＨ−であり；
Ａ^１およびＡ^３は互いに独立して１，４−フェニレン、９−メチルフルオレン−２，７−ジイル、またはフルオレン−２，７−ジイルであり；
ａおよびｃは互いに独立して４〜８の整数であり；ｂおよびｄは互いに独立して１〜２の整数であり；
Ｒ^１はメチルまたはエチルであり；
Ａ^２およびＡ^４は互いに独立して式（ａ−１）または式（ａ−２）で表される基のいずれか１つである。
式（ａ−２）中、Ｘは−ＣＮまたは−ＯＣＦ_３であり；Ｙはそれぞれ独立に水素またはフッ素である。
（ただし、式（１−１）においてＡ^１が１，４−フェニレン、Ｚ^２が−ＣＯＯ−、Ａ^２が式（ａ−２）であり、式（ａ−２）におけるＸが−ＯＣＦ_３、Ｙが水素またはフッ素である場合は、Ｚ^１は−ＣＨ_２−である。）］ 1. On a norbornene-based resin substrate on which a polymerizable liquid crystal composition containing at least one compound selected from the group of compounds represented by the following formula (1-1) and formula (1-2) has been subjected to a hydrophilic treatment Homeotropic alignment liquid crystal film obtained by directly coating and polymerizing.

[In Formula (1-1) and Formula (1-2), Z ¹ and Z ³ are each independently —CH ₂ — or —O—;
Z ² and Z ⁴ are each independently a single bond, —COO—, —OCO—, —CH═CH—COO— or —OCO—CH═CH—;
A ¹ and A ³ are independently of each other 1,4-phenylene, 9-methylfluorene-2,7-diyl, or fluorene-2,7-diyl;
a and c are each independently an integer of 4 to 8; b and d are each independently an integer of 1 to 2;
R ¹ is methyl or ethyl;
A ² and A ⁴ are each independently any one of groups represented by the formula (a-1) or the formula (a-2).
In formula (a-2), X is —CN or —OCF ₃ ; Y is independently hydrogen or fluorine.
(However, in Formula (1-1), A ¹ is 1,4-phenylene, Z ² is —COO—, A ² is Formula (a-2), and X in Formula (a-2) is —OCF ₃ , When Y is hydrogen or fluorine, Z ¹ is —CH ₂ —.)]

［式中Ｒ^２はメチルまたはエチルであり；
Ｚ^５およびＺ^８は互いに独立して−ＣＨ_２−または−Ｏ−であり（ただしｅおよびｇが０である場合は−ＣＨ_２−である）；
Ｚ^６およびＺ^９は互いに独立して−ＣＯＯ−、−ＯＣＯ−または−ＣＨ_２ＣＨ_２−ＣＯＯ−であり；
Ｚ^７およびＺ^１０は互いに独立して−ＯＣＯ−、−ＣＯＯ−または−ＯＣＯ−ＣＨ_２ＣＨ_２−であり；
Ａ^５およびＡ^８は互いに独立して１，４−フェニレンまたは３−フルオロ−１，４−フェニレンであり；
Ａ^７およびＡ^１０は互いに独立して１，４−フェニレンまたは２−フルオロ−１，４−フェニレンであり；
Ａ^６およびＡ^９は互いに独立して１，４−フェニレン、３−メチル−１，４−フェニレン、３−トリフルオロメチル−１，４−フェニレン、２，３−ビス（トリフルオロメチル）−１，４−フェニレン、９−メチルフルオレン−２，７−ジイル、９−エチルフルオレン−２，７−ジイル、または９，９−ジメチルフルオレン−２，７−ジイルであり；
ｆおよびｈは互いに独立して０または１であり；
ｅおよびｇは互いに独立して０〜１０の整数である。］ 2. The polymerizable liquid crystal composition contains at least one compound selected from the group of compounds represented by formula (1-1) and formula (1-2) as the first component, and the following formula (2) as the second component: The homeotropic alignment liquid crystal film according to item 1, which contains at least one compound selected from the group of compounds represented by -1) and formula (2-2):

[Wherein R ² is methyl or ethyl;
Z ⁵ and Z ⁸ are independently of each other —CH ₂ — or —O— (provided —CH ₂ — when e and g are 0);
Z ⁶ and Z ⁹ are independently of each other —COO—, —OCO— or —CH ₂ CH ₂ —COO—;
Z ⁷ and Z ¹⁰ are independently of each other —OCO—, —COO— or —OCO—CH ₂ CH ₂ —;
A ⁵ and A ⁸ are independently of each other 1,4-phenylene or 3-fluoro-1,4-phenylene;
A ⁷ and A ¹⁰ are independently of each other 1,4-phenylene or 2-fluoro-1,4-phenylene;
A ⁶ and A ⁹ are independently of each other 1,4-phenylene, 3-methyl-1,4-phenylene, 3-trifluoromethyl-1,4-phenylene, 2,3-bis (trifluoromethyl) -1. , 4-phenylene, 9-methylfluorene-2,7-diyl, 9-ethylfluorene-2,7-diyl, or 9,9-dimethylfluorene-2,7-diyl;
f and h are independently 0 or 1;
e and g are each independently an integer of 0 to 10; ]

式（ａ−２）中、Ｘは−ＣＮまたは−ＯＣＦ_３であり；Ｙはそれぞれ独立に水素またはフッ素であり、
（ただし、式（１−１）においてＡ^１が１，４−フェニレン、Ｚ^２が−ＣＯＯ−、Ａ^２が式（ａ−２）であり、式（ａ−２）におけるＸが−ＯＣＦ_３、Ｙが水素またはフッ素である場合は、Ｚ^１は−ＣＨ_２−である。）］
第２成分の式（２−１）において、
Ｚ^５は−ＣＨ_２−または−Ｏ−であり（ただしｅが０である場合は−ＣＨ_２−である）；
Ｚ^６は−ＣＯＯ−または−ＯＣＯ−であり；
Ｚ^７は−ＯＣＯ−または−ＣＯＯ−であり；
Ａ^５は１，４−フェニレンまたは３−フルオロ−１，４−フェニレンであり；
Ａ^６は１，４−フェニレン、３−メチル−１，４−フェニレン、９−メチルフルオレン−２，７−ジイルまたは９，９−ジメチルフルオレン−２，７−ジイルであり；
Ａ^７は１，４−フェニレンまたは２−フルオロ−１，４−フェニレンであり；
ｆは０または１であり；
ｅは０〜１０の整数であり；
第２成分の式（２−２）において、
Ｒ^２はメチルまたはエチルであり；
Ｚ^８は−ＣＨ_２−または−Ｏ−であり（ただしｇが０である場合は−ＣＨ_２−である）；
Ｚ^９は−ＣＯＯ−、−ＯＣＯ−または−ＣＨ_２ＣＨ_２−ＣＯＯ−であり；
Ｚ^１０は−ＯＣＯ−、−ＣＯＯ−または−ＯＣＯ−ＣＨ_２ＣＨ_２−であり；
Ａ^８は１，４−フェニレンまたは３−フルオロ−１，４−フェニレンであり；
Ａ^９は３−メチル−１，４−フェニレン、３−トリフルオロメチル−１，４−フェニレン、２，３−ビス（トリフルオロメチル）−１，４−フェニレン、９−メチルフルオレン−２，７−ジイル、９−エチルフルオレン−２，７−ジイルまたは９，９−ジメチルフルオレン−２，７−ジイルであり；
Ａ^１０は１，４−フェニレンまたは２−フルオロ−１，４−フェニレンであり；
ｈは０または１であり；
ｇは１〜１０の整数であることを特徴とする項２に記載のホメオトロピック配向液晶フィルム。 3. In the formula (1-1) and formula (1-2) of the first component in the polymerizable liquid crystal composition,
Z ¹ and Z ³ are independently of each other —CH ₂ — or —O—;
Z ² and Z ⁴ are each independently a single bond, —COO—, —OCO—, —CH═CH—COO— or —OCO—CH═CH—;
A ¹ and A ³ are independently of each other 1,4-phenylene or 9-methylfluorene-2,7-diyl;
a and c are independently an integer of 4 to 6;
b and d are each independently an integer of 1 to 2;
R ¹ is methyl or ethyl;
A ² and A ⁴ are each independently any one of the groups represented by the formula (a-1) or the formula (a-2);

In formula (a-2), X is —CN or —OCF ₃ ; Y is independently hydrogen or fluorine,
(However, in Formula (1-1), A ¹ is 1,4-phenylene, Z ² is —COO—, A ² is Formula (a-2), and X in Formula (a-2) is —OCF ₃ , When Y is hydrogen or fluorine, Z ¹ is —CH ₂ —.)]
In the formula (2-1) of the second component,
Z ⁵ is —CH ₂ — or —O— (when e is 0, it is —CH ₂ —);
Z ⁶ is —COO— or —OCO—;
Z ⁷ is —OCO— or —COO—;
A ⁵ is 1,4-phenylene or 3-fluoro-1,4-phenylene;
A ⁶ is 1,4-phenylene, 3-methyl-1,4-phenylene, 9-methylfluorene-2,7-diyl or 9,9-dimethylfluorene-2,7-diyl;
A ⁷ is 1,4-phenylene or 2-fluoro-1,4-phenylene;
f is 0 or 1;
e is an integer from 0 to 10;
In the formula (2-2) of the second component,
R ² is methyl or ethyl;
Z ⁸ is —CH ₂ — or —O— (when g is 0, it is —CH ₂ —);
Z ⁹ is —COO—, —OCO— or —CH ₂ CH ₂ —COO—;
Z ¹⁰ is —OCO—, —COO— or —OCO—CH ₂ CH ₂ —;
A ⁸ is 1,4-phenylene or 3-fluoro-1,4-phenylene;
A ⁹ is 3-methyl-1,4-phenylene, 3-trifluoromethyl-1,4-phenylene, 2,3-bis (trifluoromethyl) -1,4-phenylene, 9-methylfluorene-2,7 -Diyl, 9-ethylfluorene-2,7-diyl or 9,9-dimethylfluorene-2,7-diyl;
A ¹⁰ is 1,4-phenylene or 2-fluoro-1,4-phenylene;
h is 0 or 1;
3. The homeotropic alignment liquid crystal film according to item 2, wherein g is an integer of 1 to 10.

4). Item 4. The polymerizable liquid crystal composition according to items 1 to 3, wherein the content of the compound represented by formula (1-1) or formula (1-2) is 5 to 99 based on the total amount of the polymerizable liquid crystal composition. Item 5. The homeotropic alignment liquid crystal film according to any one of Items 1 to 3, wherein the liquid crystal film is% by weight.

［式（１−１）および式（１−２）中、Ｚ^１およびＺ^３は互いに独立して−ＣＨ_２−または−Ｏ−であり；
Ｚ^２およびＺ^４は互いに独立して単結合、−ＣＯＯ−または−ＯＣＯ−であり；
Ａ^１およびＡ^３は互いに独立して１，４−フェニレンまたは９−メチルフルオレン−２，７−ジイルであり；
ａおよびｃは互いに独立して４〜６の整数であり；
ｂおよびｄは互いに独立して１〜２の整数であり；
Ｒ^１はメチルまたはエチルであり；
Ａ^２およびＡ^４は互いに独立して下記式で表される基のいずれか１つであり、
式（ａ−２）中、Ｘは−ＣＮまたは−ＯＣＦ_３であり；Ｙはそれぞれ独立に水素またはフッ素であり、
（ただし、式（１−１）においてＡ^１が１，４−フェニレン、Ｚ^２が−ＣＯＯ−、Ａ^２が式（ａ−２）であり、式（ａ−２）におけるＸが−ＯＣＦ_３、Ｙが水素またはフッ素である場合は、Ｚ^１は−ＣＨ_２−である。）
式（２−１）および式（２−２）中、Ｒ^２は互いに独立してメチルまたはエチルであり；
Ｚ^５およびＺ^８は互いに独立して−ＣＨ_２−または−Ｏ−であり（ただしｅおよびｇが０である場合は−ＣＨ_２−である）；
Ｚ^６およびＺ^９は互いに独立して−ＣＯＯ−または−ＯＣＯ−であり；
Ｚ^７およびＺ^１０は互いに独立して−ＯＣＯ−または−ＣＯＯ−であり、
Ａ^５は１，４−フェニレンまたは３−フルオロ−１，４−フェニレンであり；
Ａ^６は１，４−フェニレン、３−メチル−１，４−フェニレン、９−メチルフルオレン−２，７−ジイルまたは９，９−ジメチルフルオレン−２，７−ジイルであり；
Ａ^８は１，４−フェニレンまたは３−フルオロ−１，４−フェニレンであり；
Ａ^９は３−メチル−１，４−フェニレン、３−トリフルオロメチル−１，４−フェニレン、２，３−ビス（トリフルオロメチル）−１，４−フェニレン、９−メチルフルオレン−２，７−ジイル、９−エチルフルオレン−２，７−ジイルまたは９，９−ジメチルフルオレン−２，７−ジイルであり；
Ａ^７およびＡ^１０は互いに独立して１，４−フェニレンまたは２−フルオロ−１，４−フェニレンであり；
ｆは０または１であり；
ｈは１であり；
ｅは０〜６の整数であり、ｇは０〜６の整数である。］ 5. It contains at least one compound selected from the group of compounds represented by the following formula (1-1) and formula (1-2) as the first component, and the following formula (2-1) and formula ( It is obtained by directly applying a polymerizable liquid crystal composition containing at least one compound selected from the group of compounds represented by 2-2) onto a norbornene-based resin base material that has been subjected to a hydrophilization treatment and polymerizing the composition. Homeotropic alignment liquid crystal film.

[In Formula (1-1) and Formula (1-2), Z ¹ and Z ³ are each independently —CH ₂ — or —O—;
Z ² and Z ⁴ are each independently a single bond, —COO— or —OCO—;
A ¹ and A ³ are independently of each other 1,4-phenylene or 9-methylfluorene-2,7-diyl;
a and c are independently an integer of 4 to 6;
b and d are each independently an integer of 1 to 2;
R ¹ is methyl or ethyl;
A ² and A ⁴ are each one of the groups represented by the following formulas independently of each other;
In formula (a-2), X is —CN or —OCF ₃ ; Y is independently hydrogen or fluorine,
(However, in Formula (1-1), A ¹ is 1,4-phenylene, Z ² is —COO—, A ² is Formula (a-2), and X in Formula (a-2) is —OCF ₃ , Y is hydrogen or fluorine, Z ¹ is —CH ₂ —.)
In Formula (2-1) and Formula (2-2), R ² is independently of each other methyl or ethyl;
Z ⁵ and Z ⁸ are independently of each other —CH ₂ — or —O— (provided —CH ₂ — when e and g are 0);
Z ⁶ and Z ⁹ are independently of each other —COO— or —OCO—;
Z ⁷ and Z ¹⁰ are each independently —OCO— or —COO—,
A ⁵ is 1,4-phenylene or 3-fluoro-1,4-phenylene;
A ⁶ is 1,4-phenylene, 3-methyl-1,4-phenylene, 9-methylfluorene-2,7-diyl or 9,9-dimethylfluorene-2,7-diyl;
A ⁸ is 1,4-phenylene or 3-fluoro-1,4-phenylene;
A ⁹ is 3-methyl-1,4-phenylene, 3-trifluoromethyl-1,4-phenylene, 2,3-bis (trifluoromethyl) -1,4-phenylene, 9-methylfluorene-2,7 -Diyl, 9-ethylfluorene-2,7-diyl or 9,9-dimethylfluorene-2,7-diyl;
A ⁷ and A ¹⁰ are independently of each other 1,4-phenylene or 2-fluoro-1,4-phenylene;
f is 0 or 1;
h is 1;
e is an integer of 0 to 6, and g is an integer of 0 to 6. ]

［式（１−１−Ａ）〜式（１−１−Ｄ）および式（１−２−Ａ）〜式（１−２−Ｅ）中、Ｒ^１はメチルまたはエチルであり；Ｚ^１およびＺ^３は互いに独立して−Ｏ−または−ＣＨ_２−であり；ａおよびｃは互いに独立して４〜６の整数であり；ＸはＣＮまたはＯＣＦ_３であり；Ｙは水素またはフッ素であり、式（２−１−Ａ）〜式（２−１−Ｃ）および式（２−２−Ａ）〜式（２−２−Ｂ）中、Ｒ^２はメチルまたはエチルであり；Ｚ^５およびＺ^８は互いに独立して−Ｏ−または−ＣＨ_２−であり（ただしｅおよびｇが０である場合は−ＣＨ_２−である）；ｅおよびｇは互いに独立して０〜６の整数であり；Ｌ^１およびＬ^２は互いに独立して水素またはフッ素を表し、Ｌ^３は水素またはメチルを表し、Ｌ^４およびＬ^５は互いに独立して水素、メチル、トリフルオロメチルを表すが、Ｌ^４およびＬ^５が共に水素であることはなく、Ｗ^１およびＷ^２は互いに独立して水素またはメチルを表す。］ 6). The polymerizable liquid crystal composition is represented by the following formula (1-1-A) to formula (1-1-D) and formula (1-2-A) to formula (1-2-E) as the first component. And at least one compound selected from the group of compounds having formula (2-1-A) to formula (2-1-C) and formula (2-2A) to formula (2- Item 6. The homeotropic alignment liquid crystal film according to item 5, which contains at least one compound selected from the group of compounds represented by 2-B).

[In formula (1-1-A) to formula (1-1-D) and formula (1-2-A) to formula (1-2-E), R ¹ is methyl or ethyl; Z ¹ and Z ³ is independently of each other —O— or —CH ₂ —; a and c are each independently an integer of 4 to 6; X is CN or OCF ₃ ; Y is hydrogen or fluorine In formula (2-1-A) to formula (2-1-C) and formula (2-2A) to formula (2-2B), R ² is methyl or ethyl; Z ⁵ and Z ⁸ is independently of each other —O— or —CH ₂ — (provided that when e and g are 0, it is —CH ₂ —); and e and g are each independently an integer of 0-6. There; ^{L 1} and ^{L 2} represents a hydrogen or fluorine independently of one another, ^{L 3} represents hydrogen or methyl, ^{L 4} and ^{L 5} independently of one another It represents hydrogen, methyl, trifluoromethyl Te, but never L ⁴ and which L ⁵ are both hydrogen, W ¹ and W ² represents a hydrogen or methyl independently of one another. ]

［式中、Ｒ^２はメチルまたはエチルであり；ａは互いに独立して４〜６の整数であり、ｇは２〜６の整数である］ 7). The polymerizable liquid crystal composition has at least one compound selected from the group of compounds represented by the following formula (1-1-1) and formula (1-1-15) as the first component, and the following as the second component: Item 6. The homeotropic alignment liquid crystal film according to Item 5, which contains at least one compound selected from the group of compounds represented by formula (2-1-1) and formula (2-2-1).

[Wherein R ² is methyl or ethyl; a is independently an integer of 4 to 6, and g is an integer of 2 to 6]

［式中、Ｒ^１およびＲ^２は互いに独立してメチルまたはエチルであり；ｃは互いに独立して４〜６の整数であり、ｇは２〜６の整数である］ 8). The polymerizable liquid crystal composition is at least one selected from the group of compounds represented by the following formula (1-2-1), formula (1-2-5), and formula (1-2-19) as the first component. Item 5 comprising at least one compound selected from the group of compounds represented by formula (2-1-1) and formula (2-2-1) as a second component: Homeotropic alignment liquid crystal film as described in 1.

[Wherein R ¹ and R ² are each independently methyl or ethyl; c is each independently an integer of 4-6, and g is an integer of 2-6]

［式中、Ｒ^２はメチルまたはエチルであり；ａは互いに独立して４〜６の整数であり、ｇは２〜６の整数である］ 9. The polymerizable liquid crystal composition has at least one compound selected from the group of compounds represented by the following formula (1-1-1) and formula (1-1-15) as the first component, and the following as the second component: Item 6. The homeotropic alignment liquid crystal film according to item 5, which contains at least one compound represented by formula (2-2-1).

[Wherein R ² is methyl or ethyl; a is independently an integer of 4 to 6, and g is an integer of 2 to 6]

［式中、Ｒ^１およびＲ^２は互いに独立してメチルまたはエチルであり；ｃは互いに独立して４〜６の整数であり、ｇは２〜６の整数である］ 10. One polymerizable liquid crystal composition selected from the group of compounds represented by the following formula (1-2-1), formula (1-2-5), and formula (1-2-19) as the first component And a compound containing at least one compound represented by the following formula (2-1-1) and at least one compound represented by the following formula (2-2-1) as a second component Item 6. A homeotropic alignment liquid crystal film according to Item 5.

[Wherein R ¹ and R ² are each independently methyl or ethyl; c is each independently an integer of 4-6, and g is an integer of 2-6]

11. In the polymerizable liquid crystal composition according to item 5, the content of the compound represented by formula (1-1) to formula (1-2) as the first component is based on the total amount of the polymerizable liquid crystal composition. Item 11. The homeotropic alignment liquid crystal film according to any one of Items 5 to 10, which is 5 to 99% by weight.

12 Item 6. The polymerizable liquid crystal composition according to item 5, wherein the content of the compound represented by formula (1-1) to formula (1-2) is 5 to 45% by weight based on the total amount of the polymerizable liquid crystal composition. Item 7. The homeotropic alignment liquid crystal film according to any one of Items 1 to 6.

13. Item 13. The homeotropic alignment liquid crystal film according to any one of Items 1 to 12, wherein the hydrophilization treatment of the norbornene-based resin substrate is a corona treatment or a plasma treatment.

14 Any one of Items 1 to 13 obtained by dissolving the polymerizable liquid crystal composition in a solvent containing a polar solvent, applying the solution on a norbornene-based resin base material that has been subjected to a hydrophilic treatment, and polymerizing the solution. The homeotropic alignment liquid crystal film as described.

15. Item 15. The homeotropic alignment liquid crystal film according to Item 14, wherein the solvent contains a polar solvent in an amount of 30% by weight or more based on the total weight of the solvent.

16. Item 16. The homeotropic alignment liquid crystal film according to Item 14 or 15, wherein the polar solvent is any one of ketone, acetate, ether, cellosolve, ester, and alcohol.

17. A polymerizable liquid crystal composition containing a compound represented by the formula (1-1) to the formula (1-2) is coated on a norbornene-based resin substrate subjected to a hydrophilic treatment and polymerized. A method for producing a homeotropic alignment liquid crystal film.

18. Item 18. The method for producing a homeotropic alignment liquid crystal film according to Item 17, wherein the polymerizable liquid crystal composition is the polymerizable liquid crystal composition according to any one of Items 1 to 12.

19. Item 19. An optical film having the homeotropic alignment liquid crystal film according to any one of items 1 to 16 or the homeotropic alignment liquid crystal film produced by the method according to item 17 or 18.

20. Item 20. A liquid crystal display device comprising at least one optical film of Item 19.

  The homeotropic alignment liquid crystal film using the norbornene-based resin film of the present invention as a supporting substrate is easy to manufacture because it does not require an alignment control film, and is excellent in homeotropic alignment uniformity.

  In the following description, the compound represented by the formula (1-1) may be referred to as the compound (1-1). The compounds represented by other formulas may be referred to in the same manner. That is, the compound represented by formula (1-2), formula (1-1-A), formula (1-1-1), or the like is converted into compound (1-2), compound (1-1-A), and compound. Sometimes referred to as (1-1-1). Formula (1-1) to Formula (1-2), Formula (1-1-A) to Formula (1-1-F), Formula (1-2-A) to Formula (1-2-F) The compounds represented by formula (1-1-1) to formula (1-1-25), formula (1-2-1) to formula (1-2-21), and the like are referred to as first component compounds. In the sense, it may be collectively referred to as compound (1). Similarly, other compounds represented by, for example, the formula (2-1) may be collectively referred to as the compound (2).

  Terms used in the present invention will be described. “Direct application” means direct application without forming another layer such as an orientation control film or a protective film on the substrate. “Hydrophilic treatment” is a treatment for increasing the affinity with water by any method, that is, improving the wettability with water.

  The angle formed by the orientation vector of the liquid crystal skeleton with the plane of the supporting substrate is defined as “tilt angle”. An alignment state in which the tilt angle is uniformly close to zero from one interface to the other interface and in particular is 0 to 5 ° is referred to as “homogeneous alignment”. Here, the interface is a support substrate interface provided with an alignment layer or a free interface. An alignment state in which the tilt angle is constant within a range of 5 to 85 ° from one interface to the other interface or continuously changes within a range of 0 to 90 ° is referred to as “tilt alignment”. An alignment state in which the tilt angle is uniformly 85 to 90 ° from one interface to the other interface is referred to as “homeotropic alignment”.

The meaning of “liquid crystallinity” is not limited to having a liquid crystal phase. A characteristic that can be used as a component of a liquid crystal composition when mixed with another liquid crystal compound even if it does not have a liquid crystal phase is also included in the meaning of “liquid crystallinity”. “Arbitrary” indicates that not only the position but also the number is arbitrary, but the case where the number is 0 is not included. For example, when it is expressed that any —CH ₂ — in alkyl may be replaced by —O— or —CH═CH—, a plurality of —CH ₂ — may be replaced by different groups. Examples of such cases are alkyl, alkoxy, alkoxyalkyl, alkoxyalkenyl, alkenyloxyalkyl and the like. The meaning of the phrase “any —CH ₂ — in alkyl may be replaced by —O— or —CH═CH—” is shown by way of example. A part of the group in which any —CH ₂ — in C ₄ H ₉ — is replaced by —O— or —CH═CH— is C ₃ H ₇ O—, CH ₃ —O— (CH ₂ ) ₂ —, _{CH 3 -O-CH 2 -O-,} H 2 C = CH- (CH 2) 3 -, CH 3 -CH = CH- (CH 2) 2 -, and _{CH 3 -CH = CH-CH 2} -O -. In the present invention, in consideration of the stability of the compound, two consecutive —CH ₂ — are replaced by —O— or —S—, and —O—O—, —O—S— or — It is not preferable to become SS. “(Meth) acrylate” is sometimes used as a general term for acrylate and methacrylate. Unless otherwise specified, alkyl or alkylene means alkyl including both straight-chain alkyl and branched alkyl. For example, butyl may be any of n-butyl, 2-methylpropyl and 1,1-dimethylethyl. Halogen means fluorine, chlorine or bromine. References to alkenyl or alkenylene mean alkenyl, including both straight and branched alkenyl. Cycloalkyl and cycloalkenyl include a cyclic group having a crosslinked structure in addition to a normal cyclic group.

  In the following description, polymerizable compounds other than the compound (1) and the compound (2) may be referred to as “other polymerizable compounds”. The polymerizable liquid crystal composition used in the present invention is a polymerizable liquid crystal composition containing the compound (1). A polymerizable liquid crystal composition containing only the compound (1) and the compound (2) as a polymerizable component may be referred to as a “cyclic ether-based polymerizable liquid crystal composition”.

The compound that is a component of the polymerizable liquid crystal composition will be described. Compound (1) has a liquid crystal skeleton and one polymerizable group. The polar group (—CN group, —OCF ₃ group) at one end of this compound has a tendency to interact with a substrate (norbornene resin) that has been subjected to a hydrophilic treatment, and promotes homeotropic alignment. The compound (2) has a liquid crystal skeleton and two polymerizable groups. Since the polymer obtained from this compound can have a three-dimensional structure, it gives a hard polymer as compared with a compound having one polymerizable group. Although compound (2) depends on conditions, such as a support substrate and an additive, it is easy to orientate homogeneously.

  The composition of the composition of the present invention will be described. This composition contains at least one compound (1). This composition may contain a plurality of compounds (1) and compounds (2). Further, this composition is different from the compound (1) and the compound (2), and further contains a polymerizable liquid crystal compound (3) having no non-polymerizable polar group at one end, or another polymerizable compound (4). You may contain.

This composition is classified into the following composition A, composition B and the like.
Composition A contains compound (1) and compound (2).
The composition A may further contain a compound (3), another polymerizable compound (4), an additive, an organic solvent, and the like.
Composition B contains compound (1), compound (2) and compound (3) as the polymerizable compound, but does not contain any other polymerizable compound (4).
Composition B may further contain other polymerizable compound (4).
Composition B may further contain additives, organic solvents, and the like.
Composition B has fewer components than composition A.
Composition B is preferable to composition A from the viewpoint of cost.
The composition A is more preferable than the composition B because the characteristics can be further adjusted by the other polymerizable compound (4).

In the compositions A and B, the mixing ratio of the compound (1) and the compound (2) is as follows.
A desirable ratio of compound (1) is 5% to 99% by weight. A more desirable ratio is from 10% to 45% by weight.
A desirable ratio of compound (2) is 1% to 95% by weight. A more desirable ratio is from 55% by weight to 90% by weight.
The addition amount (%) of the compound (3), the compound (4), and the additive is a ratio based on the total weight of the compound (1) and the compound (2).
The preferable addition amount of compound (3) is 0 to 25%. A more preferable addition amount is 0 to 15% or 5 to 15%.
The preferable addition amount of the other polymerizable compound (4) is 0% to 20%. A more preferable addition amount is 0% to 10% or 5 to 15%.
The amount of additives such as surfactants and polymerization initiators may be the minimum amount that achieves the purpose. The same applies to the amount of organic solvent added.

  When the content of the compound (1) is within the above range, a uniform homeotropic alignment liquid crystal film can be obtained. The compounds (1-1) to (1-2) and the compounds (2-1) to (2-2) may be used singly or in combination of two or more. . In addition, rather than using the compound (1-1) having an oxiranyl group (epoxy) and the compound (2-1) alone from the viewpoint of the curing rate, the compound (2-1) having the oxetanyl group (oxetane) and the compound ( 2-2) may be combined.

  Compounds (1) to (4) can be synthesized by appropriately combining known methods in organic synthetic chemistry. Methods for introducing or generating the desired end groups, rings, linking groups, etc. into the starting material are as follows: Organic Syntheses, John Wiley & Sons, Inc, Organic Reactions, John Wiley & Sons, Inc), Comprehensive Organic Synthesis (Pergamon Press), New Experimental Chemistry Course (Maruzen).

The method of synthesizing the compound (1) is described in Macromol. Chem. Phys. No. 2005-320317, Polymer Bulletin 25, pp 439-442 (1991), and the like, which can be synthesized according to these methods.
The synthesis method of the compound (2) is described in Macromolecules 1244-1247 26 (1993), Japanese Patent Application Laid-Open No. 2005-60373, Japanese Patent Application Laid-Open No. 2005-38985, Japanese Patent Application Laid-Open No. 2004-231638, and the like. Synthesis is possible according to the method.

Next, component compounds are exemplified.

In Formula (1-1-A) to Formula (1-1-F), Z ¹ is —O— or —CH ₂ —, Y is hydrogen or fluorine, and X is —CN or —OCF ₃ . Yes, a is an integer of 4-8.

In formulas (1-2-A) to (1-2-F), R ¹ is methyl or ethyl, Z ³ is —O— or —CH ₂ —, Y is hydrogen or fluorine, X is -CN or -OCF _3, and c is an integer of 4 to 8.

Preferred compounds (2-1) are as follows.

In formulas (2-1-A) to (2-1-D), Z ⁵ is independently —O— or —CH ₂ — (when e is 0, —CH ₂ — E is independently an integer of 0 to 6; L ¹ and L ² independently of each other represent hydrogen or fluorine, L ³ represents hydrogen or methyl, and W ¹ represents hydrogen or methyl. .

In the formula (2-2A) to the formula (2-2C), R ² is methyl or ethyl; Z ⁸ is independently —O— or —CH ₂ — (where g is 0 If it is -CH ₂ - is); g be independently of one another are an integer of 0 to 6; ^{L 1} and ^{L 2} represents a hydrogen or fluorine independently of one another, independently of ^{L 4} and ^{L 5} represents one another Hydrogen, methyl and trifluoromethyl, but L ⁴ and L ⁵ are not both hydrogen, and W ² represents hydrogen or methyl.

Specific examples of preferred compound (1-1) to compound (1-2), compound (2-1) and compound (2-2) are as follows. In the following formulas, a and c are each independently an integer of 4 to 8, e and g are each independently an integer of 2 to 6, and R ¹ and R ² are each independently methyl or ethyl It is.

  In the above, compound (1-1-1) to compound (1-1-8), compound (1-1-11) to compound (1-1-16), compound (1-1-20) to Compound (1-1-25), compound (1-2-1) to compound (1-2-5), and compound (1-2-7) to compound (1-2-21) are particularly preferable.

  Among the above, compound (2-1-1) to compound (2-1-5), compound (2-1-7), compound (2-1-9), compound (2-1-11), Compound (2-1-13), Compound (2-1-15), Compound (2-1-17), Compound (2-1-19), Compound (2-1-21), Compound (2-2) -1) to compound (2-2-4), compound (2-2-6), compound (2-2-8), compound (2-2-10), compound (2-2-12), compound (2-2-14), compound (2-2-16), compound (2-2-18) and compound (2-2-20) are particularly preferred.

  The polymerizable liquid crystal composition used in the present invention may further contain a compound (3) having no terminal polar group. The structure of the compound (3) is not limited as long as homeotropic alignment is obtained. Specific examples of the compound (3) are shown below.

The polymerizable liquid crystal composition used in the present invention may further contain other polymerizable compound (4). Examples of other polymerizable compounds (4) are epoxy resins and the like. Examples of epoxy resins are bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, novolac type epoxy resin, polycarboxylic acid polyglycidyl ester, polyol polyglycidyl ether, fatty acid type epoxy resin, alicyclic type Epoxy resin, amine epoxy resin, triphenolmethane type epoxy resin, dihydroxybenzene type epoxy resin, bisphenol full orange crisidyl ether shown below (sold from Osaka Gas Chemical Co., Ltd. BPF-G, BCF-G, BPEF-G) Etc.

  The polymerizable liquid crystal composition used in the present invention may further contain an additive such as a surfactant in order to form a thin coating film. This composition may contain additives such as a polymerization initiator and a photosensitizer suitable for polymerization. This composition may contain additives such as ultraviolet absorbers and antioxidants in order to improve the properties of the polymer.

  Examples of surfactants include imidazoline, quaternary ammonium salts, alkylamine oxides, polyamine derivatives, polyoxyethylene-polyoxypropylene condensates, polyethylene glycol and esters thereof, sodium lauryl sulfate, ammonium lauryl sulfate, amines of lauryl sulfate, alkyl Substituted aromatic sulfonates, alkyl phosphates, aliphatic or aromatic sulfonic acid formalin condensates, laurylamidopropylbetaine, laurylaminoacetic acid betaine, polyethylene glycol fatty acid esters, polyoxyethylene alkylamine, perfluoroalkylsulfonic acid Salt, perfluoroalkyl carboxylate, perfluoroalkylethylene oxide adduct, perfluoroalkyltrimethylammonium salt, perfluoroalkyl And an oligomer having a hydrophilic group, an oligomer having a perfluoroalkyl group and a lipophilic group, a urethane having a perfluoroalkyl group, a polyester-modified polydimethylsiloxane having a hydroxyl group, a polyester polyether-modified polydimethylsiloxane having a hydroxyl group, Polyether-modified polydimethylsiloxane having a hydroxyl group, polyester-modified polyalkylsiloxane, and the like. The addition amount of the surfactant varies depending on the kind of the surfactant and the composition ratio of the polymerizable liquid crystal composition, but is 0.002 to 5 parts by weight with respect to the total weight of the polymerizable liquid crystal compound in the polymerizable liquid crystal composition. The range is preferably 0.01 to 1 part by weight.

  The above-mentioned polymerizable liquid crystal composition can be added with a polymerization initiator as necessary, and polymerized with a polymerizable liquid crystal compound by irradiating with light in the atmosphere to obtain a polymer (homeotropic alignment liquid crystal film). In addition, you may perform a heating etc. in the temperature range with which a liquid crystal phase is maintained at the time of light irradiation. The polymerizable liquid crystal composition used in the present invention can be used by adding a normal photocationic polymerization initiator. Examples of the cationic photopolymerization initiator include diaryliodonium salts (hereinafter abbreviated as DAS), triarylsulfonium salts (hereinafter abbreviated as TAS), and the like.

  Examples of the DAS are diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate, diphenyliodoniumtetra (penta Fluorophenyl) borate, 4-methoxyphenylphenyliodonium tetrafluoroborate, 4-methoxyphenylphenyliodonium hexafluorophosphonate, 4-methoxyphenylphenyliodonium hexafluoroarsenate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphene Ruphenyliodonium trifluoroacetate, 4-methoxyphenylphenyliodonium-p-toluenesulfonate, 4-methoxyphenylphenyliodonium diphenyliodoniumtetra (pentafluorophenyl) borate, bis (4-t-butylphenyl) iodoniumdiphenyliodoniumtetrafluoro Borate, bis (4-t-butylphenyl) iodonium diphenyliodonium hexafluoroarsenate, bis (4-t-butylphenyl) iodonium diphenyliodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium trifluoroacetate, bis (4-t-Butylphenyl) iodonium p-toluenesulfonate, and bis (4-t-butylphenyl) It is over de iodonium diphenyl iodonium tetra (pentafluorophenyl) borate.

  DAS can be made highly sensitive by adding a photosensitizer such as thioxanthone, phenothiazine, chlorothioxanthone, xanthone, anthracene, diphenylanthracene, and rubrene.

  Examples of TAS are triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, triphenylsulfonium-p-toluenesulfonate , Triphenylsulfonium tetra (pentafluorophenyl) borate, 4-methoxyphenyldiphenylsulfonium tetrafluoroborate, 4-methoxyphenyldiphenylsulfonium hexafluorophosphonate, 4-methoxyphenyldiphenylsulfonium hexafluoroarsenate, 4-methoxyphenyldiphenylsulfonium trifluoride Lomethanesulfonate 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium-p-toluenesulfonate, 4-methoxyphenyldiphenylsulfonium triphenylsulfonium tetra (pentafluorophenyl) borate, 4-phenylthiophenyldiphenylsulfonium tetrafluoroborate, 4-phenylthiophenyldiphenylsulfonium hexafluorophosphonate, 4-phenylthiophenyldiphenylsulfonium hexafluoroarsenate, 4-phenylthiophenyldiphenylsulfonium trifluoromethanesulfonate, 4-phenylthiophenyldiphenylsulfonium-p-toluenesulfonate, and 4 -Phenylthiophenyldiphenylsulfoniu Tetra (pentafluorophenyl) borate.

  Examples of specific trade names of the cationic photopolymerization initiators are UCC's products Cyracure UVI-6990, Cyracure UVI-6974 and Cyracure UVI-6922, Asahi Denka Kogyo Co., Ltd. product Adekaoptomer SP -150, SP-152, SP-170 and SP-172, Rhodia's product PHOTOINITIATOR 2074, Ciba Specialty Chemicals 'product Irgacure 250, GE Silicones' product UV-9380C, and Midori It is DTS-102 of the product of Chemical Co., Ltd.

  The polymerizable liquid crystal composition used in the present invention can also be subjected to hybrid polymerization using a photocationic polymerization initiator in combination with an ordinary photoradical polymerization initiator. Examples of radical photopolymerization initiators are Darocur 1173 (2-hydroxy-2-methyl-1-phenylpropan-1-one) and Irgacure 184 (1-hydroxycyclohexylphenyl), products of Ciba Specialty Chemicals Co., Ltd. Ketone), Irgacure 651 (2,2-dimethoxy-1,2-diphenylethane-1-one), Irgacure 500, Irgacure 2959, Irgacure 907, Irgacure 369, Irgacure 1300, Irgacure 819, Irgacure Cure 1700, Irgacure 1800, Irgacure 1850, Darocur 4265, and Irgacure 784.

  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, 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 / methyl p-dimethylaminobenzoate, and benzophenone / methyltriethanol It is an amine mixture.

  The polymerizable liquid crystal composition used in the present invention can be polymerized by utilizing a base multiplication reaction by light (K. Arimitsu, M. Miyamoto, K. Ichimura, Angew. Chem. Int. Ed, 2000, 39). , 3425). A preferable addition amount of the photopolymerization initiator is 0.01 to 10% by weight based on the total amount of the polymerizable liquid crystal composition. A more preferable addition amount is 0.01 to 5% by weight.

  A polymerization inhibitor (polymerization inhibitor) can be added to the polymerizable liquid crystal composition in order to prevent a polymerization initiation reaction during storage. Known polymerization inhibitors can be used, but preferred examples include 2,5-di (t-butyl) hydroxytoluene (BHT), hydroquinone, methyl blue, diphenylpicric hydrazide (DPPH), benzothiazine, 4-nitrosodimethyl. Aniline (NIDI), o-hydroxybenzophenone and the like.

  In order to improve the storage stability of the polymerizable liquid crystal composition, an oxygen inhibitor (peroxide decomposer) may be added to the polymerizable liquid crystal composition. The radical generated in the composition reacts with oxygen in the atmosphere to give a peroxide via the peroxy radical, and an undesirable reaction with the polymerizable compound is promoted. In order to prevent this, it is preferable to add an oxygen inhibitor. Examples of oxygen inhibitors are phosphate esters.

  In the following description, the homeotropic alignment liquid crystal film of the present invention obtained from the polymerizable liquid crystal composition may be simply referred to as a liquid crystal film.

  When producing a liquid crystal film, the polymerizable liquid crystal composition may be used as it is, but after adding a solvent to the composition and applying or forming the solution as a solution, the solvent may be removed to produce a thin film. Solvents are useful for producing uniform thickness paint films. When the polymerizable liquid crystal composition is used as a solution, preferred solvents are benzene, toluene, heptane, xylene, mesitylene, n-butylbenzene, diethylbenzene, tetralin, methoxybenzene, 1,2-dimethoxybenzene, ethylene glycol dimethyl ether, diethylene glycol. Dimethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, ethyl acetate, alkyl lactate (such as ethyl lactate), ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, chloroform, dichloromethane, Carbon tetrachloride, dichloroethane, tetrachloroethylene, trichlorethylene, tetrachloroethane Len, chlorobenzene, THF, chloroform, 1,4-dioxane, bis (methoxyethyl) ether, γ-butyrolactone, tetramethylurea, trifluoroacetic acid, ethyl trifluoroacetate, hexafluoro-2-propanol, ethanol, 2-propanol , T-butyl alcohol, diacetone alcohol, glycerin, monoacetin, ethylene glycol, triethylene glycol, hexylene glycol, ethylene glycol monomethyl ether, ethyl cellosolve, butyl cellosolve, PGMEA, γ-butyrolactone, N-methyl-2- Pyrrolidone, dimethyl sulfoxide, N, N-dimethylacetamide, N, N-dimethylacetamide dimethyl acetal, dimethylformamide and the like. These can be used as a single solvent or a mixed solvent.

These solvents may be used under conditions that do not attack the supporting substrate used in the present invention. From the viewpoint of not corroding the norbornene-based resin as the support substrate, the content of the polar solvent is 30% by weight or more, preferably 40% by weight or more, based on the total weight of the solvent (total weight of the polar solvent and the low polarity solvent) More preferably, it is 50 weight% or more. Preferred polar solvents include ketones, acetates, ethers, cellosolves, esters and alcohols. Examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, and methyl propyl ketone.
Examples of the acetate include ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and methyl acetoacetate.
Examples of ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, 1,4-dioxane, and THF.
Examples of cellosolve include ethyl cellosolve and butyl cellosolve.
Examples of the esters include ethyl acetate, butyl acetate, alkyl lactate (methyl lactate, ethyl lactate, isopropyl lactate, n-propyl lactate, butyl lactate, ethyl hexyl lactate), ethyl trifluoroacetate and the like.
Examples of the alcohol include hexafluoro-2-propanol, ethanol, 2-propanol, t-butyl alcohol, diacetone alcohol and the like. Other solvents such as γ-butyrolactone and NMP may be used.

  Preferred examples of the low polarity solvent are benzene, toluene, heptane, xylene, mesitylene, n-butylbenzene, diethylbenzene, tetralin, methoxybenzene, 1,2-dimethoxybenzene, chloroform, dichloromethane, carbon tetrachloride, dichloroethane, tetrachloroethylene, trichloroethylene. Chlorobenzene, chloroform, bis (methoxyethyl) ether, tetramethylurea, trifluoroacetic acid, glycerin, monoacetin, ethylene glycol, triethylene glycol, hexylene glycol, ethylene glycol monomethyl ether, and the like. These may be used alone or as a mixed solvent.

  The supporting substrate is a norbornene resin. The norbornene-based resin includes a dicyclopentadiene-based resin, and preferably a hydrogenated unsaturated bond, for example, a hydrogenated product of a ring-opening polymer of a norbornene-based monomer, two or more types of norbornene. Hydrogenated copolymer of monomers, hydrogenated copolymer of norbornene monomers and olefin monomers (ethylene, α-olefin, etc.), norbornene monomers and cyclic olefin monomers (cyclopentene, cyclooctene, 5 , 6-dihydrodicyclopentadiene etc.) and hydrogenated products of these copolymers, modified products thereof, and the like. Specifically, trade names of ZEONEX, ZEONOR, JSR (JSR) Product name: ARTON, Hitachi Chemical Co., Ltd. Product name: OPTOREZ, Mitsui Chemicals The trade name: APEL, Sekisui Chemical Co., Ltd. under the trade name: such as Esushina are commercially available. When a solvent is used to apply the polymerizable liquid crystal composition, it is preferable to select a solvent-resistant norbornene-based resin as a supporting substrate, and ZEONOR can be preferably used from that viewpoint.

  These supporting substrates may be uniaxially stretched films or biaxially stretched films. These supporting base materials are preferably subjected to a surface treatment such as a hydrophilization treatment such as corona treatment or plasma treatment, or a hydrophobic treatment. These supporting base materials may be laminated films as well as single-layer films.

  Prior to the formation of the coating film of the polymerizable liquid crystal composition, a physical and mechanical surface treatment such as rubbing may be performed on the support substrate. When forming a homeotropically oriented polymerizable liquid crystal layer and a liquid crystal film, surface treatment such as rubbing is often not performed, but rubbing treatment may be performed in order to prevent alignment defects and the like. Any method can be used for the rubbing treatment, but usually a rubbing cloth made of materials such as rayon, cotton, polyamide, etc. is applied to a metal roll etc. and the roll is rotated while in contact with the support substrate or polymer film. For example, a method of moving the support base while moving the roll while fixing the roll is employed.

  When the polymerizable liquid crystal composition is applied as a solution on a support substrate, the method of uniformly applying is as follows: spin coating method, roll coating method, caten coating method, flow coating method, printing method, micro gravure coating method, gravure coating method , Wire bar coating, dip coating, spray coating, meniscus coating, and die coating.

  Examples of coating methods for obtaining a uniform liquid crystal film thickness include spin coating, roll coating, caten coating, flow coating, printing, micro gravure coating, gravure coating, wire bar coating, dip Examples thereof include a coating method, a spray coating method, a meniscus coating method, and a die coating method. In particular, a wire bar coating method in which a shearing stress is applied to the polymerizable liquid crystal composition at the time of application may be used when the alignment of the polymerizable liquid crystal composition is controlled without performing surface treatment of the supporting substrate by rubbing or the like. .

  When a solvent is used to apply the polymerizable liquid crystal composition on the support substrate, the solvent is dried and removed after application to form a coating film layer of the polymerizable liquid crystal composition having a uniform film thickness. The conditions for removing the solvent are not particularly limited. What is necessary is just to dry until a solvent is removed in general and the fluidity | liquidity of a coating-film layer 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, the coating film that has undergone the drying process can be subjected to the polymerization process without going through a heat treatment process to be described later. However, in order to make the alignment of the liquid crystal molecules in the coating film more uniform, it is preferable to heat-treat the coating film that has undergone the drying step and then to perform photopolymerization.

  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 performed at or above the liquid crystal phase transition point of the polymerizable liquid crystal composition. An example of the heat treatment method is a method in which the coating film is heated to a temperature at which the polymerizable liquid crystal composition exhibits a nematic liquid crystal phase to form a nematic alignment in the polymerizable liquid crystal composition in the coating film. The nematic alignment may be formed by changing the temperature of the coating film within a temperature range in which the polymerizable liquid crystal composition exhibits a nematic liquid crystal phase. This method is a method in which a nematic orientation is substantially completed in the coating film by heating the coating film to a high temperature region in the above temperature range, and then the order is further ordered by lowering the temperature. Whichever heat treatment method described above is employed, the preferred heat treatment temperature is room temperature to 120 ° C. A more preferable range of this temperature is room temperature to 80 ° C, and a further preferable range is room temperature to 70 ° C. A preferable heat treatment time is 5 seconds to 2 hours. A more 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 layer made of the polymerizable liquid crystal composition to a predetermined temperature, the heat treatment time is preferably 5 seconds or more. In order not to lower the productivity, it is preferable to set the heat treatment time within 2 hours.

The nematic alignment state of the polymerizable liquid crystal composition formed in the coating film is fixed by polymerizing the polymerizable liquid crystal compound in the coating film by light irradiation. The wavelength of light used for light irradiation is not particularly limited. Electron beams, ultraviolet rays, visible rays, infrared rays (heat rays), etc. can be used. Usually, ultraviolet rays or visible rays may be used. A preferable range of the wavelength is 150 to 500 nm. A more preferable range is 250 to 450 nm, and a further preferable range is 300 to 400 nm. Examples of light sources are low-pressure mercury lamps (sterilization lamps, fluorescent chemical lamps, black lights), high-pressure discharge lamps (high-pressure mercury lamps, metal halide lamps), short arc discharge lamps (super-high pressure mercury lamps, xenon lamps, mercury xenon lamps), etc. It is. Preferred examples of the light source are a metal halide lamp, a xenon 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 coating layer of the polymerizable liquid crystal composition and passing only a specific wavelength region. A preferable range of the amount of light emitted from the light source is ² to 5000 mJ / cm ² . A more preferred range is 10~3000mJ / cm ^2, furthermore preferably 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.

  When an alignment layer made of a polymerizable liquid crystal composition and a liquid crystal film obtained by polymerizing the alignment layer with light or heat are used in various optical elements, or when applied as an optical compensation element used in a liquid crystal display device, Control of the tilt angle distribution in the thickness direction is extremely important.

  One method of controlling the tilt angle is a method of adjusting the type and composition ratio of the liquid crystal compound used in the polymerizable liquid crystal composition. The tilt angle can also be controlled by adding other components to the polymerizable liquid crystal composition. The tilt angle of the liquid crystal film is also controlled by the type of solvent added to the polymerizable liquid crystal composition, the solute concentration in the solution of the polymerizable liquid crystal composition, and the type and amount of surfactant added as one of the other components. can do. The tilt angle of the liquid crystal film can also be controlled by the type of support substrate, rubbing conditions, coating film drying conditions, heat treatment conditions, and the like. Furthermore, the irradiation atmosphere in the photopolymerization step after alignment, the temperature at the time of irradiation, etc. also affect the tilt angle of the liquid crystal film. That is, it can be considered that almost all conditions in the manufacturing process of the liquid crystal film affect the tilt angle to some extent. Therefore, by optimizing the polymerizable liquid crystal composition and appropriately selecting various conditions for the production process of the liquid crystal film, an arbitrary tilt angle can be obtained.

  In the homeotropic alignment, the tilt angle is uniformly distributed from 85 ° to 90 ° from the support substrate interface to the free interface. This alignment state is obtained by coating a polymerizable liquid crystal composition containing the compound (1) on a norbornene-based resin substrate. In order to form a uniform homeotropic alignment, the surface of the norbornene-based resin substrate is subjected to a hydrophilic treatment by corona treatment or plasma treatment. The degree of hydrophilization treatment can be evaluated by measuring the contact angle with water. In order to form a uniform homeotropic orientation, the contact angle with water is 80 ° or less, preferably 1 ° to 65 °, more preferably Is from 5 ° to 50 °. The compound (1) is more preferably 5 to 99% by weight of the total amount of the polymerizable liquid crystal composition, but in order to maintain the mechanical properties such as heat resistance of the liquid crystal film, it is about 10 to 45% by weight. It is particularly preferable that

  In the hydrophilization treatment when the polymerizable liquid crystal composition is applied onto the norbornene-based resin base material, the higher the hydrophilization treatment, the more uniform and stable homeotropic alignment can be obtained. The method for hydrophilization treatment is not particularly limited, but corona treatment or plasma treatment is preferred. A particularly preferred method is plasma treatment. For the plasma treatment, a method described in JP 2002-226616 A, JP 2002-121648 A, or the like may be used. Such homeotropic alignment can be obtained even if the surface of the polymer film formed on the support substrate is not mechanically or physically treated by rubbing or the like. If alignment defects or the like occur when the coating is performed without performing the rubbing treatment, uniform homeotropic alignment can be obtained by performing the rubbing treatment or the like.

  The thickness of the liquid crystal film varies depending on the retardation corresponding to the target element and the birefringence of the liquid crystal film. Therefore, although the range cannot be determined strictly, the preferable thickness of the liquid crystal film is 0.05 to 50 μm. And a more preferable range is 0.1-20 micrometers, and a still more preferable range is 0.5-10 micrometers. The preferred haze value of the liquid crystal film 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 liquid crystal film is also useful as an optical compensation element integrated with a polarizing plate or the like. Examples of liquid crystal display element types suitable for using this liquid crystal film as an optical compensation film are TN type (twisted nematic), STN type (super twisted nematic), and ECB type (electrically controlled). Birefringence), OCB type (optically compensated birefringence), DAP type (alignment phase deformation effect), CSH type (color super homeotropic), VAN / VAC type (vertically oriented nematic / cholesteric) ), OMI type (optical mode interference), SBE type (super birefringence effect), and the like. Further, there are phase letterers such as guest-host type, IPS type (in-plane switching), ferroelectric type, and antiferroelectric type. Note that the optimum values of parameters such as the thickness distribution and thickness of the tilt angle required for the liquid crystal film 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 polymer film may be used for each of blue, green, and red pixels in the liquid crystal display element. For example, see Japanese Patent Application Laid-Open No. 2001-222009. When a liquid crystalline compound is dispersed in a polymer film, there are uses such as a polymer dispersion type liquid crystal display element and a holographic polymer-dispersed type liquid crystal display element. For example, see JP-A-6-340587. A polymer film obtained from a composition containing an optically active compound has a twist alignment in which liquid crystal molecules are regularly twisted so as to draw a spiral. When the length of the helical pitch is about several μm, it has a function as an azimuth rotator.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these Examples.

Below, the evaluation method performed in the Example is shown.
(1) Polymerization conditions of the polymerizable liquid crystal composition: In the atmosphere, at room temperature, a 250 W ultrahigh pressure mercury lamp was used to irradiate light having an intensity of 30 mW / cm ² (365 nm) for 30 seconds.
(2) Support base material and surface treatment: Norbornene resin (ZEONOR film / ZEONOR1600R manufactured by Nippon Zeon Co., Ltd., JP 2004-4641 A) was used. For the hydrophilization treatment (plasma treatment) of the support substrate, an atmospheric pressure plasma surface treatment apparatus (AP-T02-L) was used. Plasma discharge conditions were set according to Japanese Patent Application Laid-Open No. 2002-226616.
(3) Confirmation of contact angle: Using a contact angle meter CA-A (manufactured by Kyowa Interface Chemical Co., Ltd.), the contact angle of pure water dropped on a norbornene resin substrate was measured at 25 ° C.
(4) Uniformity of homeotropic alignment: When two polarizing plates are placed in a crossed nicols state, a liquid crystal film is inserted between them, and when observed from the front, the light spot derived from alignment defects of the liquid crystal is not visually confirmed. (Dark field) was in a uniformly oriented state.
(5) Retardation angle dependency of retardation: Retardation (retardation; phase delay) was measured using an OPTIPRO ellipsometer manufactured by Shintech Co., Ltd. The polymer film was irradiated with light having a wavelength of 550 nm, and the retardation was measured while tilting the incident angle of this light from the direction perpendicular to the film surface. The retardation is expressed by Δn × d. The symbol Δn is the optical anisotropy, and the symbol d is the thickness of the polymer film.

化合物（２−１−１）は式（２−１−１）で表される化合物であり、Macromolecules 1993,26,1244-1247記載の方法で合成した。化合物（２−２−１）は式（２−２−１）で表され、ｇ＝６であり、Ｒ^２＝Ｅｔである化合物であり、特開２００５−６０３７３号公報に記載の方法で合成した。化合物（１−２−５）は式（１−２−５）で表され、ｃ＝６であり、Ｒ^１＝Ｅｔである化合物であり、特表２００３−５１３１０７（あるいはJ.Polymer Science:PartA:Polymer Chemistry,Vol.35, 2843-2855(1997)）に記載されている方法に準じて合成した。すなわち特表２００３−５１３１０７に開示されているのは光学活性アルコキシを有する化合物であるが、光学活性アルコキシを有する中間原料をシアノビフェニルを有する中間原料に置き換えた。
上記の組成物にトルエンとシクロヘキサノンの混合溶媒（混合比（重量比）はトルエン／シクロヘキサノン＝１／１）を加えて、２５重量％溶液とした。このようにして得られた組成物を重合性液晶組成物−１［ＭＩＸ１］とする。
なお、ＤＴＳ−１０２は、みどり化学（株）の光カチオン重合開始剤の製品を表す。 Example 1
<Preparation of polymerizable liquid crystal composition-1 [MIX-1]>

The compound (2-1-1) is a compound represented by the formula (2-1-1), and was synthesized by the method described in Macromolecules 1993, 26, 1244-1247. The compound (2-2-1) is a compound represented by the formula (2-2-1), g = 6, and R ² = Et, and synthesized by the method described in JP-A-2005-60373. did. The compound (1-2-5) is a compound represented by the formula (1-2-5), c = 6, and R ¹ = Et, and Japanese Translation of PCT International Publication No. 2003-513107 (or J. Polymer Science: Part A : Polymer Chemistry, Vol. 35, 2843-2855 (1997)). That is, what is disclosed in JP-T-2003-513107 is a compound having optically active alkoxy, but the intermediate material having optically active alkoxy was replaced with an intermediate material having cyanobiphenyl.
A mixed solvent of toluene and cyclohexanone (mixing ratio (weight ratio): toluene / cyclohexanone = 1/1) was added to the above composition to obtain a 25 wt% solution. The composition thus obtained is designated as polymerizable liquid crystal composition-1 [MIX1].
DTS-102 represents a product of a photocationic polymerization initiator of Midori Chemical Co., Ltd.

化合物（１−２−１）は式（１−２−１）で表され、ｃ＝６であり、Ｒ^１＝Ｅｔである化合物であり、Polymer Bulletin 25、ｐｐ439-442（1991）に記載されている方法に準じて合成した。
上記の組成物にトルエンとシクロヘキサノンの混合溶媒（混合比（重量比）はトルエン／シクロヘキサノン＝１／１）を加えて、２５重量％溶液とした。このようにして得られた組成物を重合性液晶組成物−２［ＭＩＸ−２］とする。 Example 2
<Preparation of polymerizable liquid crystal composition-2 [MIX-2]>

The compound (1-2-1) is a compound represented by the formula (1-2-1), c = 6, and R ¹ = Et, and is described in Polymer Bulletin 25, pp 439-442 (1991). It was synthesized according to the method.
A mixed solvent of toluene and cyclohexanone (mixing ratio (weight ratio): toluene / cyclohexanone = 1/1) was added to the above composition to obtain a 25 wt% solution. The composition thus obtained is designated as polymerizable liquid crystal composition-2 [MIX-2].

化合物（１−１−１）は式（１−１−１）で表され、ａ＝４である化合物であり、Macromol.Chem.Phys.196 2941-2945(1995) に記載されている方法に準じて合成した。
上記の組成物にトルエンとシクロヘキサノンの混合溶媒（混合比（重量比）はトルエン／シクロヘキサノン＝２／１）を加えて、２５重量％溶液とした。このようにして得られた組成物を重合性液晶組成物−３［ＭＩＸ−３］とする。 Example 3
<Preparation of polymerizable liquid crystal composition-3 [MIX-3]>

Compound (1-1-1) is a compound represented by the formula (1-1-1) and having a = 4, and the method described in Macromol. Chem. Phys. 196 2941-2945 (1995). Synthesized accordingly.
A mixed solvent of toluene and cyclohexanone (mixing ratio (weight ratio): toluene / cyclohexanone = 2/1) was added to the above composition to obtain a 25 wt% solution. The composition thus obtained is designated as polymerizable liquid crystal composition-3 [MIX-3].

化合物（１−２−１９）は式（１−２−１９）で表され、ｃ＝６であり、Ｒ^１＝Ｅｔである化合物であり、特開２００５−３２０３１７号公報に記載されている方法に準じて合成した。
上記の組成物にトルエンとシクロヘキサノンの混合溶媒（混合比（重量比）はトルエン／シクロヘキサノン＝１／１）を加えて、２５重量％溶液とした。このようにして得られた組成物を重合性液晶組成物−４［ＭＩＸ−４］とする。 Example 4
<Preparation of polymerizable liquid crystal composition-4 [MIX-4]>

The compound (1-2-19) is a compound represented by the formula (1-2-19), c = 6, R ¹ = Et, and the method described in JP-A-2005-320317 Synthesized according to
A mixed solvent of toluene and cyclohexanone (mixing ratio (weight ratio): toluene / cyclohexanone = 1/1) was added to the above composition to obtain a 25 wt% solution. The composition thus obtained is designated as polymerizable liquid crystal composition-4 [MIX-4].

化合物（１−１−１８）は式（１−１−１８）で表され、ａ＝４である化合物であり、特願２００４−２０１５６２に記載されている方法に準じて合成した。
上記の組成物にトルエンとシクロヘキサノンの混合溶媒（混合比（重量比）はトルエン／シクロヘキサノン＝１／１）を加えて、２５重量％溶液とした。このようにして得られた組成物を重合性液晶組成物−５［ＭＩＸ−５］とする。 Example 5
<Preparation of polymerizable liquid crystal composition-5 [MIX-5]>

The compound (1-1-18) is a compound represented by the formula (1-1-18) and a = 4, and was synthesized according to the method described in Japanese Patent Application No. 2004-201562.
A mixed solvent of toluene and cyclohexanone (mixing ratio (weight ratio): toluene / cyclohexanone = 1/1) was added to the above composition to obtain a 25 wt% solution. The composition thus obtained is designated as polymerizable liquid crystal composition-5 [MIX-5].

Example 6
On a norbornene-based resin base material (contact angle with water is 30 °) obtained by hydrophilizing the polymerizable liquid crystal composition-1 obtained in Example 1 by plasma treatment using a wire bar (wet thickness: 12 μm). It was applied to. Next, the solvent was removed by heating on a hot plate at 70 ° C. for 3 minutes, and then UV irradiation was performed in the air to obtain an optical film (homeotropic alignment liquid crystal film) having a uniform homeotropic alignment. . When the two polarizing plates were placed in a crossed Nicol state and the obtained optical film was sandwiched, it was a dark field, and the inclination angle dependency of the retardation of this optical film was measured. The result was as shown in FIG. .

Example 7
Except that the polymerizable liquid crystal composition-1 was changed to the polymerizable liquid crystal composition-2, it was carried out in the same manner as in Example 6 to obtain an optical film having a uniform homeotropic alignment. The inclination angle dependency of the retardation of the optical film had the same tendency as in Example 6.

Example 8
Except that the polymerizable liquid crystal composition-1 was changed to the polymerizable liquid crystal composition-3, the same procedure as in Example 6 was performed to obtain an optical film having uniform homeotropic alignment. The inclination angle dependency of the retardation of the optical film had the same tendency as in Example 6.

Example 9
Except that the polymerizable liquid crystal composition-1 was changed to the polymerizable liquid crystal composition-4, the same procedure as in Example 6 was performed to obtain an optical film having uniform homeotropic alignment. The inclination angle dependency of the retardation of the optical film had the same tendency as in Example 6.

Example 10
Except that the polymerizable liquid crystal composition-1 was changed to the polymerizable liquid crystal composition-5, the same procedure as in Example 6 was performed to obtain an optical film having uniform homeotropic alignment. The inclination angle dependency of the retardation of the optical film had the same tendency as in Example 6.

Example 11
An optical film having uniform homeotropic alignment was obtained in the same manner as in Example 1 except that the mixing ratio (weight ratio) of the mixed solvent of the polymerizable liquid crystal composition-4 was changed to toluene / cyclohexanone = 2/1. Obtained. The inclination angle dependency of the retardation of the optical film had the same tendency as in Example 6.

Example 12
The same procedure as in Example 6 was performed except that the polymerizable liquid crystal composition-1 was a polymerizable liquid crystal composition-4 and the mixing ratio (weight ratio) of the mixed solvent of the polymerizable liquid crystal composition-4 was only cyclohexanone. However, an optical film having a uniform homeotropic orientation was obtained. The inclination angle dependency of the retardation of the optical film had the same tendency as in Example 6.

Comparative Example 1
A liquid crystal film was produced in the same manner as in Example 6 or Example 9 except that the compound (1-2-5) or the compound (1-2-19) was not included. It was cloudy and had a problem with the appearance.

Comparative Example 2
A liquid crystal film was obtained in the same manner as in Example 7, Example 8 or Example 10 except that it did not contain compound (1-2-1), compound (1-1-1) or compound (1-1-18). As a result, the liquid crystal was not aligned and the film was also clouded, which had a problem in appearance.

Comparative Example 3
A liquid crystal film was produced in the same manner as in Example 11 except that it did not contain the compound (1-2-5). As a result, the liquid crystal was not aligned and the film was also clouded, causing a problem in appearance.

Comparative Example 4
A liquid crystal film was prepared in the same manner as in Example 9 except that the mixing ratio (weight ratio) of the mixed solvent of the polymerizable liquid crystal composition-4 was only toluene, and the liquid crystal was aligned, but the norbornene resin The deformation (curl) of the substrate was confirmed, and it was confirmed that the support substrate was eroded by the solvent.

Comparative Example 5
The coating was carried out in the same manner as in Example 6 except that the hydrophilization treatment of the norbornene-based resin base material was not performed (contact angle with water was 97 °), but remarkable repellency was confirmed and was not worthy of evaluation. .

  According to the above results, by using a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound having a non-polymerizable polar group at the molecular terminal and a polar solvent as a solvent, the norbornene-based resin as a supporting substrate is eroded. It can be seen that a uniform homeotropic alignment liquid crystal film can be obtained.

  According to the present invention, a uniform homeotropic alignment liquid crystal film can be obtained without forming an alignment control film or the like on a norbornene resin substrate by using a hydrophilized norbornene resin substrate and a polar solvent. .

About the optical film obtained in Example 6, the result of having measured the retardation, making it incline from a perpendicular direction with respect to a film surface is shown. The inclination angle is an angle when the polymer film is irradiated with light. When the light is perpendicular to the film, the tilt angle is 0 °.

Claims (20)

On a norbornene-based resin substrate on which a polymerizable liquid crystal composition containing at least one compound selected from the group of compounds represented by the following formula (1-1) and formula (1-2) has been subjected to a hydrophilic treatment Homeotropic alignment liquid crystal film obtained by directly coating and polymerizing.

[In Formula (1-1) and Formula (1-2), Z ¹ and Z ³ are each independently —CH ₂ — or —O—;
Z ² and Z ⁴ are each independently a single bond, —COO—, —OCO—, —CH═CH—COO— or —OCO—CH═CH—;
A ¹ and A ³ are independently of each other 1,4-phenylene, 9-methylfluorene-2,7-diyl, or fluorene-2,7-diyl;
a and c are each independently an integer of 4 to 8; b and d are each independently an integer of 1 to 2;
R ¹ is methyl or ethyl;
A ² and A ⁴ are each independently any one of groups represented by the formula (a-1) or the formula (a-2).
In formula (a-2), X is —CN or —OCF ₃ ; Y is independently hydrogen or fluorine.
(However, in Formula (1-1), A ¹ is 1,4-phenylene, Z ² is —COO—, A ² is Formula (a-2), and X in Formula (a-2) is —OCF ₃ , When Y is hydrogen or fluorine, Z ¹ is —CH ₂ —.)] The polymerizable liquid crystal composition contains at least one compound selected from the group of compounds represented by formula (1-1) and formula (1-2) as the first component, and the following formula (2) as the second component: The homeotropic alignment liquid crystal film according to claim 1, comprising at least one compound selected from the group of compounds represented by -1) and formula (2-2).

[Wherein R ² is methyl or ethyl;
Z ⁵ and Z ⁸ are independently of each other —CH ₂ — or —O— (provided —CH ₂ — when e and g are 0);
Z ⁶ and Z ⁹ are independently of each other —COO—, —OCO— or —CH ₂ CH ₂ —COO—;
Z ⁷ and Z ¹⁰ are independently of each other —OCO—, —COO— or —OCO—CH ₂ CH ₂ —;
A ⁵ and A ⁸ are independently of each other 1,4-phenylene or 3-fluoro-1,4-phenylene;
A ⁷ and A ¹⁰ are independently of each other 1,4-phenylene or 2-fluoro-1,4-phenylene;
A ⁶ and A ⁹ are independently of each other 1,4-phenylene, 3-methyl-1,4-phenylene, 3-trifluoromethyl-1,4-phenylene, 2,3-bis (trifluoromethyl) -1. , 4-phenylene, 9-methylfluorene-2,7-diyl, 9-ethylfluorene-2,7-diyl, or 9,9-dimethylfluorene-2,7-diyl;
f and h are independently 0 or 1;
e and g are each independently an integer of 0 to 10; ] In the formula (1-1) and formula (1-2) of the first component in the polymerizable liquid crystal composition,
Z ¹ and Z ³ are independently of each other —CH ₂ — or —O—;
Z ² and Z ⁴ are each independently a single bond, —COO—, —OCO—, —CH═CH—COO— or —OCO—CH═CH—;
A ¹ and A ³ are independently of each other 1,4-phenylene or 9-methylfluorene-2,7-diyl;
a and c are independently an integer of 4 to 6;
b and d are each independently an integer of 1 to 2;
R ¹ is methyl or ethyl;
A ² and A ⁴ are each independently any one of the groups represented by the formula (a-1) or the formula (a-2);

In formula (a-2), X is —CN or —OCF ₃ ; Y is independently hydrogen or fluorine,
(However, A1 is 1,4-phenylene in the formula (1-1), ^{Z 2} is -COO-, ^{A 2} is formula (a-2), X in the formula (a-2) is -OCF _3, When Y is hydrogen or fluorine, Z ¹ is —CH ₂ —.)]
In the formula (2-1) of the second component,
Z ⁵ is —CH ₂ — or —O— (when e is 0, it is —CH ₂ —);
Z ⁶ is —COO— or —OCO—;
Z ⁷ is —OCO— or —COO—;
A ⁵ is 1,4-phenylene or 3-fluoro-1,4-phenylene;
A ⁶ is 1,4-phenylene, 3-methyl-1,4-phenylene, 9-methylfluorene-2,7-diyl or 9,9-dimethylfluorene-2,7-diyl;
A ⁷ is 1,4-phenylene or 2-fluoro-1,4-phenylene;
f is 0 or 1;
e is an integer from 0 to 10;
In the formula (2-2) of the second component,
R ² is methyl or ethyl;
Z ⁸ is —CH ₂ — or —O— (when g is 0, it is —CH ₂ —);
Z ⁹ is —COO—, —OCO— or —CH ₂ CH ₂ —COO—;
Z ¹⁰ is —OCO—, —COO— or —OCO—CH ₂ CH ₂ —;
A ⁸ is 1,4-phenylene or 3-fluoro-1,4-phenylene;
A ⁹ is 3-methyl-1,4-phenylene, 3-trifluoromethyl-1,4-phenylene, 2,3-bis (trifluoromethyl) -1,4-phenylene, 9-methylfluorene-2,7 -Diyl, 9-ethylfluorene-2,7-diyl or 9,9-dimethylfluorene-2,7-diyl;
A ¹⁰ is 1,4-phenylene or 2-fluoro-1,4-phenylene;
h is 0 or 1;
3. The homeotropic alignment liquid crystal film according to claim 2, wherein g is an integer of 1 to 10.   4. The polymerizable liquid crystal composition according to claim 1, wherein the content of the compound represented by formula (1-1) and formula (1-2) is 5 to 5 based on the total amount of the polymerizable liquid crystal composition. The homeotropic alignment liquid-crystal film of any one of Claims 1-3 which is 99 weight%. It contains at least one compound selected from the group of compounds represented by the following formula (1-1) and formula (1-2) as the first component, and the following formula (2-1) and formula ( It is obtained by directly applying a polymerizable liquid crystal composition containing at least one compound selected from the group of compounds represented by 2-2) onto a norbornene-based resin base material that has been subjected to a hydrophilization treatment and polymerizing the composition. Homeotropic alignment liquid crystal film.

[In Formula (1-1) and Formula (1-2), Z ¹ and Z ³ are each independently —CH ₂ — or —O—;
Z ² and Z ⁴ are each independently a single bond, —COO— or —OCO—;
A ¹ and A ³ are independently of each other 1,4-phenylene or 9-methylfluorene-2,7-diyl;
a and c are independently an integer of 4 to 6;
b and d are each independently an integer of 1 to 2;
R ¹ is methyl or ethyl;
A ² and A ⁴ are each one of the groups represented by the following formulas independently of each other;
In formula (a-2), X is —CN or —OCF ₃ ; Y is independently hydrogen or fluorine,
(However, in Formula (1-1), A ¹ is 1,4-phenylene, Z ² is —COO—, A ² is Formula (a-2), and X in Formula (a-2) is —OCF ₃ , Y is hydrogen or fluorine, Z ¹ is —CH ₂ —.)
In Formula (2-1) and Formula (2-2), R ² is independently of each other methyl or ethyl;
Z ⁵ and Z ⁸ are independently of each other —CH ₂ — or —O— (provided —CH ₂ — when e and g are 0);
Z ⁶ and Z ⁹ are independently of each other —COO— or —OCO—;
Z ⁷ and Z ¹⁰ are each independently —OCO— or —COO—,
A ⁵ is 1,4-phenylene or 3-fluoro-1,4-phenylene;
A ⁶ is 1,4-phenylene, 3-methyl-1,4-phenylene, 9-methylfluorene-2,7-diyl or 9,9-dimethylfluorene-2,7-diyl;
A ⁸ is 1,4-phenylene or 3-fluoro-1,4-phenylene;
A ⁹ is 3-methyl-1,4-phenylene, 3-trifluoromethyl-1,4-phenylene, 2,3-bis (trifluoromethyl) -1,4-phenylene, 9-methylfluorene-2,7 -Diyl, 9-ethylfluorene-2,7-diyl or 9,9-dimethylfluorene-2,7-diyl;
A ⁷ and A ¹⁰ are independently of each other 1,4-phenylene or 2-fluoro-1,4-phenylene;
f is 0 or 1;
h is 1;
e is an integer of 0 to 6, and g is an integer of 0 to 6. ] The polymerizable liquid crystal composition is represented by the following formula (1-1-A) to formula (1-1-D) and formula (1-2-A) to formula (1-2-E) as the first component. And at least one compound selected from the group of compounds having formula (2-1-A) to formula (2-1-C) and formula (2-2A) to formula (2- The homeotropic alignment liquid crystal film according to claim 5, comprising at least one compound selected from the group of compounds represented by 2-B).

[In formula (1-1-A) to formula (1-1-D) and formula (1-2-A) to formula (1-2-E), R ¹ is methyl or ethyl; Z ¹ and Z ³ is independently of each other —O— or —CH ₂ —; a and c are each independently an integer of 4 to 6; X is —CN or —OCF ₃ ; Y is hydrogen or fluorine In the formula (2-1-A) to the formula (2-1-C) and the formula (2-2A) to the formula (2-2B), R ² is independently of each other methyl or ethyl. Z ⁵ and Z ⁸ are independently of each other —O— or —CH ₂ — (provided that when e and g are 0, they are —CH ₂ —); and e and g are independently of each other. It is an integer of Less than six; ^{L 1} and ^{L 2} represents a hydrogen or fluorine independently of one another, ^{L 3} represents hydrogen or methyl, ^{L 4} Oyo L ⁵ represents independently of one another are hydrogen, methyl, represents a trifluoromethyl, never L ⁴ and which L ⁵ are both hydrogen, W ¹ and W ² represents a hydrogen or methyl independently of one another. ] The polymerizable liquid crystal composition has at least one compound selected from the group of compounds represented by the following formula (1-1-1) and formula (1-1-15) as the first component, and the following as the second component: The homeotropic alignment liquid crystal film according to claim 5, comprising at least one compound selected from the group of compounds represented by formula (2-1-1) and formula (2-2-1). .

[Wherein R ² is methyl or ethyl; a is independently an integer of 4 to 6, and g is an integer of 2 to 6]
The polymerizable liquid crystal composition is at least one selected from the group of compounds represented by the following formula (1-2-1), formula (1-2-5), and formula (1-2-19) as the first component. And at least one compound selected from the group of compounds represented by the following formulas (2-1-1) and (2-2-1) as a second component: 5. A homeotropic alignment liquid crystal film according to 5.

[Wherein R ¹ and R ² are each independently methyl or ethyl; c is each independently an integer of 4-6, and g is an integer of 2-6] The polymerizable liquid crystal composition has at least one compound selected from the group of compounds represented by the following formula (1-1-1) and formula (1-1-15) as the first component, and the following as the second component: The homeotropic alignment liquid crystal film according to claim 5, comprising at least one compound represented by the formula (2-2-1).

[Wherein R ² is methyl or ethyl; a is independently an integer of 4 to 6, and g is an integer of 2 to 6] One polymerizable liquid crystal composition selected from the group of compounds represented by the following formula (1-2-1), formula (1-2-5), and formula (1-2-19) as the first component And a compound containing at least one compound represented by the following formula (2-1-1) and at least one compound represented by the following formula (2-2-1) as a second component The homeotropic alignment liquid crystal film according to claim 5.

[Wherein R ¹ and R ² are each independently methyl or ethyl; c is each independently an integer of 4-6, and g is an integer of 2-6]   6. The polymerizable liquid crystal composition according to claim 5, wherein the content of the compound represented by the formula (1-1) to the formula (1-2) as the first component is based on the total amount of the polymerizable liquid crystal composition. The homeotropic alignment liquid crystal film according to claim 5, which is 5 to 99% by weight.   6. The polymerizable liquid crystal composition according to claim 5, wherein the content of the compound represented by formula (1-1) to formula (1-2) is 5 to 45 wt.% Based on the total amount of the polymerizable liquid crystal composition. The homeotropic alignment liquid crystal film according to claim 1, wherein the homeotropic alignment liquid crystal film is%.   The homeotropic alignment liquid crystal film according to any one of claims 1 to 12, wherein the hydrophilization treatment of the norbornene-based resin substrate is a corona treatment or a plasma treatment.   14. The polymerizable liquid crystal composition obtained by dissolving in a solvent containing a polar solvent, applying the polymerized liquid on a norbornene-based resin substrate subjected to a hydrophilic treatment, and polymerizing the composition. Homeotropic alignment liquid crystal film as described in 1.   15. The homeotropic alignment liquid crystal film according to claim 14, wherein the solvent contains a polar solvent in an amount of 30% by weight or more based on the total weight of the solvent.   The homeotropic alignment liquid crystal film according to claim 14 or 15, wherein the polar solvent is any one of ketone, acetate, ether, cellosolve, ester, and alcohol.   A polymerizable liquid crystal composition containing a compound represented by the formula (1-1) to the formula (1-2) is coated on a norbornene-based resin substrate subjected to a hydrophilic treatment and polymerized. A method for producing a homeotropic alignment liquid crystal film.   The method for producing a homeotropic alignment liquid crystal film according to claim 17, wherein the polymerizable liquid crystal composition is the polymerizable liquid crystal composition according to any one of claims 1 to 12.   The optical film which has a homeotropic alignment liquid crystal film of any one of Claims 1-16, or the homeotropic alignment liquid crystal film manufactured by the method of Claim 17 or 18. A liquid crystal display device comprising at least one optical film according to claim 19.

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