JP4984842B2 - Homeotropic alignment liquid crystal film and method for producing the same - Google Patents

Description

  The present invention relates to a homeotropic alignment liquid crystal film, a method for producing the same, and uses of the liquid crystal film.

  In recent years, it has been proposed to apply a polarizing plate, a retardation plate, or the like using a photopolymerizable liquid crystal to an optical element. Such an optical element is 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 optical anisotropy can be obtained. Hereinafter, the above-described alignment state may be simply referred to as “having homogeneous alignment”, “having tilt alignment”, “having homeotropic alignment”, or “having twist alignment”.

Here, the polymer having homeotropic alignment has the optical axis direction in the _nz direction, and the refractive index in the optical axis direction is larger than the refractive index in the orthogonal direction. Classified into plates. This positive C-plate is combined with a film having other optical functions for optical compensation in a horizontally aligned liquid crystal mode, so-called IPS (In-Plane Switching) mode, for example, for improving the viewing angle characteristics of a polarizing plate. Application is possible (for example, see Non-Patent Documents 1 and 2 and Patent Document 1).

  As a method for forming such homeotropic alignment, for example, a method of applying a surfactant having a long chain alkyl group, a coupling agent or a metal complex to a supporting substrate such as glass, Methods using molecules have been proposed (see, for example, Non-Patent Document 3 and Patent Documents 2 to 5).

  However, in the conventional method, the uniformity and stability of homeotropic alignment is insufficient, the number of steps until film formation is increased, repelling, pinholes, etc. when coating polymerizable liquid crystal There were problems such as poor coating. In addition, a polyimide-based polymer film for vertical alignment used in a liquid crystal display element is coated on a supporting substrate such as glass and fired at a temperature of about 200 ° C. (imidation proceeds) to obtain it. There was a problem that the polymerizable liquid crystal composition could not be applied to the surface. In addition, when an optical plastic film such as TAC (triacetyl cellulose) or norbornene resin is selected as the supporting substrate, there is a problem that it cannot be used from the viewpoint of heat resistance under the baking temperature conditions.

  The present inventors have so far cured a polymerizable liquid crystal layer comprising a polymerizable liquid crystal composition containing an acrylate-based polymerizable liquid crystal compound and an organosilicon compound having a primary amine by irradiation with ultraviolet rays in an inert atmosphere. It has been found that a polymerizable liquid crystal film having homeotropic alignment can be obtained (see Patent Document 6). However, since it is necessary to form an inert atmosphere at the time of curing, there are problems that the manufacturing process is complicated and the cost is high.

In order to solve this problem, the present inventors have found a polymerizable liquid crystal composition containing a liquid crystal compound having a polymerizable epoxy (cyclic ether) group (see Patent Documents 7 to 9). However, there are cases where polymerizable liquid crystal compounds having the same polymerizable group cannot obtain sufficient curability, and the structure of the compound is special and expensive.
MSPark et al, IDW '04 FMC8-4 M.Nakata et al, SID '06 P-58 Quarterly Chemical Review No. 22 “Liquid Crystal Chemistry”, The Chemical Society of Japan, pp. 99-100 (1994) WO05 / 38517A1 brochure Japanese Patent Laid-Open No. 10-319408 JP-A-11-240890 JP 2002-365635 A JP 2003-2927 A JP 2006-126757 A JP 2006-23656 A JP 2006-23657 A Japanese Patent Application No. 2006-105888

  SUMMARY OF THE INVENTION The present invention is intended to solve the above-described problems, and exhibits a uniform homeotropic alignment and has sufficient curability without forming an inert atmosphere during curing of the polymerizable liquid crystal composition. It aims at providing the method of manufacturing this liquid crystal film.

  Another object of the present invention is to provide an optical compensation element and an optical element using the liquid crystal film having the homeotropic alignment, a liquid crystal display device having the optical compensation element or the optical element, and the like.

The present inventors diligently studied to solve the above problems, and completed the present invention having the following configuration.
[1] A polymerizable liquid crystal composition containing at least one compound selected from the group of polymerizable liquid crystal compounds represented by the following formulas (1-1) to (1-3), a support group having a polar surface A homeotropic alignment liquid crystal film obtained by coating and polymerizing on a material.

Wherein R ¹ is methyl or ethyl; Z ¹ is a single bond, —COO—, —OCO—, —CH═CH—COO— or —CH ₂ CH ₂ —COO—; Z ² is —COO -Or -O
Y is independently hydrogen or fluorine; X is —OCF ₃ or —CN; w is 0, 1 or 2; a is an integer from 1 to 10.

  [2] The polymerizable liquid crystal composition includes at least one compound selected from the group of polymerizable liquid crystal compounds represented by the formulas (1-1) to (1-3), and the following formula (2-1): And at least one compound selected from the group of polymerizable liquid crystal compounds represented by (2-2). The liquid crystal film of item [1].

Wherein R ² is independently methyl or ethyl; Z ³ is a single bond or —O—; Z ^{4 to} Z ⁷ are independently —COO—, —OCO—, —CH ₂ CH ₂ COO. —, —OCOCH ₂ CH ₂ —, —CH═CHCOO—, —OCOCH═CH—, —CH ₂ CH ₂ —, —C≡C—, —CH ₂ O— or —OCH ₂ —; L ¹ to L ⁴ is independently hydrogen, fluorine, chlorine, methyl, trifluoromethyl, or cyano; m is an integer from 0 to 10, and when m is 0, Z ³
Is a single bond; n is 0 or 1; A ¹ is 1,4-phenylene, 3-methyl-1,
4-phenylene, 2-trifluoromethyl-1,4-phenylene, 3-trifluoromethyl-1,4-phenylene, 2,3-bis (trifluoromethyl) -1,4-phenylene, 3,5-dimethyl Biphenyl-4,4′-diyl, 3,5-dimethylterphenyl-4,4 ″ -diyl, 9-methylfluorene-2,7-diyl or 9,9-dimethylfluorene-2,7-diyl; A ² is any one of the groups represented by the following formula.

[3] In the formulas (1-1) to (1-3), R ¹ is methyl or ethyl; Z ¹ is a single bond, —COO— or —OCO—; Z ² is —COO—. or a -OCO-; Y is independently hydrogen or fluorine; X is be -OCF ₃ or -CN; w
Is 0 or 1; a is an integer from 1 to 10,
In formulas (2-1) to (2-2), R ² is independently methyl or ethyl; Z ³ is a single bond or —O—; Z ^{4 to} Z ⁷ are independently − COO-, -OCO-, -C
H ₂ CH ₂ COO—, —OCOCH ₂ CH ₂ —, —CH═CHCOO— or —OCOCH═CH—; L ^{1 to} L ⁴ are independently hydrogen or fluorine; m is an integer of 0 to 10 And when m is 0, Z ³ is a single bond; n is 0 or 1; A ¹ is 1,4-phenylene, 3-methyl-1,4-phenylene, 2-trifluoromethyl- 1,4-phenylene, 3-trifluoromethyl-1,4-phenylene, 2,3-bis (trifluoromethyl) -1,4-phenylene, 9-methylfluorene-2,7-diyl or 9,9- the liquid crystal film according to [2], wherein, wherein the a ² is any one of groups represented by the following formula: There dimethyl-2,7-diyl.

[4] In the formulas (1-1) to (1-3), R ¹ is methyl or ethyl; Z ¹ is a single bond, —COO— or —OCO—; Z ² is —COO—. or a -OCO-; Y is independently hydrogen or fluorine; X is be -OCF ₃ or -CN; w
Is 0 or 1; a is an integer from 1 to 10,
In Formula (2-1) to Formula (2-2), Z ³ is a single bond or —O—; Z ⁴ and Z ⁵ are independently —COO—, —OCO—, —CH ₂ CH _2. COO—, —OCOCH ₂ CH ₂ —, —CH═CHCOO— or —OCOCH═CH—; Z ⁶ and Z ⁷ are independently —COO—, —OCO—, —CH ₂ CH ₂ COO— or — OCOCH ₂ CH ₂ —; L ^{1 to} L ⁴ are independently hydrogen or fluorine; m is an integer of 0 to 10, and when m is 0, Z ³ is a single bond; n is 0 Or A ¹ is 1,4-phenylene, 3-methyl-1,4-phenylene, 9-methylfluorene-2,7-diyl or 9,9-dimethylfluorene-2,7-diyl; A ² is 9-methylfluorene-2,7-diyl or 9,9-dimethylphenol. The liquid crystal film as described in the item [2], which is Luolene-2,7-diyl.

[5] In the formula (1-1) to formula (1-3), R ¹ is methyl or ethyl; Z ¹ is a single bond, —COO— or —OCO—; Z ² is —COO—. or a -OCO-; Y is independently hydrogen or fluorine; X is be -OCF ₃ or -CN; w
Is 0 or 1; a is an integer from 1 to 10,
In the above formulas (2-1) to (2-2), Z ³ is a single bond or —O—; Z ⁴ is —COO—; Z ⁵ is —OCO—; Z ⁶ is — Z ⁷ is —OCO—; L ^{1 to} L ⁴ are independently hydrogen or fluorine; m is an integer from 0 to 10, and when m is 0, Z ³ is a single bond N is 0 or 1; A ¹ is 1,4-phenylene, 3-methyl-1,4-phenylene, 9-methylfluorene-2,7-diyl or 9,9-dimethylfluorene-2, 7-diyl; A ² is 9-methylfluorene-2,7-diyl or 9,9-dimethylfluorene-2,7-diyl;
The ratio of the compound represented by Formula (1-1)-Formula (1-3) is the compound represented by Formula (1-1)-Formula (1-3), and Formula (2-1)-Formula ( The liquid crystal film as described in the item [2], which is 3 to 70% by weight based on 100% by weight of the total amount of the compound represented by 2-2).

[6] In the formula (1-1) to formula (1-3), R ¹ is methyl or ethyl; Z ¹ is a single bond, —COO— or —OCO—; Z ² is —COO—. or a -OCO-; Y is independently hydrogen or fluorine; X is be -OCF ₃ or -CN; w
Is 0 or 1; a is an integer from 1 to 10,
In the formula (2-1), m is an integer of 0 to 3; n is 0; Z ³ is a single bond; Z ⁴ is —COO—; L ¹ and L ² are hydrogen. Yes; A ¹ is 1,4-phenylene;
In the above formula (2-2), Z ³ is a single bond or —O—; Z ⁶ is —COO—; Z ⁷ is —OCO—; L ^{1 to} L ⁴ are independently hydrogen or Fluorine; m is 0-10
And when m is 0, Z ³ is a single bond; n is 0 or 1; A ² is 9-methylfluorene-2,7-diyl;
The ratio of the compound represented by Formula (1-1)-Formula (1-3) is the compound represented by Formula (1-1)-Formula (1-3), and Formula (2-1)-Formula ( The liquid crystal film as described in the item [2], which is 5 to 50% by weight based on 100% by weight of the total amount of the compound represented by 2-2).

  [7] m in the formula (2-2) is an integer of 4 to 8, and the ratio of the compounds represented by the formula (1-1) to the formula (1-3) is represented by the formula (1- 1) to 5 to 35% by weight with respect to 100% by weight of the total amount of the compound represented by Formula (1-3) and the compound represented by Formula (2-1) to Formula (2-2). The liquid crystal film as described in the item [6].

  [8] The support substrate having a polar surface is a support substrate that has been surface-treated by any one of a film treatment with a polymer having a polar group, a corona treatment, and a plasma treatment. The liquid crystal film according to any one of [1] to [7].

  [9] The support substrate having the polar surface is a support substrate that has been surface-treated by a combination of two or more methods of coating treatment with a polymer having a polar group, corona treatment, and plasma treatment. The liquid crystal film according to any one of [1] to [7], wherein:

[10] The liquid crystal film of item [8] or [9], wherein the polymer having a polar group has a carboxyl group and / or an amino group in a molecular chain.
[11] The liquid crystal film of item [8] or [9], wherein the polymer having a polar group is a polyimide polymer.

  [12] The liquid crystal film according to item [11], wherein the polyimide polymer includes at least one component selected from the group consisting of polyamic acid, polyamic acid amide, and polyamic acid ester.

[13] The liquid crystal film as described in the item [11], wherein the polyimide polymer is a polyamic acid.
[14] The liquid crystal film of item [8] or [9], wherein the polymer having a polar group is a water-soluble silsesquioxane derivative having an amino group.

  [15] The water-soluble silsesquioxane derivative having an amino group is a partial hydrolyzate of a silicon compound having an amino group-containing group and three hydrolyzable groups. A liquid crystal film according to 1.

  [16] The liquid crystal film of item [15], wherein the water-soluble silsesquioxane derivative having an amino group is a partial hydrolyzate of trialkoxysilane having an amino group.

[17] The liquid crystal film according to any one of [1] to [16], wherein the supporting base material is a glass substrate.
[18] The liquid crystal film according to any one of [1] to [16], wherein the supporting base material is a plastic substrate.

  [19] The plastic substrate is polyimide, polyamideimide, polyamide, polyetherimide, polyetheretherketone, polyetherketone, polyketonesulfide, polyethersulfone, polysulfone, polyphenylenesulfide, polyphenyleneoxide, polyethyleneterephthalate, polybutyleneterephthalate. Polyethylene naphthalate, polyacetal, polycarbonate, polyarylate, acrylic resin, polyvinyl alcohol, polypropylene, cellulose, triacetyl cellulose, triacetyl cellulose partially saponified product, epoxy resin, phenol resin or cycloolefin resin The liquid crystal film according to item [18].

  [20] Any one of [1] to [19], wherein the polymerizable liquid crystal composition contains a solvent, and the solvent contains 5% by weight or more of a polar solvent based on the total weight of the solvent. A liquid crystal film according to 1.

  [21] The liquid crystal film of item [20], wherein the polar solvent is at least one selected from the group consisting of ketones, acetates, ethers, cellosolves, esters, and alcohols. .

  [22] A homeotropic alignment liquid crystal characterized by forming a homeotropic alignment state by applying the polymerizable liquid crystal composition according to the item [1] onto a support substrate having a polar surface and polymerizing the composition. A method for producing a film.

  [23] The support substrate having the polar surface is a support substrate that has been surface-treated by a coating treatment with a polymer having a polar group, and the coating film is formed of a 180 ° C. coating film made of the polymer. The method according to item [22], which is formed by firing at the following temperature.

[24] The production method according to item [23], wherein the polymer having a polar group is a polyimide polymer having an imidization ratio of 45% or less.
[25] The production method according to item [22], wherein the support substrate having a polar surface is a cycloolefin resin substrate subjected to plasma treatment.

[26] An optical compensation element comprising the homeotropic alignment liquid crystal film according to any one of [1] to [21].
[27] An optical compensator having a homeotropic alignment liquid crystal film produced by the method according to any one of [22] to [25].

[28] An optical element comprising the homeotropic liquid crystal film according to any one of [1] to [21] and a polarizing plate.
[29] An optical element comprising a homeotropic alignment liquid crystal film produced by the method according to any one of [22] to [25] and a polarizing plate.

[30] A liquid crystal display device comprising the optical compensation element according to the item [26] or [27] on an inner surface or an outer surface of a liquid crystal cell.
[31] A liquid crystal display device comprising the optical element according to the item [28] or [29] on an outer surface of a liquid crystal cell.

  According to the present invention, a liquid crystal film having uniform homeotropic alignment and good curability can be easily produced without forming an inert atmosphere when the polymerizable liquid crystal composition is cured. Therefore, facilities for forming an inert atmosphere are not necessary, and the manufacturing process can be simplified.

  Hereinafter, the homeotropic alignment liquid crystal film according to the present invention (hereinafter sometimes simply referred to as “liquid crystal film”), a method for producing the liquid crystal film, and uses of the liquid crystal film will be described in detail.

[Explanation of terms]
First, terms used in the present invention will be described.
In this specification, the polymerizable liquid crystal compounds represented by formulas (1-1), (1-2), and (1-3) are referred to as “compound (1-1)” and “compound (1-2)”, respectively. And “compound (1-3)”, and these compounds (1-1) to (1-3) may be collectively referred to as “compound (1)”. Similarly, compounds represented by other formulas may be referred to simply and generically in the same manner.

  “Tilt angle” refers to the angle formed by the orientation vector of the liquid crystal skeleton with the plane of the supporting substrate. 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 orientation state in which the tilt angle is constant in the range of 5 to 85 ° from one interface to the other interface or continuously changes in the range of 0 to 90 ° is referred to as “tilt orientation”. 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, in alkyl, any —CH ₂ — is —O— or —CH═.
When expressing that it may be replaced with CH—, a plurality of —CH ₂ — may be replaced with different groups. Specifically, C ₄ H ₉ - in any -CH ₂ - of -O-
Or Examples of groups is replaced by _{-CH = CH-, 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- etc. are mentioned. In the present invention, in consideration of the stability of the compound, two consecutive —CH ₂ — are replaced with —O—,
It is not preferable to become —O—O—.

  When it is described as alkyl without particular notice, it means alkyl including both linear alkyl and branched alkyl. For example, butyl may be any of n-butyl, 2-methylpropyl and 1,1-dimethylethyl. Reference to alkenyl means alkenyl including both straight and branched alkenyl. The same applies to alkylene and alkenylene. Further, cycloalkyl and cycloalkenyl include a cyclic group having a crosslinked structure in addition to a normal cyclic group.

[Homeotropic alignment liquid crystal film]
The liquid crystal film of the present invention comprises a polymerizable liquid crystal composition containing at least one compound selected from the group consisting of the above compounds (1-1) to (1-3) on a supporting substrate having a polar surface. It is obtained by coating and polymerizing.

(Polymerizable liquid crystal composition)
The compound which is a component of the polymerizable liquid crystal composition used in the present invention 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 support substrate having a particularly polar surface, and promotes homeotropic alignment. Compound (1-1) is easy to produce and low in cost. Compound (1-2) and compound (1-3) have good liquid crystallinity.

  From the viewpoint of curing speed, in the above polymerizable liquid crystal composition, it is preferable to use the compound (2) having a polymerizable group at both ends in addition to the compound (1). It is also preferable to use a compound having an oxiranyl (epoxy) group and a compound having an oxetanyl (oxetane) group in combination. 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 structure of the polymerizable liquid crystal composition used in 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). The mixing ratio of the compound (1) and the compound (2) in the polymerizable liquid crystal composition is as follows when the total amount thereof is 100% by weight. The proportion of compound (1) is preferably 3 to 70% by weight, more preferably 5 to 50% by weight, and still more preferably 5 to 35% by weight. The proportion of compound (2) is preferably 30 to 97% by weight, more preferably 50 to 95% by weight, and still more preferably 65 to 95% by weight.

  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 (1-3) and the compounds (2-1) to (2-2) may be used singly or in combination of two or more. . In addition, it is preferable to combine as follows from a viewpoint of a cure rate and mechanical characteristics.

(a) Compound (1-1) and Compound (2-1)
(b) Compound (1-1), Compound (1-2) and Compound (2-1)
(c) Compound (1-1), Compound (1-3) and Compound (2-1)
(d) Compound (1-2) and Compound (2-2)
(e) Compound (1-3) and Compound (2-2)
Compounds (1) to (2) can be synthesized by appropriately combining known techniques in organic synthetic chemistry. Organic Syntheses (Organic Syntheses) can be used to introduce a desired end group, ring, linking group, etc. into a starting material, or to produce a compound with the desired end group, ring, linking group, etc. , John Wiley & Sons, Inc
), Organic Reactions (John Wiley & Sons, Inc),
It is described in Comprehensive Organic Synthesis (Pergamon Press), New Experimental Chemistry Course (Maruzen), etc. For details, see WO97 /
No. 04349, JP-A 2006-117564, JP-A 2006-45195, JP-T 2003-513107, JP-A 2005-320317, JP-A 2006-241116, JP-A 2004-231638. JP-A-2004-182702, JP-A-2005-60373, JP-A-2006-225607, Japanese Patent Application No. 2006-149411, and the like describe synthesis methods.

  Next, component compounds are exemplified. In the following paragraphs, Me in the chemical structural formula means methyl, and Et means ethyl.

In formula (1-1-A) to formula (1-1-D), R ¹ is methyl or ethyl;
Is hydrogen or fluorine and X is —CN or —OCF ₃ .

  In Formula (1-2-A) and Formula (1-2-B), Y is hydrogen or fluorine, and a is an integer of 1 to 10.

In formula (1-3-A), a is an integer of 1-10.
Preferred compounds (2-1) are as follows.

In formulas (2-1-A) to (2-1-I), Z ³ is a single bond or —O—; L ² and L ³ are independently hydrogen or fluorine; Q ¹ is hydrogen Or is methyl; Q ² is independently hydrogen, methyl or trifluoromethyl; m is an integer of 0 to 10, and when m is 0, Z ³ is a single bond.

In formulas (2-2A) to (2-2O), R ² is methyl or ethyl; Z ³ is a single bond or —O—; L ^{1 to} L ⁴ are independently hydrogen. Or fluorine; Q ¹ is hydrogen or methyl; Q ² is independently hydrogen, methyl, or trifluoromethyl; m
Is an integer from 0 to 10, and when m is 0, Z ³ is a single bond.

Preferred examples of compound (1-1) are as follows. In the following formula, R ¹ is methyl or ethyl.

  Preferred examples of compound (1-2) and compound (1-3) are as follows. In the following formula, a is an integer of 4 to 8.

Among the above specific examples, the compounds (1-1-1), (1-1-5), and the compounds (1-2-1) and (1-3-1) in which a is an integer of 4-6. ) Is preferred.
Specific examples of compound (2-1) and compound (2-2) are shown below.

  Among the above, the compound (2-1-1), the compound (2-1-3), the compound (2-1-4), the compound (2-1-7), the compound (2-1-8), Compound (2-1-9), Compound (2-2-2), Compound (2-2-4), Compound (2-2-5), Compound (2-2-6), Compound (2-2) -8), compound (2-2-9), compound (2-2-10), compound (2-2-11) and compound (2-2-22) are preferred.

The polymerizable liquid crystal composition used in the present invention may further contain a polymerizable liquid crystal compound other than the compounds (1) and (2). Such other polymerizable liquid crystal compound only needs to have a structure capable of obtaining homeotropic alignment, and examples thereof include compound (3) in which one terminal is a non-polymerizable and non-polar group. The addition ratio of compound (3) is 0-0.25 by weight ratio with respect to the total amount of compound (1) and compound (2), preferably 0-0.15. The minimum of the preferable weight ratio when using a compound (3) is 0.05. Preferred examples of compound (3) are the following compound (3-1) and compound (3-2). Compound (3) differs from compound (1) in that it does not have a non-polymerizable polar group at its terminal.

In the above formula, Sp is alkylene having 1 to 20 carbon atoms. When the number of carbon atoms is 2 or more, —CH ₂ — in the alkylene may be replaced by —O—; G is a single bond, —O -, -COO
-Or -OCO-; u is 0 or 1; W ¹ is hydrogen, fluorine or alkyl or alkoxy having 1 to 25 carbon atoms; R ² is methyl or ethyl; MG
Is a mesogenic skeleton represented by the following formula (3 ′).

In the formula (3 ′), A ³ is 1,4-phenylene or 1,4-cyclohexylene; A ⁴ is 1,4-phenylene, 1,4-cyclohexylene or fluorene-2,7-diyl. A ⁵ is 1,4-phenylene or 3-fluoro-1,4-phenylene; Z ⁸ is a single bond or —COO—; Z ⁹ is a single bond or —OCO—; f is 0 or 1.

  Specific examples of compound (3) are shown below. In addition, these compounds can be used in the range which does not inhibit the effect of this invention. You may use the compound which has an epoxy group as described in Japanese translations of PCT publication No. 2000-507932 or WO97 / 04349 pamphlet.

  Among compounds (3), compound (3-1-1), compound (3-1-4), compound (3-2-1), compound (3-2-2), compound (3-2-2) 3) and compound (3-2-4) are preferred.

  The polymerizable liquid crystal composition has a polymerizable compound other than the polymerizable liquid crystal compounds (1) to (3) (hereinafter also referred to as “compound (4)”) within a range not impairing the effects of the present invention. May be blended. Compound (4) may not be liquid crystalline. The addition ratio of the compound (4) varies depending on the structure of the polymerizable liquid crystal compounds (1) to (3) and the composition ratio thereof, but is a weight ratio with respect to the total amount of the compound (1) and the compound (2). It is 0-0.20, Preferably it is 0-0.10. The lower limit of the preferred weight ratio when using the compound (4) is 0.05. When the addition ratio of the compound (4) is within this range, the liquid crystallinity of the composition is maintained, and phase separation of the liquid crystal phase hardly occurs.

  An example of the compound (4) is an epoxy resin. Specifically, 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 epoxy resin, alicyclic epoxy Resin, amine epoxy resin, triphenolmethane type epoxy resin, dihydroxybenzene type epoxy resin, bisphenol full orange crisidyl ether shown below (Osaka Gas Chemical Co., Ltd., BPF-G, BPEF-G, BCF-G), etc. It is.

  If necessary, a cationic photopolymerization initiator is added to the polymerizable liquid crystal composition, and the composition is irradiated with light in the air to polymerize the polymerizable compound to obtain a polymer. 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. Examples of the photocationic polymerization initiator include diaryliodonium salts (hereinafter abbreviated as “DAS”), triarylsulfonium salts (hereinafter abbreviated as “TAS”), and the like. When carrying out photocationic polymerization, preferred polymerizable groups in the present invention are organic groups having oxiranyl (epoxy), oxetanyl (oxetane) or thiirane (episulfide).

Examples of the DAS include diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate, diphenyliodoniumtetra ( Pentafluorophenyl) borate, 4-methoxyphenylphenyliodonium tetrafluoroborate, 4-methoxyphenylphenyliodonium hexafluorophosphonate, 4-methoxyphenylphenyliodonium hexafluoroarsenate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4- Toxiphenylphenyliodonium trifluoroacetate, 4-methoxyphenylphenyliodonium-p-toluenesulfonate, 4-methoxyphenylphenyliodoniumdiphenyliodoniumtetra (pentafluorophenyl) borate, bis (4-tert-butylphenyl) iodoniumdiphenyliodoniumtetra Fluoroborate, bis (4-tert-butylphenyl) iodonium diphenyliodonium hexafluoroarsenate, bis (4-tert-butylphenyl) iodonium diphenyliodonium trifluoromethanesulfonate, bis (4-tert-butylphenyl) iodonium trifluoroacetate, Bis (4-tert-butylphenyl) iodonium p-toluenesulfone Door and bis (4-ter
and t-butylphenyl) iodonium diphenyliodonium tetra (pentafluorophenyl) borate.

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

  Examples of the TAS include 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-methoxyphenyldiphenyl Sulfonium trifluorome Sulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium-p-toluenesulfonate, 4-methoxyphenyldiphenylsulfonium triphenylsulfonium tetra (pentafluorophenyl) borate, 4-phenylthiophenyldiphenylsulfonium tetrafluoro Borate, 4-phenylthiophenyldiphenylsulfonium hexafluorophosphonate, 4-phenylthiophenyldiphenylsulfonium hexafluoroarsenate, 4-phenylthiophenyldiphenylsulfonium trifluoromethanesulfonate, 4-phenylthiophenyldiphenylsulfonium-p-toluenesulfonate and 4-Phenylthiophenyl diphe Such as Le sulfonium tetra (pentafluorophenyl) borate.

  Commercially available products of the above-mentioned photocationic polymerization initiator include, for example, “Syracure UVI-6990”, “Syracure UVI-6974” and “Syracure UVI-6972” manufactured by UCC, “Adekatop” manufactured by Asahi Denka Kogyo Co., Ltd. Mar SP-150, SP-152, SP-170, SP-172 ", Rhodia's" PHOTOINITITOR 2074 ", Ciba Specialty Chemicals '" Irgacure 250 ", GE Silicones'" UV-9380C " And “DTS-102” manufactured by Midori Chemical Co., Ltd.

  If necessary, a thermal polymerization initiator is added to the polymerizable liquid crystal composition, and the composition is heated to polymerize the polymerizable liquid crystal compound to obtain a polymer. Examples of the thermal polymerization initiator include benzylsulfonium salts, benzylammonium salts, benzylpyridinium salts, benzylphosphonium salts, hydrazinium salts, carboxylic acid esters, sulfonic acid esters, amine imides, antimony pentachloride-acetyl chloride complex, Examples include diaryliodonium salts-dibenzyloxycopper, boron halide-tertiary amine adducts, and the like.

The polymerizable liquid crystal composition used in the present invention can also be subjected to hybrid polymerization using the above-mentioned photocationic polymerization initiator or thermal polymerization initiator in combination with a normal photoradical polymerization initiator. Examples of the photo radical polymerization initiator include “Darocur 1173” (2-hydroxy-2-methyl-1-phenylpropan-1-one), “Irgacure 184” (1) manufactured by Ciba Specialty Chemicals Co., Ltd. -Hydroxycyclohexyl phenyl ketone), "Irgacure 651" (2,2-dimethoxy-1,2-diphenylethane-1-one), "Irgacure 500", "Irgacure 2959", "Irgacure 907", " “Irgacure 369”, “Irgacure 1300”, “Irgacure 8”
19 ”,“ Irgacure 1700 ”,“ Irgacure 1800 ”,“ Irgacure 1850 ”,“ Darocur 4265 ”,“ Irgacure 784 ”and the like.

  As other radical photopolymerization initiators other than the above, for example, 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-methylpropane- 1-one, benzyldimethyl ketal, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2,4-diethylxanthone / methyl p-dimethylaminobenzoate and benzophenone / Methyltriethanolamine mixed And the like.

  The polymerizable liquid crystal composition used in the present invention can be polymerized by utilizing a base proliferation reaction by light (K. Arimitsu, M. Miyamoto, K. Ichimura, Angew. Chem. Int. Ed, 2000, 39, 3425). The addition amount of a photoinitiator is 0.01-10 weight part with respect to 100 weight part of total amounts of a polymeric liquid crystal compound, More preferably, it is 0.01-5 weight part.

  A polymerization inhibitor (polymerization inhibitor) may be added to the polymerizable liquid crystal composition in order to prevent a polymerization initiation reaction during storage. As the polymerization inhibitor, known ones can be used. For example, 2,5-di (t-butyl) hydroxytoluene (BHT), hydroquinone, methyl blue, diphenylpicric acid hydrazide (DPPH), benzothiazine, 4-nitroso Examples thereof include dimethylaniline (NIDI) and o-hydroxybenzophenone.

  An oxygen inhibitor (peroxide decomposer) may be added to the polymerizable liquid crystal composition in order to improve storage stability. 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 the oxygen inhibitor include phosphate esters.

  When producing the liquid crystal film of the present invention, the polymerizable liquid crystal composition may be used as it is, but after adding or adding a solvent to form a solution, the solvent is removed to produce a thin film. Also good.

Examples of the solvent include 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, and 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, trichloroethylene, tetrachloroethylene , Chlorobenzene, THF, 1,4-dio Sun, 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, N-methyl-2-pyrrolidone (NMP), dimethyl sulfoxide, N, N-dimethylacetamide, N , N-dimethylacetamide dimethylacetal, dimethylformamide and the like. Even if these are used alone,
Two or more kinds may be mixed and used.

  What is necessary is just to use the said solvent on the conditions which do not corrode the support base material used by this invention. For example, the polar solvent can be used in an amount of 5% by weight or more, preferably 10 to 50% by weight, more preferably 10 to 30% by weight based on the total weight of the solvent (total weight of the polar solvent and the low polarity solvent). . In particular, when a norbornene-based resin is selected as the support substrate, the polar solvent is 30% by weight or more, preferably 40% by weight or more, more preferably based on the total weight of the solvent (total weight of the polar solvent and the low-polar solvent). By containing 50% by weight or more, erosion due to the solvent can be avoided.

  Preferred polar solvents include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, and methyl propyl ketone; ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl acetoacetate Acetates such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, ethers such as 1,4-dioxane and THF; cellosolves such as ethyl cellosolve, butyl cellosolve and PGMEA; ethyl acetate, butyl acetate, alkyl lactate (methyl lactate, Ethyl lactate, isopropyl lactate, lactate-n-propyl, butyl lactate, ethyl hexyl lactate), trifluoro Esters such as ethyl; hexafluoro-2-propanol, ethanol, 2-propanol, t- butyl alcohol, alcohols such as diacetone alcohol; .gamma.-butyrolactone, NMP and the like. These may be used alone or in combination of two or more.

  Preferred low polarity solvents include, for example, benzene, toluene, heptane, xylene, mesitylene, n-butylbenzene, diethylbenzene, tetralin, methoxybenzene, 1,2-dimethoxybenzene, chloroform, dichloromethane, carbon tetrachloride, dichloroethane, trichloroethylene, Examples include tetrachloroethylene, chlorobenzene, bis (methoxyethyl) ether, tetramethylurea, trifluoroacetic acid, glycerin, monoacetin, ethylene glycol, triethylene glycol, hexylene glycol, and ethylene glycol monomethyl ether. These may be used alone or in combination of two or more.

  In order to facilitate the application of the composition or to control the orientation of the liquid crystal phase, the polymerizable liquid crystal composition has an interface within a range that does not impair the effects of the present invention and the curability of the composition. An activator may be added.

  Examples of the surfactant include imidazoline, quaternary ammonium salts, alkylamine oxides, polyamine derivatives, polyoxyethylene-polyoxypropylene condensates, polyethylene glycol and esters thereof, sodium lauryl sulfate, ammonium lauryl sulfate, and lauryl sulfate amines. , Alkyl-substituted aromatic sulfonates, alkyl phosphates, aliphatic or aromatic sulfonic acid formalin condensates, laurylamidopropylbetaine, laurylaminoacetic acid betaine, polyethylene glycol fatty acid esters, polyoxyethylene alkylamine, perfluoroalkyl Sulfonate, perfluoroalkylcarboxylate, perfluoroalkylethylene oxide adduct, perfluoroalkyltrimethylammonium salt, Oligomers having a fluoroalkyl group and a hydrophilic group, oligomers having a perfluoroalkyl group and a lipophilic group, and urethane having a perfluoroalkyl group.

  The amount of the surfactant added varies depending on the type of the surfactant, the composition ratio of the polymerizable liquid crystal composition, etc., but is 0.002 to 100 parts by weight of the polymerizable liquid crystal compound in the polymerizable liquid crystal composition. 5 parts by weight, preferably in the range of 0.01 to 1 part by weight.

[Supporting substrate]
As the support substrate on which the polymerizable liquid crystal composition is applied, a support substrate having a polar surface is used. By using a support substrate having such a polar surface, a uniform and stable homeotropic alignment state can be formed. The material of the support substrate is glass or plastic resin.

  Examples of the plastic resin include polyimide, polyamideimide, polyamide, polyetherimide, polyetheretherketone, polyetherketone, polyketonesulfide, polyethersulfone, polysulfone, polyphenylenesulfide, polyphenyleneoxide, polyethyleneterephthalate, and polybutyleneterephthalate. Polyethylene naphthalate, polyacetal, polycarbonate, polyarylate, acrylic resin, polyvinyl alcohol, polypropylene, cellulose, triacetyl cellulose (TAC), partially saponified product of triacetyl cellulose, epoxy resin, phenol resin and cycloolefin resin, etc. It is done.

  The cycloolefin-based resin is not particularly limited, and examples thereof include norbornene-based resins and dicyclopentadiene-based resins. Among them, those having no unsaturated bond or hydrogenated unsaturated bond are preferably used. For example, a ring-opening (co) polymer of one or more norbornene-based monomers is used. Hydrogenated products, addition (co) polymers of one or more norbornene monomers, addition copolymers of norbornene monomers and olefin monomers (ethylene, α-olefin, etc.), norbornene monomers and cycloolefins Examples thereof include addition copolymers with system monomers (cyclopentene, cyclooctene, 5,6-dihydrodicyclopentadiene, etc.) and modified products thereof. Specifically, ZEONEX, ZEONOR (manufactured by Nippon Zeon), ARTON (manufactured by JSR), TOPAS (manufactured by Chicona), APEL (manufactured by Mitsui Chemicals), ESCINA (manufactured by Sekisui Chemical Co., Ltd.), OPTOREZ (Hitachi Chemical) Etc.).

  When a plastic film is used as the support substrate, it may be a uniaxially stretched film or a biaxially stretched film. Further, it may be a single layer film or a laminated film.

  The support substrate is subjected to a surface treatment in order to impart polarity to the substrate surface. As such a surface treatment, a film treatment, a corona treatment and a plasma treatment with a polymer having a polar group are preferable, and two or more methods can be performed even if any one of the film treatment, the corona treatment and the plasma treatment is performed. You may carry out in combination. Note that as the plasma treatment, a method described in JP 2002-226616 A, JP 2002-121648 A, or the like may be used.

  The polarity of the substrate surface after the surface treatment such as corona treatment or plasma treatment is applied to the plastic film can be evaluated by measuring the contact angle with water, and contact for obtaining uniform and stable homeotropic orientation The angle is 80 ° or less, preferably 5 ° to 65 °, more preferably 5 ° to 50 °.

  Examples of the polymer having a polar group used in the coating treatment include a polymer having a carboxyl group and / or an amino group in a molecular chain, and a polyimide polymer and a water-soluble silsesquioxy having an amino group. Sun derivatives are preferred.

<Polyimide polymer>
The polyimide polymer can be used as a polyimide varnish. The polyimide varnish is a varnish composition in which a polymer component such as polyamic acid, polyamic acid amide, polyamic acid ester, soluble polyimide, and polyamideimide is dissolved in a solvent. After the varnish composition is applied on a supporting substrate, the solvent is dried and removed to form a polymer film. The polymer component constituting the polymer film may be a copolymer such as a random copolymer or a block copolymer, or may be used alone or in combination of two or more.

  A preferred polyimide polymer is a polymer having an amide bond, an imide bond, a carboxyl group that is an imidization reaction residue, a group in which the carboxyl group is amidated, or a group in which the carboxyl group is esterified. Preferred examples of such polymers are polyamic acids, polyamic acid amides and polyamic acid esters. Among these, polyamic acid and polyamic acid amide are more preferable, and polyamic acid is particularly preferable.

  Examples of the tetracarboxylic dianhydride and diamine used for obtaining the polyamic acid, polyamic acid amide, or polyamic acid ester include compounds described on pages 234 to 243 of JP-A-2006-23657. These compounds may be used alone or in combination of two or more.

  The purpose is to improve the molecular weight of the polyamic acid, polyamic acid amide, polyamic acid ester, soluble polyimide or polyamideimide used in the present invention, the concentration of the polymer component in the polyimide varnish, the solvent used together with the polymer component, and coating properties. The other solvent, various additives, and a method for applying the polyimide varnish may be based on the method described on pages 243 to 244 of JP-A-2006-23657.

  The polarity of the substrate surface after the coating treatment using the polyimide polymer can be evaluated by measuring the imidization rate. The rate of dehydration / ring-closure reaction (imidization reaction) of the polyimide varnish is preferably as low as possible in order to promote homeotropic orientation. The imidation ratio of the polyimide polymer coating is 45% or less, preferably 0 to 35%, more preferably 0 to 20%. When the imidization ratio is within the above range, the reason is not clear, but the ratio of polar groups such as carboxyl groups and amide bonds in the polyimide polymer coating increases, and polymerizable liquid crystals having non-polymerizable polar groups It is considered that the interaction between the polymer film and the polyimide polymer film is strengthened, and as a result, homeotropic alignment of the polymerizable liquid crystal is easily obtained.

  Therefore, the drying step after varnish application is preferably carried out at a relatively low temperature within a range in which the solvent can be evaporated in order to promote homeotropic alignment of the polymerizable liquid crystal. Specifically, it is preferable to carry out at 180 ° C. or less, preferably 40 ° C. to 180 ° C., more preferably 50 ° C. to 150 ° C., and further preferably 70 ° C. to 120 ° C. Furthermore, as another means for keeping the imidization rate low, a method of esterifying or amidating a part of the carboxyl group of the polyamic acid prior to the imidation reaction may be employed. The polyamic acid amide and the polyamic acid ester are polymers thus obtained.

<Water-soluble silsesquioxane derivative having an amino group>
The water-soluble silsesquioxane derivative having an amino group can be obtained by the method described on pages 203 to 205 of JP-A-2006-23656.

When forming the polymer film which consists of said water-soluble silsesquioxane derivative which has the said amino group on a support base material, it is preferable to use the said water-soluble silsesquioxane derivative which has the said amino group as aqueous solution. At this time, the component concentration is not particularly limited, but is preferably 0.1 to 60% by weight. When the concentration of the silsesquioxane derivative is 60% by weight or less, the viscosity becomes good, and water can be easily mixed when the aqueous solution is diluted with water for film thickness adjustment. In the spinner method or printing method, in order to keep the film thickness good, the content is usually 40% by weight or less in many cases. In other coating methods such as dipping and ink jet methods, the concentration may be further reduced. On the other hand, when the concentration of the silsesquioxane derivative is 0.1% by weight or more, a polymer film having a good film thickness tends to be obtained. Therefore, the component concentration of the aqueous silsesquioxane derivative solution having an amino group is 0.1% by weight or more, preferably 1 to 40% by weight in the usual spinner method or printing method. However, depending on the application method of this aqueous solution, it may be used at a dilute concentration.

  In the aqueous solution, a solvent capable of dissolving the silsesquioxane derivative component may be used in combination. Such a solvent can be appropriately selected according to the purpose of use from solvents that are usually used in the production process and application of the silsesquioxane derivative component. This solvent is preferably water-soluble and can be selected from alcohol solvents, ketone solvents, aprotic polar solvents, and the like.

  Examples of the solvent include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, ethyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, THF, 1,4-dioxane, bis (methoxyethyl) ether, γ-butyrolactone, tetramethylurea, trifluoroacetic acid, ethyl trifluoroacetate, hexafluoro-2-propanol, t-butyl alcohol, diacetone alcohol, glycerin, Monoacetin, ethylene glycol, triethylene glycol, hexylene glycol, ethyl Glycol monomethyl ether, ethyl cellosolve, butyl cellosolve, PGMEA, 2-pyrrolidone, N-methyl-2-pyrrolidone, dimethyl sulfoxide, N, N-dimethylacetamide, N, N-dimethylacetamide dimethylacetal and dimethylformamide Can be mentioned.

  As a coating method of the silsesquioxane derivative aqueous solution having an amino group, for example, a spinner method, a printing method, a dipping method, a dropping method, an ink jet method, or the like can be employed. As a heating method in the drying step, for example, a heat treatment method in an oven or an infrared furnace, a heat treatment method on a hot plate, or the like can be employed.

  The drying step after applying the amino group-containing silsesquioxane derivative aqueous solution is preferably carried out at a temperature within a range where the solvent can be evaporated and at a temperature lower than the heat resistant temperature of the supporting substrate. In particular, when the supporting substrate is a plastic substrate, the drying temperature is 80 to 150 ° C., preferably 90 to 120 ° C., which is not higher than the glass transition temperature of the supporting substrate to be used.

  The polarity of the substrate surface after the coating treatment using the water-soluble silsesquioxane derivative having an amino group can be evaluated by measuring the contact angle of water. As described above, the contact angle for obtaining uniform and stable homeotropic alignment is 80 ° or less, preferably 5 ° to 65 °, more preferably 5 ° to 50 °.

<Rubbing treatment>
As described above, after the surface of the supporting substrate is treated so as to have polarity, physical / mechanical surface treatment such as rubbing may be further performed prior to coating film formation of the polymerizable liquid crystal composition. Good. When a homeotropic alignment liquid crystal film is formed, surface treatment such as rubbing is often not performed, but rubbing treatment may be performed to prevent alignment defects. 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.

[Method for producing homeotropic alignment liquid crystal film]
Examples of a method for uniformly coating the polymerizable liquid crystal composition on a support substrate having a polar surface include spin coating, roll coating, caten coating, flow coating, printing, and microgravure coating. Method, gravure coating method, wire bar coating method, dip coating method, spray coating method, meniscus coating method, die coating method and the like.

  When the solution of the polymerizable liquid crystal composition is applied on the support substrate, the solvent is dried and removed after the 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, and it may be dried until the solvent is almost removed and the fluidity of the coating layer is lost. 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 which passed through the drying process can be used for the polymerization process without going through the heat treatment process 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. Therefore, 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. As an example of the heat treatment method, there 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. 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. 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 from room temperature to 120 ° C, more preferably from room temperature to 100 ° C, and even more preferably from room temperature to 70 ° C. A preferable heat treatment time is 5 seconds to 2 hours, more preferably 10 seconds to 40 minutes, and still more preferably 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. Electron beams, ultraviolet rays, visible rays, infrared rays (heat rays), etc. can be used. Usually, ultraviolet rays or visible rays may be used. Although the wavelength of the light used for light irradiation is not specifically limited, Preferably it is 150-500 nm, More preferably, it is 250-450 nm, More preferably, it is 300-400 nm.

Examples of the light source include 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 (ultra-high-pressure mercury lamps, xenon lamps, mercury xenon lamps). A metal halide lamp, a xenon lamp, and a high-pressure mercury lamp are preferable.

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. Amount of light emitted from the light source is preferably 2~5000mJ / cm ^2, more preferably 10~3000mJ / cm ^2, more preferably from 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 a liquid crystal film obtained by polymerizing an alignment layer made of a polymerizable liquid crystal composition by light or heat is used in various optical elements or as an optical compensation element used in a liquid crystal display device, the tilt angle in the thickness direction The control of the distribution 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, and the like 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 of the manufacturing process of the liquid crystal film, an arbitrary tilt angle can be obtained.

  In order to obtain a stable and uniform homeotropic alignment, the content of the compound (1) in the polymerizable liquid crystal composition is 3 to 70 wt% when the total amount of the polymerizable liquid crystal compounds is 100 wt%. %, Preferably 5 to 50% by weight, more preferably 5 to 35% by weight. Moreover, in order to maintain the mechanical properties such as heat resistance of the liquid crystal film, it is preferable that the content be about 10 to 35% by weight.

  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, it is preferably 0.05 to 50 μm, more preferably 0.1 to 20 μm, and still more preferably 0.5 to 10 μm.

  The haze value of the liquid crystal film is preferably 1.5% or less, more preferably 1.0% or less, and the transmittance is preferably 80% or more, more preferably 95% or more. The transmittance preferably satisfies these conditions in the visible light region.

<Application>
The liquid crystal film of the present invention is effective as an optical compensation element applied to liquid crystal display elements (particularly active matrix type and passive matrix type liquid crystal display elements). Examples of types of liquid crystal display elements suitable for using the liquid crystal film of the present invention as an optical compensation film include 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 aligned nematic / cholesteric), OMI type (optical mode interference), SBE type (super birefringence effect), and the like. Furthermore, the liquid crystal film can be used as a phase letter for display elements 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 liquid crystal film of the present invention can also be used as an optical element integrated with a polarizing plate or the like, and in this case, it is disposed on the outer surface of the liquid crystal cell.
[Example]
EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples.

[Evaluation]
Evaluation methods performed in Examples and the like are shown below.
<Uniformity of homeotropic alignment>
When two polarizing plates are placed in a crossed Nicol state, a liquid crystal film is inserted between them, and when observed from the front, when the dark spot derived from alignment defects in the liquid crystal is not visually confirmed (dark field), the state of uniform alignment did. In this state, the film was tilted and light was incident from an oblique direction. Similarly, observation was performed with crossed Nicols, and the case where light transmission was confirmed was defined as homeotropic alignment.

<Measurement 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 the substrate was measured at 25 ° C.

<Measurement of imidization ratio>
First, measure the FT-IR of the polyimide polymer film was prepared by heating 30 minutes at separately 280 ° C., and the absorption spectrum of the imide groups in the vicinity of 1770 cm ^-1, and the absorption spectrum of the phenyl groups in the vicinity of 1500 cm ^-1 The value of the area ratio (Abs1770 / Abs1500) was determined, and this value was taken as the value when the imidization rate was 100%. Next, the value of the area ratio (Abs1770 / Abs1500) of the polyimide polymer film to be evaluated was determined, and the imidization rate was determined from the relative value to the value when the imidization rate was 100%.

[Preparation Example of Polymerizable Liquid Crystal Composition]
The compound (1-1-1) used below was synthesized by replacing 3-fluoro-4-trifluoromethoxyphenol with a raw material having cyanobiphenyl according to the method described in JP-A-2005-320317. did. Compound (1-1-5) was synthesized by the method described in JP-A-2005-320317. Compound (1-2-1) was synthesized by the method described in JP-A-2006-117564. Compound (1-3-1) was synthesized by the method described in JP-A No. 2006-241116. Compound (2-1-1) was synthesized by the method described in Macromolecules 1993, 26, 1244-1247. Compound (2-2-22) was synthesized by the method described in JP-A-2005-60373.

<Preparation Example 1>
An initiator (DTS-102: manufactured by Midori Chemical Co., Ltd.) was added to the mixture of polymerizable liquid crystal compounds shown below at a ratio of 0.03 by weight to the total amount of polymerizable liquid crystal compounds. To this, a mixed solvent of toluene and cyclohexanone (mixing ratio (weight ratio): toluene / cyclohexanone = 1/1) was added to obtain a 25 wt% solution to obtain a polymerizable liquid crystal composition-1.

<Preparation Example 2>
A polymerizable liquid crystal composition-2 was prepared in the same manner as in Preparation Example 1, except that the following mixture of polymerizable liquid crystal compounds was used.

<Preparation Example 3>
A polymerizable liquid crystal composition-3 was prepared in the same manner as in Preparation Example 1, except that the following mixture of polymerizable liquid crystal compounds was used.

<Preparation Example 4>
A polymerizable liquid crystal composition-4 was prepared in the same manner as in Preparation Example 1, except that the mixture of polymerizable liquid crystal compounds shown below was used.

<Preparation Example 5>
A polymerizable liquid crystal composition-5 was prepared in the same manner as in Preparation Example 1, except that the following mixture of polymerizable liquid crystal compounds was used.

<Preparation Example 6>
A polymerizable liquid crystal composition-6 was prepared in the same manner as in Preparation Example 1, except that the following mixture of polymerizable liquid crystal compounds was used.

[Preparation example of polyimide varnish]
The meanings of the symbols used in the following are as follows.
DDM: 4,4′-diaminodiphenylmethane DDEt: 4,4′-diaminodiphenylethane APM-CH: 1,1-bis (4-((4-aminophenyl) methyl) phenyl) -4-heptylcyclohexane DABD: 5 -(4- (4- (4-pentylcyclohexyl) cyclohexyl) phenyl) methyl-1,3-diaminobenzene CBDA: cyclobutanetetracarboxylic dianhydride PMDA: pyromellitic dianhydride NMP: N-methyl-2- Pyrrolidone BC: Butyl cellosolve GPC was used to measure the molecular weight of the polyimide varnish, polystyrene was used as the standard solution, and DMF was used as the eluent.

<Preparation Example 7>
In a 200 mL 4-necked flask, DDM (3.02 g; 1.52 × 10 ⁻² mol) and dehydrated NMP (54.0 g) were charged and dissolved by stirring under a dry nitrogen stream. Lowered. CBDA (2.98 g; 1.52 × 10 ⁻² mol) was added thereto and reacted for 30 hours. At this time, the temperature of the reaction system was not particularly controlled. Finally, BC
(40.0 g) was added to prepare a polyamic acid varnish A1 having a polymer component concentration of 6.0% by weight. The resulting polyamic acid had a weight average molecular weight of 50,000. In addition, the weight average molecular weight was measured at a column temperature of 50 ° C. using a GPC measuring apparatus (Chromatopack C-R7A) manufactured by Shimadzu Corporation.

  In addition, preparation of the said varnish advanced the thickening reaction, checking a viscosity. Then, when the increase in viscosity decreased, BC was added to stop the progress of the thickening reaction. After adding BC, the viscosity of the varnish was adjusted by heating, and the heating operation was stopped when the viscosity reached 60 mPa · s. The viscosity was measured at 25 ° C. using an E-type viscometer. The obtained varnish was stored at a low temperature.

<Preparation Example 8>
As a diamine, DDET (1.07 g; 5.02 × 10 ⁻³ mol) and APM-CH (2.74 g; 5.02 × 10 ⁻³ mol) were used instead of DDM, and CBDA was used as a tetracarboxylic dianhydride. A polyamic acid varnish A2 was prepared in the same manner as in Preparation Example 7, except that PMDA (2.19 g; 1.00 × 10 ⁻² mol) was used instead of. The obtained polyamic acid had a weight average molecular weight of 60,000.

<Preparation Example 9>
The polyamic acid varnish A1 obtained in Preparation Example 7 and the polyamic acid varnish A2 obtained in Preparation Example 8 were mixed so that the weight ratio of the polymer components contained in each was A1: A2 = 9: 1 Thus, polyamic acid varnish A3 was obtained.

[Example 1]
The polyamic acid varnish A1 obtained in Preparation Example 7 was applied onto a glass substrate (Panasonic glass slide, thickness 1.0 mm) by spin coating, pre-baked at 80 ° C. for 3 minutes, and then heated at 110 ° C. for 30 minutes ( A polymer film was formed by performing main firing. The imidation ratio of the obtained polymer film was 5%. Since the imidation rate was less than 100%, it was confirmed that the polymer molecular chain of the polymer film had a carboxyl group.

Next, the polymerizable liquid crystal composition-1 obtained in Preparation Example 1 is applied by spin coating on the polymer film that has not been subjected to surface treatment such as rubbing and heated at 70 ° C. for 3 minutes. The solvent was removed. Next, a liquid crystal film having a transparent appearance is obtained by polymerizing the polymerizable liquid crystal compound by irradiating the coating film with 30 mW / cm ² (365 nm) light for 30 seconds using a 250 W super high pressure mercury lamp at room temperature in the atmosphere. Got.

  Since the two polarizing plates were in a crossed Nicol state, the obtained liquid crystal film was in a dark field, and when the liquid crystal film was tilted from the direction perpendicular to the film surface, a phase difference was confirmed. It was confirmed that a liquid crystal film having uniform homeotropic alignment was obtained.

[Example 2]
The same operation as in Example 1 was performed except that the polymerizable liquid crystal composition-2 was used instead of the polymerizable liquid crystal composition-1. It was confirmed that the obtained liquid crystal film was transparent in appearance and had a uniform homeotropic alignment.

Example 3
The same operation as in Example 1 was performed except that the polymerizable liquid crystal composition-3 was used instead of the polymerizable liquid crystal composition-1. It was confirmed that the obtained liquid crystal film was transparent in appearance and had a uniform homeotropic alignment.

Example 4
The same operation as in Example 1 was performed except that the polymerizable liquid crystal composition-4 was used instead of the polymerizable liquid crystal composition-1. It was confirmed that the obtained liquid crystal film was transparent in appearance and had a uniform homeotropic alignment.

Example 5
The same operation as in Example 1 was performed except that the polymerizable liquid crystal composition-5 was used instead of the polymerizable liquid crystal composition-1. It was confirmed that the obtained liquid crystal film was transparent in appearance and had a uniform homeotropic alignment.

Example 6
The same operation as in Example 1 was performed except that the polymerizable liquid crystal composition-6 was used instead of the polymerizable liquid crystal composition-1. It was confirmed that the obtained liquid crystal film was transparent in appearance and had a uniform homeotropic alignment.

Example 7
The same procedure as in Example 1 was conducted except that the polyamic acid varnish A3 was used instead of the polyamic acid varnish A1, and the imidation ratio of the obtained polymer film was 8%. It was confirmed that the obtained liquid crystal film was transparent in appearance and had a uniform homeotropic alignment.

Example 8
The same operation as in Example 7 was performed except that the polymerizable liquid crystal composition-2 was used instead of the polymerizable liquid crystal composition-1. It was confirmed that the obtained liquid crystal film was transparent in appearance and had a uniform homeotropic alignment.

Example 9
The same operation as in Example 7 was performed except that the polymerizable liquid crystal composition-4 was used instead of the polymerizable liquid crystal composition-1. It was confirmed that the obtained liquid crystal film was transparent in appearance and had a uniform homeotropic alignment.

Example 10
The main baking temperature of the coating film made of the polyamic acid varnish A1 was set at 150 ° C. for 30 minutes, and the imidation ratio of the obtained polymer film was 15%. It was confirmed that the obtained liquid crystal film was transparent in appearance and had a uniform homeotropic alignment.

Example 11
The same operation as in Example 10 was performed except that the polymerizable liquid crystal composition-2 was used instead of the polymerizable liquid crystal composition-1. It was confirmed that the obtained liquid crystal film was transparent in appearance and had a uniform homeotropic alignment.

[Comparative Example 1]
In the same manner as in Example 1, except that the polymerizable liquid crystal composition-1 ′ prepared without using the compound (1-1-5) in Preparation Example 1 was used instead of the polymerizable liquid crystal composition-1. When a liquid crystal film was produced, the liquid crystal was not aligned and the film was also clouded, causing a problem in appearance.

[Comparative Example 2]
In the same manner as in Example 2, except that the polymerizable liquid crystal composition-2 ′ prepared without using the compound (1-1-5) in Preparation Example 2 was used instead of the polymerizable liquid crystal composition-2. When a liquid crystal film was produced, the liquid crystal was not aligned and the film was also clouded, causing a problem in appearance.

[Comparative Example 3]
In the same manner as in Example 4 except that the polymerizable liquid crystal composition-4 ′ prepared without using the compound (1-1-1) in Preparation Example 4 was used instead of the polymerizable liquid crystal composition-4. When a liquid crystal film was produced, the liquid crystal was not aligned and the film was also clouded, causing a problem in appearance.

[Comparative Example 4]
In the same manner as in Example 5 except that the polymerizable liquid crystal composition-5 ′ prepared without using the compound (1-2-1) in Preparation Example 5 was used instead of the polymerizable liquid crystal composition-5. When a liquid crystal film was produced in the same manner, the liquid crystal was not aligned, and the film was also clouded, causing a problem in appearance.

[Comparative Example 5]
In the same manner as in Example 6 except that the polymerizable liquid crystal composition-6 ′ prepared without using the compound (1-3-1) in Preparation Example 6 was used instead of the polymerizable liquid crystal composition-6. When a liquid crystal film was produced in the same manner, the liquid crystal was not aligned, and the film was also clouded, causing a problem in appearance.

[Comparative Example 6]
The main baking temperature of the coating film made of the polyamic acid varnish A1 was performed at 210 ° C. for 30 minutes, and the imidation ratio of the obtained polymer film was 75%, which was performed in the same manner as in Example 1, and the liquid crystal film As a result, the liquid crystal was not aligned and the film was also clouded, which had a problem in appearance.

Example 12
Chisso Co., Ltd., which is a partial hydrolyzate of 3-aminopropyltriethoxysilane on a saponification TAC film (manufactured by Aiki Sangyo Co., Ltd., thickness 80 μm, contact angle with water 30 °) as a supporting substrate “SF330” (50% by weight aqueous solution diluted to 25% by weight aqueous solution) was applied by spin coating. Then, it dried at 100 degreeC for 3 minute (s), and formed the polymer film. The contact angle on the surface of the base material on which the polymer film was formed was 25 °. Next, the polymerizable liquid crystal composition-1 was applied in the same manner as in Example 1. It was confirmed that the obtained liquid crystal film was transparent in appearance and had a uniform homeotropic alignment.

Example 13
A cycloolefin resin (thickness 50 μm, ZEONOR film / ZEONOR1600R, manufactured by Nippon Zeon Co., Ltd.), specially prepared by subjecting the polymerizable liquid crystal composition-2 obtained in Preparation Example 2 to a hydrophilic treatment by plasma treatment using a wire bar. (See Kakai 2004-4641)) (wet thickness: 12 μm). The surface hydrophilization treatment (plasma treatment) was performed using an atmospheric pressure plasma surface treatment apparatus (AP-T02-L). Plasma discharge conditions were set according to Japanese Patent Application Laid-Open No. 2002-226616. When the degree of hydrophilization treatment was evaluated by measuring the contact angle (25 ° C.) of pure water dropped on the cycloolefin resin substrate, the contact angle was 97 ° before treatment and 40 ° after treatment. 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 a liquid crystal film. It was confirmed that the obtained liquid crystal film was transparent in appearance and had a uniform homeotropic alignment.

Example 14
Example 13 except that the polymerizable liquid crystal composition obtained by changing the mixing ratio (weight ratio) of the mixed solvent of the polymerizable liquid crystal composition-2 in Preparation Example 2 to toluene / cyclohexanone = 2/1 was used. And performed in the same manner. It was confirmed that the obtained liquid crystal film was transparent in appearance and had a uniform homeotropic alignment.

Example 15
The same procedure as in Example 13 was performed except that the polymerizable liquid crystal composition obtained by changing the mixed solvent of the polymerizable liquid crystal composition-2 in preparation example 2 to only cyclohexanone was used. It was confirmed that the obtained liquid crystal film was transparent in appearance and had a uniform homeotropic alignment.

[Comparative Example 7]
In the same manner as in Example 13, except that the polymerizable liquid crystal composition-2 ′ prepared without using the compound (1-1-5) in Preparation Example 2 was used instead of the polymerizable liquid crystal composition-2. When a liquid crystal film was produced, the liquid crystal was not aligned and the film was also clouded, causing a problem in appearance.

[Comparative Example 8]
A liquid crystal film was produced in the same manner as in Example 13 except that the polymerizable liquid crystal composition obtained by changing the solvent of the polymerizable liquid crystal composition-2 to only toluene in Preparation Example 2 was used. An oriented liquid crystal film could be obtained. However, deformation (curl) of the cycloolefin-based resin substrate was confirmed, and it was confirmed that the support substrate was eroded by the solvent.

  From the results of the above examples and comparative examples, the use of a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound having a polar group at the molecular terminal and a solvent containing a polar solvent as the solvent is used so as to have polarity. It was confirmed that a liquid crystal film having uniform homeotropic alignment was obtained on the surface-treated support substrate.

Claims (10)

5 to 35% by weight of at least one compound selected from the group of polymerizable liquid crystal compounds represented by formula (1-1) to formula (1-3), the following formula (2-1) and formula (2-2) And polymerizing a polymerizable liquid crystal composition containing 65 to 95% by weight of at least one compound selected from the group of polymerizable liquid crystal compounds represented by formula (1) on a support substrate having a polar surface. obtained by,
The supporting substrate having the polar surface is a glass substrate surface-treated by a film treatment with a polymer having a polar group,
The homeotropic alignment liquid crystal film, wherein the polymerizable liquid crystal composition contains any combination of the following (i) to (iii) .
(i) Compound represented by Formula (1-1) and Compound represented by Formula (2-1)
(ii) Compound represented by formula (1-2) and compound represented by formula (2-2)
(iii) Compound represented by Formula (1-3) and Compound represented by Formula (2-2)

Wherein R ¹ is methyl or ethyl; Z ¹ is a single bond, —COO—, —OCO—, —CH═CH—COO— or —CH ₂ CH ₂ —COO—; Z ² is — COO— or —OCO—; Y is independently hydrogen or fluorine; X is —OCF ₃ or —CN; w is 0, 1 or 2; a is an integer from 1 to 10 . ]

Wherein R ² is independently methyl or ethyl; Z ³ is a single bond or —O—; Z ^{4 to} Z ⁷ are independently —COO—, —OCO—, —CH ₂ CH _2. COO—, —OCOCH ₂ CH ₂ —, —CH═CHCOO—, —OCOCH═CH—, —CH ₂ CH ₂ —, —C≡C—, —CH ₂ O— or —OCH ₂ —; L ¹ hydrogen ~L ⁴ is independently fluorine, chlorine, methyl, trifluoromethyl, or cyano; m is an integer of 0, Z ³ when m is 0 is a single bond; n is 0 Or A ¹ is 1,4-phenylene, 3-methyl-1,4-phenylene, 2-trifluoromethyl-1,4-phenylene, 3-trifluoromethyl-1,4-phenylene, 2, 3-bis (trifluoromethyl) -1,4-phenylene, 3,5-dimethyl Phenyl-4,4′-diyl, 3,5-dimethylterphenyl-4,4 ″ -diyl, 9-methylfluorene-2,7-diyl or 9,9-dimethylfluorene-2,7-diyl; A ² is any one of the groups represented by the following formula.]

In formula (1-1) to formula (1-3), R ¹ is methyl or ethyl; Z ¹ is a single bond, —COO— or —OCO—; Z ² is —COO— or —OCO Y is independently hydrogen or fluorine; X is —OCF ₃ or —CN; w is 0 or 1; a is an integer from 1 to 10;
In formulas (2-1) to (2-2), R ² is independently methyl or ethyl; Z ³ is a single bond or —O—; Z ^{4 to} Z ⁷ are independently − COO -, - OCO -, - CH 2 CH 2 COO -, - OCOCH 2 CH 2 -, - CH = CHCOO- or -OCOCH = CH- and is; L ¹ ~L ⁴ are independently hydrogen or fluorine M is an integer of 0 to 10, and when m is 0, Z ³ is a single bond; n is 0 or 1; A ¹ is 1,4-phenylene, 3-methyl-1,4- Phenylene, 2-trifluoromethyl-1,4-phenylene, 3-trifluoromethyl-1,4-phenylene, 2,3-bis (trifluoromethyl) -1,4-phenylene, 9-methylfluorene-2, 7-diyl or 9,9-dimethylfluorene-2,7-diyl There; liquid crystal film according to claim 1, A ² is characterized in that any one of the groups represented by the following formula.

The liquid crystal film according to claim 1 , wherein the polymer having a polar group has a carboxyl group and / or an amino group in a molecular chain. A homeotropic alignment state is formed by applying and polymerizing the polymerizable liquid crystal composition according to claim 1 on a support substrate having a polar surface , and the support substrate having the polar surface. Is a glass substrate surface-treated by a coating treatment with a polymer having a polar group, a method for producing a homeotropic alignment liquid crystal film. An optical compensation element comprising the homeotropic alignment liquid crystal film according to any one of claims 1 to 3 . An optical compensation element comprising a homeotropic alignment liquid crystal film produced by the method according to claim 4 . An optical element comprising the homeotropic alignment liquid crystal film according to any one of claims 1 to 3 and a polarizing plate. An optical element comprising a homeotropic alignment liquid crystal film produced by the method according to claim 4 and a polarizing plate. A liquid crystal display device comprising the optical compensation element according to claim 5 or 6 on an inner surface or an outer surface of a liquid crystal cell. A liquid crystal display device comprising the optical element according to claim 7 or 8 on an outer surface of a liquid crystal cell.