KR20140046973A - Polymerizable liquid crystal composition and optical anisotropy film - Google Patents

Abstract

The purpose of the present invention is to provide a polymerizable liquid crystal composition for not using an organic solvent, enabling to be coated on a substrate and having a high refractive index anisotropy. To achieve the purpose, the present invention provides the polymerizable liquid crystal composition characterized by comprising a compound indicated as Formula (1-1). [In Formula (1-1), R1 refers to hydrogen or methyl; W1 and W2 independently to hydrogen, fluorine, methyl and methoxy; and R2 to alkyl having 1-10 carbons or alkoxy having 1-10 carbons, wherein at least one -CH2- in the alkyl or the alkoxy can be substituted with -O-.].

Description

Polymerizable liquid crystal composition and optically anisotropic film {POLYMERIZABLE LIQUID CRYSTAL COMPOSITION AND OPTICAL ANISOTROPY FILM}

This invention relates to the polymeric liquid crystal composition containing a polymeric liquid crystal compound, the film (optical anisotropic film) which has the optical anisotropy obtained using this composition, and the liquid crystal display element containing this optically anisotropic film.

A polymeric liquid crystal compound is used for optically anisotropic films, such as a polarizing plate, a polarizing reflection plate, and a retardation plate (patent document 1). It is because this compound shows optical anisotropy in a liquid crystal state, and this anisotropy is fixed by superposition | polymerization. Since the optical characteristics required for an optically anisotropic film differ according to the objective, the compound which has the characteristic according to the objective is needed. Since the compound used for the use of an optically anisotropic body is difficult to control the anisotropy mentioned above alone, it may be used as a composition in combination with various compounds.

A polymerizable liquid crystal composition may be used as ink which added the organic solvent for the purpose of adjusting the coating property. In order to manufacture the film which has optically anisotropy using a polymeric liquid crystal composition, the ink which melt | dissolved a polymeric liquid crystal compound, a photoinitiator, surfactant, etc. in the organic solvent, and adjusted solution viscosity, leveling property, etc. is prepared. This ink is applied to the alignment-treated transparent substrate, the solvent is dried, and the polymerizable liquid crystal composition is oriented on the substrate. Next, ultraviolet rays are irradiated and polymerized to fix the alignment state.

Recently, a method of using a lenticular lens for stereoscopic image display has been proposed (Patent Document 2). The lenticular lens is a fine fish cake-shaped convex lens, and by installing this lens on the surface of the image, it can be separated for right eye recognition and left eye recognition, and stereoscopic vision is possible due to unsighted eyesight. Done. Moreover, in order to improve the optical characteristic and visibility of a lenticular lens, the technique using a polymeric liquid crystal composition is proposed (nonpatent literature 1). By using a material having high optical anisotropy, there is also an advantage such that the lens can be thinned.

When manufacturing a lenticular lens using a polymeric liquid crystal composition, a polymeric liquid crystal composition is inject | poured, the orientation is carried out, and it is immobilized by ultraviolet irradiation in the mold which has a dent of a fish cake type | mold. At this time, when an ink containing an organic solvent is used, a step of drying the solvent is required, which may result in remarkably inferior productivity. Therefore, a material with a low liquid crystal lower limit temperature is required so that a polymerizable liquid crystal composition can be injected into a mold without using an organic solvent.

In addition, when manufacturing optically anisotropic films, such as a lenticular lens, using a polymeric liquid crystal composition, after apply | coating a polymeric liquid crystal composition to a base material, it maintains a liquid crystal state without crystallizing until it is immobilized by ultraviolet irradiation. There is a need. Depending on manufacturing conditions, it may be left to apply for a long time until it is immobilized after apply | coating to a base material, and it is calculated | required to maintain a liquid crystal state at room temperature as long as possible.

As a material with a low liquid crystal lower limit temperature, the bicyclic phenylene type (meth) acrylate monomer is proposed (patent document 3, nonpatent literature 2). However, since the liquid crystal lower limit temperature of the said monomer is 40 degreeC or more, such a material has a high possibility that it will be difficult to maintain a liquid crystal state for a long time at room temperature, when combining a material and a composition with a relatively high liquid crystal lower limit temperature, and a liquid crystal lower limit further. Low temperature materials are required. Moreover, the material containing a cyclohexane ring is also known as a material with low liquid crystal lower limit temperature (patent document 4). However, since such an material has low optical anisotropy, in order to obtain desired optical characteristics, it is necessary to thicken the thickness of the optically anisotropic film, and thus it is difficult to make full use of the advantages of the polymerizable liquid crystal composition. Moreover, it is known that the compound which has bulky substituents, such as a long chain alkyl group, is also a material with low liquid crystal lower limit temperature (patent document 5). However, such a material is concerned about deterioration of optical characteristics due to inferior alignment uniformity.

Japanese Patent Application Publication No. 2002-372623 Japanese Patent Application Publication No. 6-214323 Japanese Patent Application Publication No. Hei 10-195138 Japanese Patent Application Publication No. Hei 9-316032 Japanese Patent Application Publication No. 2009-184974

IDW '04, pages 1495-1496 Mol. Cryst. Liq. Cryst., 261, 593-603 (1995)

The 1st objective of this invention is to provide the polymeric liquid crystal composition with low liquid crystal lower limit temperature and high optical anisotropy. A 2nd object is to provide the optically anisotropic film according to a use which the orientation of the film which consists of this polymeric liquid crystal composition is uniform. A 3rd object is to provide the liquid crystal display element containing this optically anisotropic film.

As a result of thorough examination, it discovered that the said subject was solved by using the polymeric liquid crystal composition which has the bicyclic phenylene type polymeric liquid crystal compound which has fluorine, and came to complete this invention. The polymerizable liquid crystal composition of the present invention is shown in the following [1].

[1] A polymerizable liquid crystal composition comprising a compound represented by formula (1).

[In Formula (1), R <^1> is hydrogen or methyl; Z <^1> is -COO- or -OCO-; W <^1> and W <^2> are respectively independently hydrogen, halogen, C1-C5 alkyl, or C1-C5 Alkoxy of 5; R ² is alkyl having 1 to 20 carbon atoms or alkoxy having 1 to 20 carbon atoms, at least one of -CH ² -in the alkyl and alkoxy may be substituted with -O-; n is 1 Or 2.]

Phenylene having fluorine as a substituent can lower the liquid crystal lower limit temperature. In addition, the compound of formula (1), which is a bicyclic phenylene-based polymerizable liquid crystal compound having fluorine, not only has a low liquid crystal lower limit temperature, but also has excellent compatibility with other liquid crystal compounds, excellent alignment uniformity, and the like. Since it has the characteristic of, it is useful as a structural component of a polymeric liquid crystal composition. The optically anisotropic film made of the polymerizable liquid crystal composition of the present invention can be used for, for example, a retardation plate, a polarizing element, a selective reflection film, a brightness enhancement film, and a viewing angle compensation film which are components of a liquid crystal display element.

The term in this specification is used as follows. A liquid crystal compound is a general term for the compound which has a liquid crystal phase, and the compound which does not have a liquid crystal phase but is useful as a component of a liquid crystal composition. The liquid crystal phase is a nematic phase, a smectic phase, a cholesteric phase or the like, and in most cases, a nematic phase. Liquid crystal lower limit temperature is the temperature of the minimum which shows a liquid crystal phase, and is a temperature which transitions from a liquid crystal phase to a crystal. Polymerization means the ability of a monomer to polymerize by means of light, heat, a catalyst, etc., and to provide a polymer. The compound represented by Formula (1) may be represented by compound (1). About the compound represented by another formula, it may be called according to the same simplified method. The meaning of the term "liquid crystallinity" is not limited only to having a liquid crystal phase. Even if it does not have a liquid crystal phase itself, when mixed with another liquid crystal compound, the characteristic which can be used as a component of a liquid crystal composition is also included in the meaning of liquid crystal. The term "at least one" used when describing the structure of a compound means that it is at least 1 with respect to the number as well as a position. For example, the expression "at least one A may be substituted with B, C, or D" means that at least one A is substituted with B, at least one A is substituted with C, and at least one It is meant to include not only the case where A is substituted with D but also the case where a plurality of A is substituted with at least two of B to D. However, the definition that at least one -CH ² -may be substituted with -O- does not include the substitution which results in the coupling group -OO- as a result. In addition, when at least 1 -CH ² -is substituted with -O-, carbon number does not exceed the range described. For example, R ² in formula (1) is alkylene having 1 to 20 carbon atoms, and in this alkylene, at least one -CH ² -may be substituted with -O-, but is substituted with -O-. The carbon number of the alkylene containing this in this case does not exceed 20. This rule is the same for other definitions.

The optically active compound which has a polymeric group may be called a polymeric optically active compound, an optically active compound, or just a compound. Similarly, the polymerizable liquid crystal composition may be referred to as a liquid crystal composition or only a composition. The case where a compound has one polymeric group may be called monofunctional. In addition, when a compound has two or more polymeric groups, it may be called polyfunctional or the name corresponding to the number of polymeric groups.

Here, the meaning of-(F) n in Formula (1) is demonstrated. This indicates that hydrogen at any of positions 2, 3, 5, and 6 on 1,4-phenylene may be substituted with fluorine, and the number of substitutions thereof is represented by n. That is, when n = 1, it represents that hydrogen in any of positions 2, 3, 5, 6 on 1,4-phenylene is substituted with fluorine, and when n = 2, 1,4-phenyl It shows that two hydrogens in positions 2, 3, 5, and 6 on the lene are substituted with fluorine.

The invention consists of the following items [1] to [11].

[1] A polymerizable liquid crystal composition comprising a compound represented by formula (1).

[In Formula (1), R <^1> is hydrogen or methyl; Z <^1> is -COO- or -OCO-; W <^1> and W <^2> are independently hydrogen, halogen, C1-C5 alkyl, or C1-C5 R ² is alkyl having 1 to 20 carbon atoms or alkoxy having 1 to 20 carbon atoms, and at least one -CH ² -in the alkyl and alkoxy may be substituted with -O-; n is 1 or 2]

[2] The polymerizable liquid crystal composition according to [1], wherein formula (1) is a compound of formula (1-1).

[In Formula (1-1), R <^1> is hydrogen or methyl; W <^1> and W <^2> are independently hydrogen, fluorine, methyl, or methoxy; R <^2> is C1-C10 alkyl or C1-C10 Alkoxy, and at least one -CH ² -in this alkyl and alkoxy may be substituted with -O-.]

[3] The polymerizable liquid crystal composition according to [1] or [2], which contains at least one compound selected from compounds represented by formulas (M1), (M2) and (M3).

[In formula (M1), (M2), and (M3), R <^1> is hydrogen or methyl; A <^1> is respectively independently ¹ , 4- phenylene, 1, 4- cyclohexylene, or naphthalene-2, 6-. Diyl, in this 1,4-phenylene, at least one hydrogen may be substituted with fluorine, alkyl having 1 to 5 carbon atoms or alkoxy having 1 to 5 carbon atoms; A ² is 1,4-phenylene, 1 , 4-cyclohexylene, naphthalene-2,6-diyl or fluorene-2,7-diyl, in which 1,4-phenylene, at least one hydrogen is fluorine, chlorine, cyano, hydroxy, It may be substituted with formyl, acetoxy, acetyl, trifluoromethyl, alkyl of 1 to 5 carbon atoms, alkoxy of 1 to 5 carbon atoms or alkyl ester of 1 to 5 carbon atoms, and in fluorene-2,7-diyl , Hydrogen at position 9 may be substituted with alkyl having 1 to 5 carbon atoms; Z ² is each independently a single bond, -C ₂ H _4- , -COO-, -OCO-, -C≡C-,- CH = CHCOO-, -OCOCH = CH-, -COOC ₂ H _4- , -C ₂ H ₄ OCO-, -C ₂ H ₄ C OO- or -OCOC2H4-; W ¹ and W ² are each independently hydrogen, fluorine, methyl or methoxy; Y is cyano, alkyl of 1 to 10 carbon atoms or alkoxy of 1 to 10 carbon atoms, and the alkyl and At least one CH ² — in alkoxy may be substituted with —O—; Q is a single bond, —O—, —COO—, —OCO— or —OCOO—; p is an integer from 1 to 12; R is each independently an integer of 0 to 12; a is 1 or 2; b is an integer of 0 to 2, c and d are each independently an integer of 0 to 2, and satisfies 1≤c + d≤3; []

[4] The polymerizable liquid crystal composition according to [1] to [3], which contains a compound represented by formula (1) and at least one compound selected from compounds represented by formula (M2-1).

[In Formula (M2-1), R <^1> is hydrogen or methyl; Z <^2> is each independently a single bond, -COO-, -OCO-, -C≡C-, -CH = CHCOO-, -OCOCH = CH -, -C ₂ H ₄ COO- or -OCOC ₂ H _4- ; W ¹ and W ² are each independently hydrogen, fluorine, methyl or methoxy; W ³ is independently hydrogen or alkyl having 1 to 5 carbon atoms Q is -O-, -COO-, -OCO- or -OCOO-; r is an integer of 1 to 12.]

[5] The polymerizable liquid crystal composition according to any one of [1] to [4], wherein the compound represented by the formula (1) is a compound represented by the formula (1-1-a).

[In formula (1-1-a), R <^2> is C2-C10 alkyl and at least 1 CH <^2> -in this alkyl may be substituted by -O-.]

[6] The polymerizable liquid crystal composition according to [1] to [5], which is nematic at room temperature.

[7] 10-50% by weight of the compound represented by Formula (1) with respect to 100% by weight of the total amount of the compound represented by Formula (1), Formula (M1), Formula (M2), and Formula (M3). The polymeric liquid crystal composition as described in any one of [1]-[6] containing 50-90 weight% of compounds represented by (M1) and a formula (M2).

[8] The polymerizable liquid crystal composition according to any one of [1] to [7], which can be applied to a substrate without using a solvent.

[9] An optically anisotropic film obtained by polymerizing the polymerizable liquid crystal composition according to any one of [1] to [8].

[10] The optically anisotropic film according to [9], wherein the refractive anisotropy is 0.15 or more.

[11] A liquid crystal display device having the optically anisotropic film according to [9] or [10].

The composition of this invention contains at least 1 compound chosen from the group of the compound represented by Formula (1) as (A) component.

In formula (1),

R ¹ is hydrogen or methyl, preferably hydrogen.

Z ¹ is -COO- or -OCO-, and preferably -COO-.

W ¹ and W ² are each independently hydrogen, halogen, alkyl having 1 to 5 carbon atoms or alkoxy having 1 to 5 carbon atoms, preferably hydrogen, fluorine, methyl or methoxy, and more preferably hydrogen.

R ² is alkoxy of 1 to 20 carbon atoms or alkyl of 1 to 20 carbon atoms, at least one -CH ² in the alkyl and alkoxy - may be substituted with -O-, preferably of 1 to 10 carbon atoms Alkyl or C1-C10 alkoxy, More preferably, they are C2-C10 alkyl.

n is 1 or 2, Preferably it is 1.

The composition of this invention contains at least 1 compound chosen from the group of the compound represented by Formula (M1), (M2), and (M3) as (B) component.

In formula (M1),

R ¹ is hydrogen or methyl.

A ¹ is independently 1,4-phenylene, 1,4-cyclohexylene or naphthalene-2,6-diyl, and in this 1,4-phenylene, at least one hydrogen is fluorine or 1 to 5 carbon atoms. Or alkyl having 1 to 5 carbon atoms. Z ² is independently a single bond, -C ₂ H _4- , -COO-, -OCO-, -C≡C-, -CH = CHCOO-, -OCOCH = CH-, -COOC ₂ H _4- , -C ₂ H ₄ OCO—, —C ₂ H ₄ COO— or —OCOC ₂ H ₄ —.

W ¹ and W ² are each independently hydrogen, fluorine, methyl or methoxy.

Y is cyano, alkyl having 1 to 10 carbon atoms or alkoxy having 1 to 10 carbon atoms, and at least one -CH ² -in the alkyl and alkoxy may be substituted with -O-.

p is an integer from 1 to 12.

a is 1 or 2.

In formula (M2),

R ¹ is hydrogen or methyl.

A ² is 1,4-phenylene, 1,4-cyclohexylene, naphthalene-2,6-diyl or fluorene-2,7-diyl, and in this 1,4-phenylene, at least one hydrogen May be substituted with fluorine, chlorine, cyano, hydroxy, formyl, acetoxy, acetyl, trifluoromethyl, alkyl of 1 to 5 carbon atoms, alkoxy of 1 to 5 carbon atoms or alkyl ester of 1 to 5 carbon atoms, In fluorene-2,7-diyl, hydrogen at position 9 may be substituted with alkyl having 1 to 5 carbon atoms.

Z ² is independently a single bond, -C ₂ H _4- , -COO-, -OCO-, -C≡C-, -CH = CHCOO-, -OCOCH = CH-, -COOC ₂ H _4- , -C ₂ H ₄ OCO—, —C ₂ H ₄ COO— or —OCOC ₂ H ₄ —.

W ¹ and W ² are each independently hydrogen, fluorine, methyl or methoxy.

Q is a single bond, -O-, -COO-, -OCO- or -OCOO-.

r is independently an integer of 0-12.

b is an integer of 0-2.

In formula (M3),

R ¹ is hydrogen or methyl.

A ¹ is independently 1,4-phenylene, 1,4-cyclohexylene or naphthalene-2,6-diyl, and in this 1,4-phenylene, at least one hydrogen is fluorine or 1 to 5 carbon atoms. Or alkyl having 1 to 5 carbon atoms.

Z ² is independently a single bond, -C ₂ H _4- , -COO-, -OCO-, -C≡C-, -CH = CHCOO-, -OCOCH = CH-, -COOC ₂ H _4- , -C ₂ H ₄ OCO—, —C ₂ H ₄ COO— or —OCOC ₂ H ₄ —.

Q is a single bond, -O-, -COO-, -OCO- or -OCOO-.

r is independently an integer of 0-12.

c and d are each independently integers of 0 to 2 and satisfy 1≤c + d≤2.

As (B) component, it is more preferable to contain at least 1 compound chosen from the group of the compound represented by Formula (M2-1).

R ¹ is hydrogen or methyl.

Each Z ¹ is independently a single bond, -COO-, -OCO-, -C≡C-, -CH = CHCOO-, -OCOCH = CH-, -C ₂ H ₄ COO- or -OCOC ₂ H _4- .

W ¹ and W ² are each independently hydrogen, fluorine, methyl or methoxy.

W ³ is independently hydrogen or alkyl having 1 to 5 carbon atoms.

Q is -O-, -COO-, -OCO- or -OCOO-.

r is an integer from 1 to 12.

The composition of this invention contains the compound represented by Formula (1) as (A) component, and at least 1 compound chosen from the group of the compound represented by Formula (M1), (M2), and (M3) ( It is preferable to contain as B) component.

Moreover, with respect to 100 weight% of total amounts of (A) component and (B) component, 10-50 weight% of (A) component and 50-90 weight% of (B) component are contained.

The composition of the present invention may further contain a nonionic surfactant. Examples of nonionic surfactants are fluorine-based, silicon-based or hydrocarbon-based. Nonionic surfactant has the effect of improving the smoothness of a coating film.

The composition of this invention has a nematic phase and a smectic liquid crystal phase at room temperature. When the composition of this invention is apply | coated and formed into a film on the plastic substrate which is subjected to the orientation processing, such as a rubbing process, or the thin film of plastic, it becomes homogeneous orientation or hybrid orientation. Moreover, when a nonpolymerizable or polymeric optically active compound is added to the composition of this invention, it becomes a twist orientation. When a compound having a cardo structure or a monofunctional polymerizable liquid crystal compound is added to the composition of the present invention, homeotropic orientation can be easily obtained.

The compound used for the composition of this invention is demonstrated.

Compound (1) has a bicyclic structure composed of phenylene having fluorine as a substituent and another phenylene as mesogen, and has one (meth) acryl group as the polymerizable group. This compound shows liquid crystallinity in the vicinity of room temperature, and shows relatively large optical anisotropy exceeding (DELTA) n = 0.1.

Compound (M1) is a monofunctional polymerizable liquid crystal compound, but unlike compound (1), it has a spacer between the polymerizable group and the mesogen. Compound (M2) is a bifunctional polymerizable liquid crystal compound, and since this polymer has a three-dimensional structure, it becomes a hard polymer compared with the compound which has one polymerizable group. Compound (M3) is a trifunctional polymerizable liquid crystal compound, and this polymer can form a strong network and becomes a harder polymer than a compound having one and two polymerizable groups. Thereafter, the compounds (M1), (M2) and (M3) and the compounds derived therefrom may be collectively referred to as compound (M).

The composition of this invention may contain the other polymeric compound different from compound (1), (M1), (M2), (M3), and a nonionic surfactant. This composition may contain a silane coupling agent in order to improve the adhesiveness of a coating film and a support base material. This composition may contain additives, such as a polymerization initiator and a photosensitizer suitable for a polymerization reaction. In order to improve the characteristic of a polymer, this composition may contain additives, such as a ultraviolet absorber, antioxidant, a radical trapping agent, a light stabilizer, and a chain transfer agent. This composition may contain the organic solvent.

The preferable ratio in the case of adding a nonionic surfactant is 0.0001-0.03 by the weight ratio with respect to the total weight of (A) component and (B) component. The range of more preferable weight ratio is 0.0001-0.005.

The preferable ratio in the case of adding a silane coupling agent is 0.01-0.15 by the weight ratio with respect to the total weight of (A) component and (B) component. The range of more preferable weight ratio is 0.03-0.10.

When adding another polymeric compound, the preferable ratio is 0.01-0.50 in the weight ratio with respect to the total weight of (A) component and (B) component, More preferably, it is 0.03-0.30. When using additives, such as a polymerization initiator, the usage-amount should just be the minimum amount which achieves the objective.

Next, the preferable example of compound (1) is shown below.

Preferable examples of the compound (M1) are shown below.

In formulas (M1-1) to (M1-15), R ¹ is independently hydrogen or methyl, and p is an integer of 1 to 12 independently.

Preferable examples of the compound (M2) are shown below.

In formulas (M2-1-1) to (M2-1-10) and formulas (M2-2-1) to (M2-2-22), R ¹ is independently hydrogen or methyl, and r is independently It is an integer of 1-12, and when there are two or more r in a formula, arbitrary two r may be same or different.

Preferred examples of the compound (M3) are shown below.

In formulas (M3-1) to (M3-10), R ¹ is independently hydrogen or methyl, r is independently an integer of 1 to 12, and when there are two or more r in the formula, any two r may be the same and may differ.

Next, a nonionic surfactant is illustrated.

Examples of the silicone-based nonionic surfactants include polyflow ATF-2, granol 100, granol 115, granol 400, and granol manufactured by Kyoeisha Chemical Co., Ltd., which are mainly composed of unmodified silicone or modified silicone. 410, Granol 435, Granol 440, Granol 450, Granol B-1484, Polyflow KL-250, Polyflow KL-260, Polyflow KL-270, Polyflow KL-280, BYK-300, BYK- 302, BYK-306, BYK-307, BYK-310, BYK-315, BYK-320, BYK-322, BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-337, BYK-341, BYK-342, BYK-344, BYK-345, BYK-346, BYK-347, BYK-348, BYK-370, BYK-375, BYK-377, BYK-378, BYK-3500, BYK- 3510, and BYK-3570.

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

Examples of hydrocarbon-based nonionic surfactants include polyflow No. 3, polyflow No. 50 EHF, polyflow No. 54N, polyflow No. 75, polyflow No. 77, and polyflow based on acrylic polymers. No.85HF, Polyflow No.90, Polyflow No.95, Polyflow No.99C, BYK-350, BYK-352, BYK-354, BYK-355, BYK-358N, BYK-361N, BYK-380N, BYK-381, BYK-392, and BYK-Silclean 3700.

In addition, the said polyflow and granol are the names of the products currently sold by Kyoisha Chemicals. BYK is the name of the product sold by Big Chemi Japan Co., Ltd. Pgentant, FTX and KB are the names of products sold in Neos. The said surfactant may be used independently and may be used in mixture of 2 or more.

Next, another polymeric compound, an additive, and the organic solvent are illustrated. These compounds may be commercially available products. Examples of other polymerizable compounds are compounds having one polymerizable group, compounds having two polymerizable groups, and polyfunctional compounds having three or more polymerizable groups.

Examples of the compound having one polymerizable group include styrene, nuclear substituted styrene, acrylonitrile, vinyl chloride, vinylidene chloride, vinyl pyridine, N-vinylpyrrolidone, vinylsulfonic acid, fatty acid vinyl (e.g. vinyl acetate), α, β-ethylenically unsaturated carboxylic acid (e.g., acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, etc.), alkyl ester of (meth) acrylic acid (C1-C18 alkyl), hydroxy of (meth) acrylic acid Alkyl ester (C1-C18 of hydroxyalkyl), aminoalkyl ester of (meth) acrylic acid (C1-C18 of aminoalkyl), ether oxygen containing alkyl ester of (meth) acrylic acid (C3-C of ether oxygen containing alkyl) 18, for example: methoxyethyl ester, ethoxyethyl ester, methoxypropyl ester, methyl carbyl ester, ethyl carbyl ester, and butyl carbyl ester), N-vinylacetamide, vinyl p-tert-butylbenzoate, N, N -D Vinylyl benzoate, vinyl benzoate, vinyl pivalate, vinyl 2,2-dimethylbutyrate, vinyl 2,2-dimethylpentanoate, vinyl 2-methyl-2-butyrate, vinyl propionate, vinyl stearate, 2-ethyl-2 Vinyl methyl butyrate, dicyclopentanyloxyl (meth) acrylate, isobornyloxyl ethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dimethyladamantyl (meth) Acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, 2-acryloyloxyethyl phthalic acid , 2-acryloyloxyethyl-2-hydroxyethyl phthalic acid, 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, polyethyleneglycol of the polymerization degree 1-100, polypropylene glycol, ethylene Oxid Polyethylene having a degree of polymerization of 1 to 100 blocked by a mono (meth) acrylic acid ester or di (meth) acrylic acid ester of polyalkylene glycol such as a copolymer of propylene oxide or an alkyl group having 1 to 6 carbon atoms It is mono (meth) acrylic acid ester of polyalkylene glycol, such as glycol, a polypropylene glycol, and the copolymer of ethylene oxide and a propylene oxide.

Examples of the compound having two polymerizable groups include 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, neopentyl glycol diacrylate, and dimethylol tri Cyclodecane diacrylate, triethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, tetraethylene glycol diacrylate, bisphenol A EO addition diacrylate, bisphenol A glycidyl diacrylate (Bis coat V # 700), polyethyleneglycol diacrylate, and methacrylate compounds of these compounds.

Examples of the compound having three or more polymerizable groups include pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylol EO addition tri (meth) acrylate, and tris (meth) acryloyl Oxyethyl phosphate, tris (meth) acryloyloxyethyl) isocyanurate, alkyl modified dipentaerythritol tri (meth) acrylate, EO modified trimethylolpropane tri (meth) acrylate, PO modified trimethylolpropane tree (Meth) acrylate, pentaerythritol tetra (meth) acrylate, alkyl modified dipentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate , Dipentaerythritol monohydroxypenta (meth) acrylate, alkyl modified dipentaerythritol penta (meth) acrylate, biscoat V ＃ 802 ( Functional groups = 8), and biscot V ＃ 1000 (functional groups = average 14). "Bis Court" is a trade name of Osaka Organic Chemical Co., Ltd. The functional group having 16 or more functional groups is obtained by acrylating Boltorn H20 (16 functional), Boltorn H30 (32 functional) and Boltorn H40 (64 functional) sold by Perstorp Specialty Chemicals.

In addition, you may contain the polymeric bisphenol fluorene derivative which has a cardo structure. These compounds are suitable for further controlling the orientation direction and increasing the degree of curing of the polymer. Examples of the polymerizable bisphenol fluorene derivative having a cardo structure are shown in formulas (α-1) to (α-6).

In order to optimize the superposition | polymerization rate of a polymeric liquid crystal composition, you may use a well-known radical photopolymerization initiator. The preferable addition amount of a radical photopolymerization initiator is 0.0001-0.20 by the weight ratio with respect to the total weight of (A) component and (B) component. The ranges more preferable than this weight ratio are 0.001-0.15. The more preferable range is 0.01 to 0.15. Examples of the radical photopolymerization initiator include 2-hydroxy-2-methyl-1-phenylpropan-1-one (Darcure 1173), 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-1,2 -Diphenylethan-1-one (irgacure 651), 1-hydroxyylcyclohexyl-phenyl-ketone (irgacure 184), irgacure 127, irgacure 500 (irgacure 184 and benzophene Rice flour mixture), Irgacure 2959, Irgacure 907, Irgacure 369, Irgacure 379, Irgacure 754, Irgacure 1300, Irgacure 819, Irgacure 1700, Irgacure 1800, Ir Cure 1850, Irgacure 1870, Darocure 4265, Darocure MBF, Darocure TPO, Irgacure 784, Irgacure 754, Irgacure OXE01, and Irgacure OXE02. The Tarocure and Irgacure are both names of products sold by BASF Japan. Known sensitizers for these [isopropyl thioxanthone, diethyl thioxanthone, ethyl-4-dimethylaminobenzoate (Darocure EDB), 2-ethylhexyl-4-dimethylaminobenzoate (Darocure EHA), etc. ] May be added.

As the radical photopolymerization initiator, the following radical photopolymerization initiators can also be used.

p-methoxyphenyl-2,4-bis (trichloromethyl) triazine, 2- (p-butoxystyryl) -5-trichloromethyl-1,3,4-oxadiazole, 9-phenyla Chridine, 9,10-benzphenazine, benzophenone / mihilerketone mixture, hexaarylbiimidazole / mercapto benzimidazole mixture, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl Propane-1-one, benzyldimethyl ketal, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2,4-diethylxanthone / p-dimethylaminobenzoic acid Methyl mixture, benzophenone / methyltriethanol amine mixture.

One or two or more chain transfer agents may be added to the polymerizable liquid crystal composition to control the mechanical properties of the polymer. By using a chain transfer agent, the length of a polymer chain or the length of two crosslinked polymer chains in a polymer film can be controlled. These lengths can be controlled simultaneously. When the amount of the chain transfer agent is increased, the length of the polymer chain decreases. A preferred chain transfer agent is a thiol compound. An example of a monofunctional thiol is dodecanethiol, 2-ethylhexyl- (3-mercaptopropionate). Examples of the polyfunctional thiol include trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), and 1,4-bis (3-mercaptobutyryloxy) Butane (Carenz MT BD1), pentaerythritol tetrakis (3-mercaptobutylate) (Carenz MT PE1), and 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3, 5-triazine 2,4,6 (1H, 3H, 5H) -trione (Carenz MT NR1). "Carens" is a trade name of Showa Denko Co., Ltd.

A polymerization inhibitor can be added to a polymerizable liquid crystal composition in order to prevent the polymerization start at the time of storage. Known polymerization inhibitors can be used, and preferable examples thereof are 2,5-di (tert-butyl) hydroxytoluene (BHT), hydroquinone, methyl blue, diphenylpic acid hydrazide (DPPH), benzothia Gin, 4-nitrosodimethylaniline (NIDI), o-hydroxybenzophenone.

In order to improve the storage property of a polymeric liquid crystal composition, you may add a polymerization inhibitor. When radicals are generated in the composition or the composition solution, the polymerization reaction of the polymerizable compound is accelerated. It is preferable to add a polymerization inhibitor for the purpose of preventing this. As a polymerization inhibitor, a phenolic antioxidant, sulfur antioxidant, and phosphoric acid antioxidant can be used.

In order to further improve the weather resistance of the polymerizable liquid crystal composition, an ultraviolet absorber, a light stabilizer (radical scavenger), an antioxidant, or the like may be added. Examples of ultraviolet absorbers include Tinuvin PS, Tinuvin P, Tinuvin 99-2, Tinuvin 109, Tinuvin 213, Tinuvin 234, Tinuvin 326, Tinuvin 328, Tinuvin 329, Tinuvin 384-2, Tinuvin 571, Tinuvin 900, Tinuvin 928, Tinuvin 1130, Tinuvin 400, Tinuvin 405, Tinuvin 460, Tinuvin 479, Tinuvin 5236, Adecastab LA-32, Adecastab LA- Adecastab LA-36, adecastab LA-31, adecastab 1413, and adecastab LA-51. "Tinuvin" is a brand name of BASF Japan Co., Ltd., and "adecastab" is a brand name of ADEKA.

Examples of light stabilizers include Tinuvin 111 FDL, Tinuvin 123, Tinubin 144, Tinubin 152, Tinubin 292, Tinubin 622, Tinubin 770, Tinubin 765, Tinubin 780, Tinubin 905, Tinubin 5100 , Tinuvin 5050, 5060, Tinuvin 5151, Kimasorb 119 FL, Kimasorb 944 FL, Kimasorb 944 LD, Adecastab LA-52, Adecastab LA-57, Adecastab LA-62, Manufactured by Adecastab LA-67, Adecastab LA-63 P, Adecastab LA-68 LD, Adecastab LA-77, Adecastab LA-82, Adecastab LA-87, Cytec Saisorb UV-3346, and Goodlite UV-3034 manufactured by Goodrich. "Kimasorb" is a trade name of BASF Japan.

Examples of antioxidants include smistizers BHT and smistizers sold by ADEKA Adecastab AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, Sumitomo Chemical Co., Ltd. BBM-S, and Smizer GA-80, and Irganox 1076, Irganox1010, Irganox3114, and Irganox245 sold by BASF Japan. You may use these commercial items.

In order to control adhesiveness with a board | substrate, you may further add a silane coupling agent to a polymeric liquid crystal composition. Specifically, vinyltrialkoxysilane, 3-isocyanatepropyltriethoxysilane, N- (2-aminoethyl) 3-aminopropyltrialkoxysilane, N- (1,3-dimethylbutylidene) -3- ( Trialkoxysilyl) -1-propanamine, 3-glycidoxypropyltrialkoxysilane, 3-chlorotrialkoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrialkoxysilane, and the like. Another example is dialkoxymethylsilane in which one of the alkoxy groups (three) is substituted with methyl in these compounds.

Since the liquid crystal lower limit temperature is low, the polymeric liquid crystal composition of this invention can be apply | coated to a board | substrate surface as it is. However, in order to facilitate application, the polymerizable liquid crystal composition is diluted using a solvent, or each component of the polymerizable liquid crystal composition is mixed with a solvent to prepare a solution of the polymerizable liquid crystal composition comprising the polymerizable liquid crystal composition and the solvent. You may prepare and apply this solution. This solvent can be used independently, and may mix and use two or more. Examples of the solvent include ester solvents, amide solvents, alcohol solvents, ether solvents, glycol monoalkyl ether solvents, aromatic hydrocarbon solvents, halogenated aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, halogenated aliphatic hydrocarbon solvents, and alicyclic solvents. It is a hydrocarbon type solvent, a ketone solvent, and an acetate solvent.

Preferred examples of the ester solvent include alkyl acetates (e.g. methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, 3-methoxybutyl, isobutyl acetate, pentyl acetate and isopentyl acetate) and trifluoro Ethyl roacetate, alkyl propionate (e.g. methyl propionate, methyl 3-methoxypropionate, ethyl propionate, propyl propionate and butyl propionate), alkyl butyrate (e.g. methyl butyrate, ethyl butyrate, butyl butyrate, isobutyl butyrate and butyric acid propyl) , Dialkyl maronic acid (e.g. diethyl maronic acid), alkyl glycolate (e.g. methyl glycolate and ethyl glycolate), alkyl lactic acid (e.g. methyl lactate, ethyl lactate, isopropyl lactate, n-propyl lactic acid, lactic acid Butyl and ethylhexyl lactate), monoacetin, γ-butyrolactone and γ-valerolactone.

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

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

Preferred examples of the ether solvents are ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, bis (2-propyl) ether, 1,4-dioxane and tetrahydrofuran (THF).

Preferable examples of the glycol monoalkyl ether solvents include ethylene glycol monoalkyl ethers (such as ethylene glycol monomethyl ether and ethylene glycol monobutyl ether), diethylene glycol monoalkyl ethers (such as diethylene glycol monoethyl ether) Ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether (e.g. propylene glycol monobutyl ether), dipropylene glycol monoalkyl ether (e.g. dipropylene glycol monomethyl ether), ethylene glycol monoalkyl ether acetate (e.g. ethylene glycol mono) Butyl ether acetate), diethylene glycol monoalkyl ether acetate (e.g. diethylene glycol monoethyl ether acetate), triethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate (e.g. propylene glycol monomethyl ether acetate, propylene glycol Monoethyl ether It is dipropylene glycol monomethyl ether acetate), and diethylene glycol methyl ethyl ether acetate and propylene glycol monobutyl ether acetate), dipropylene glycol monoalkyl ether acetate (e.

Preferred examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, mesitylene, ethylbenzene, diethylbenzene, i-propyl benzene, n-propyl benzene, tert-butylbenzene, s-butylbenzene, n-butylbenzene, And tetralin. A preferable example of the halogenated aromatic hydrocarbon solvent is chlorobenzene. Preferred examples of the aliphatic hydrocarbon solvents are hexane and heptane. Preferred examples of the halogenated aliphatic hydrocarbon solvent include chloroform, dichloromethane, carbon tetrachloride, dichloroethane, trichlorethylene and tetrachlorethylene. Preferred examples of the alicyclic hydrocarbon solvent are cyclohexane and decalin.

Preferred examples of the ketone solvents are acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, and methyl propyl ketone.

Preferred examples of the acetate solvent are ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl acetoacetate, and 1-methoxy-2-propyl acetate.

From the viewpoint of the solubility of the polymerizable liquid crystal compound, it is preferable to use an amide solvent, an aromatic hydrocarbon solvent, a ketone solvent, and considering the boiling point of the solvent, an ester solvent, an alcohol solvent, an ether solvent, It is also preferable to use a glycol monoalkyl ether solvent together. Although there is no restriction | limiting in particular about selection of a solvent, When using a plastic substrate as a support base material, it is necessary to lower a drying temperature and to prevent a solvent from eroding a board | substrate in order to prevent deformation of a board | substrate. The solvent preferably used in this case is an aromatic hydrocarbon solvent, a ketone solvent, an ester solvent, an ether solvent, an alcohol solvent, an acetate solvent or a glycol monoalkyl ether solvent.

The proportion of the solvent in the solution of the polymerizable liquid crystal composition is 10 to 95% based on the total weight of the solution. The preferable range of this ratio is 10 to 70%, and a more preferable range is 10 to 50%.

In the following description, the polymer (optical anisotropic film) obtained by superposing | polymerizing a polymeric liquid crystal composition may be called a liquid crystal film. A liquid crystal film can be obtained as follows. First, a polymeric liquid crystal composition is apply | coated on a support substrate in a fluid state, and a coating film is formed. When preparing the solution of a polymeric liquid crystal composition, it apply | coats on a support substrate, it is dried, and a coating film is formed. The coating film is irradiated with light to polymerize the polymerizable liquid crystal composition to fix the nematic alignment formed by the composition in the coating film in the liquid crystal state. Support substrates that can be used are glass and plastic films. Examples of the plastic film include polyimide, polyamideimide, polyamide, polyetherimide, polyether ether ketone, polyether ketone, polyketone sulfide, polyether sulfone, polysulfone, polyphenylene sulfide, polyphenylene oxide , Polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyacetal, polycarbonate, polyallylate, acrylic resin, polyvinyl alcohol, polypropylene, cellulose, triacetylcellulose and its partial saponified products, epoxy resins, phenols Resins and cycloolefin resins.

Although norbornene-type resin, dicyclopentadiene type resin, etc. are mentioned as cycloolefin resin, It is not limited to these. Of these, those having no unsaturated bond or having an unsaturated bond hydrogenated are preferably used. For example, a hydrogenated product of a ring-opening (co) polymer of one or two or more norbornene monomers, an addition (co) polymer of one or two or more norbornene monomers, a norbornene monomer and an olefin monomer ( Addition copolymers of ethylene, α-olefin, etc.), addition copolymers of norbornene-based monomers and cycloolefin-based monomers (cyclopentene, cyclooctene, 5,6-dihydrodicyclopentadiene, etc.), and modified products thereof Specific examples include ZEONEX, ZEONOR (manufactured by Japan Zeon), ARTON (manufactured by JSR Corporation), TOPAS (manufactured by Tiko Corporation), APEL (manufactured by Mitsui Chemicals Corporation), Eshina (manufactured by Sekisui Chemical Co., Ltd.), OPTOREZ (Made by Hitachi Chemical Co., Ltd.) is mentioned.

These plastic films may be a uniaxial stretched film or a biaxially stretched film. These plastic films may be subjected to surface treatment such as hydrophilization treatment such as corona treatment or plasma treatment, or hydrophobization treatment. The hydrophilization treatment method is not particularly limited, but a corona treatment or a plasma treatment is preferable, and a particularly preferable method is a plasma treatment. For the plasma treatment, methods described in Japanese Patent Application Laid-Open No. 2002-226616, Japanese Patent Application Laid-Open No. 2002-121648, and the like may be used. Moreover, in order to improve adhesiveness of a liquid crystal film and a plastic film, you may provide an anchor coat layer. If such an anchor coat layer improves the adhesiveness of a liquid crystal film and a plastic film, there will be no problem with any material of an inorganic type and an organic type. The plastic film may be a laminated film. Instead of the plastic film, a metal substrate such as aluminum, iron or copper having a slit-shaped groove on the surface thereof, or a glass substrate such as alkali glass, borosilicate glass, lead glass, etc., which has been etched into the slit surface thereof may be used.

Prior to the coating film formation of a polymeric liquid crystal composition, when forming the liquid crystal film of homogeneous orientation and a hybrid orientation, these glass, a plastic film, etc. support physical and mechanical surface treatment by rubbing etc. are performed. When forming the liquid crystal film of homeotropic orientation, surface treatment, such as rubbing, is not performed in many cases, but you may perform a rubbing process from the point which prevents orientation defects. Any method may be employed for the rubbing treatment, but a method in which a rubbing cloth made of a material such as rayon, cotton or polyamide is usually wound on a metal roll or the like and moved while rotating the roll while being in contact with a supporting substrate or a polymer film, The method etc. which move the support substrate side in the state which fixed the roll are employ | adopted. The rubbing treatment may be performed directly on the supporting substrate, or a polymer coating such as polyimide generally called an alignment film may be previously formed on the supporting substrate, and the rubbing treatment may be performed on the polymeric coating. The rubbing treatment method is as described above. Depending on the type of the supporting substrate, silicon oxide may be obliquely deposited on the surface to impart orientation capability.

Moreover, when forming the liquid crystal film of homogeneous orientation and hybrid orientation, in addition to the physical and mechanical surface treatment by rubbing etc., the polymer film, such as polyimide and polyacrylate generally called a photo-alignment film on a support substrate previously, You may form and polarize-UV treatment to this polymer film.

Examples of coating methods for obtaining a uniform film thickness when applying the polymerizable liquid crystal composition or a solution thereof include spin coating method, micro gravure coating method, gravure coating method, wire bar coating method, dip coating method and spray coating method. , Meniscus coat method and die coat method. In particular, the wire bar coating method or the like in which shearing stress is applied to the liquid crystal composition at the time of coating may be used when the orientation of the liquid crystal composition is controlled since the surface treatment of the substrate by rubbing or the like is not performed.

When apply | coating the solution of the polymeric liquid crystal composition of this invention, you may heat-process in order to form the polymeric liquid crystal layer of a uniform film thickness, ie, the layer of a polymeric liquid crystal composition, on a support substrate after application | coating. As the heat treatment, hot plates, drying furnaces, or the like may be used for blowing hot air or hot air.

The temperature and time at the time of heat-processing a coating film, the wavelength of the light used for light irradiation, the quantity of light irradiated from a light source, etc. are the kind and composition ratio of the compound used for a polymeric liquid crystal composition, the presence or absence of addition of a photoinitiator, According to the addition amount etc., a preferable range differs. Therefore, the conditions regarding the temperature and time of heat processing of the coating film demonstrated below, the wavelength of the light used for light irradiation, and the quantity of light irradiated from a light source show the approximate range to the last.

It is preferable to perform heat processing of a coating film on the conditions which can obtain the uniform orientation of a polymeric liquid crystal. You may perform above the liquid crystal phase transition point of a polymeric liquid crystal composition. An example of a heat processing method is a method of heating a coating film to the temperature which the said polymeric liquid crystal composition shows a nematic liquid crystal phase, and forming a nematic orientation in the polymeric liquid crystal composition in a coating film. You may form a nematic orientation by changing the temperature of a coating film in the temperature range in which a polymeric liquid crystal composition shows a nematic liquid crystal phase. This method is a method in which the nematic orientation is roughly completed in the coating film by heating the coating film to a high temperature range of the above temperature range, and then the temperature is lowered to give an ordered orientation. Even if any of the above heat treatment methods are employed, the heat treatment temperature is from room temperature to 120 ° C. The preferable range of this temperature is room temperature to 80 degreeC, and a more preferable range is room temperature to 60 degreeC. The heat treatment time is 5 seconds to 2 hours. The preferable range of this time is 10 second-40 minutes, and a more preferable range is 20 second-20 minutes. In order to raise the temperature of the layer which consists of a polymeric liquid crystal composition to predetermined temperature, it is preferable to make heat processing time into 5 second or more. In order not to reduce productivity, it is preferable to make heat processing time into 2 hours or less. In this way, the polymerizable liquid crystal layer of the present invention can be obtained.

The nematic alignment state of the polymerizable liquid crystal compound formed in the polymerizable liquid crystal layer is fixed by polymerizing the polymerizable liquid crystal compound by light irradiation. The wavelength of light used for light irradiation is not particularly limited. An electron beam, an ultraviolet ray, a visible ray, and an infrared ray (hot line). Usually, ultraviolet rays or visible light may be used. The wavelength range is 150-500 nm. The preferable range is 250-450 nm, and a more preferable range is 300-400 nm. Examples of the light source 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 (ultra high pressure mercury lamps, xenon lamps, mercury xenon lamps). . Preferable examples of the light source include a metal halide lamp, a xenon lamp, an ultra-high pressure mercury lamp, and a high-pressure mercury lamp. You may select the wavelength range of an irradiation light source by providing a filter etc. between a light source and a polymeric liquid crystal layer, and passing only a specific wavelength range. The amount of light irradiated from the light source is ² to 5000 mJ / cm ² at the time of reaching the coating film surface. The preferable range of light quantity is 10-3000 mJ / cm <^2> , and a more preferable range is 100-2000 mJ / cm <^2> . It is preferable that the temperature conditions at the time of light irradiation are set similarly to the said heat processing temperature. In addition, although the atmosphere of a polymerization environment may be any of nitrogen atmosphere, inert gas atmosphere, and air atmosphere, nitrogen atmosphere or inert gas atmosphere is preferable from a viewpoint of improving sclerosis | hardenability.

When using the polymerizable liquid crystal layer of this invention and the liquid crystal film which superposed | polymerized by light, heat, etc. in various optical elements, or when applying it as an optical compensation element used for a liquid crystal display device, tilt in the thickness direction It is extremely important to control the distribution of angles.

One method of controlling a tilt angle is a method of adjusting the kind, composition ratio, etc. of the liquid crystal compound used for a polymeric liquid crystal composition. The tilt angle can also be controlled by adding other components to the polymerizable liquid crystal compound. The tilt angle of the liquid crystal film can also be controlled by the kind, the amount of the surfactant added as one of the solvent, the solute concentration, and other components in the polymerizable liquid crystal composition. The tilt angle of the liquid crystal film can also be controlled by the kind of the supporting substrate or the polymer film, the rubbing conditions, the drying conditions of the coating film of the polymerizable liquid crystal composition, the heat treatment conditions, or the like. Moreover, the irradiation atmosphere in the photopolymerization process after orientation, the temperature at the time of irradiation, etc. also affect the tilt angle of a liquid crystal film. That is, it is thought that almost all the conditions in the manufacturing process of a liquid crystal film affect the tilt angle which was large or small. Therefore, arbitrary tilt angles can be made by selecting various conditions of the manufacturing process of a liquid crystal film suitably with optimization of a polymeric liquid crystal composition.

In the homogeneous orientation, the tilt angle is uniformly close to 0 ° from the substrate interface to the free interface, and is particularly distributed at 0 ° to 5 °. This orientation state is obtained by apply | coating the polymeric liquid crystal composition of this invention to the support substrate surface which surface-treated, such as rubbing, and forming a coating film.

The composition of this invention may contain the liquid crystalline compound which does not have a polymeric group. Examples of such non-polymerizable liquid crystalline compounds are described in LichCryst, LCI Publisher GmbH, Hamburg, Germany, which is a database of liquid crystalline compounds. As a specific example of the liquid crystalline compound which does not have a polymeric group, it is described in Unexamined-Japanese-Patent No. 2011-148762 p.66-69. The polymerizable liquid crystal composition of the present invention has good compatibility with other liquid crystal compounds. Such a polymerizable liquid crystal composition may further contain additives such as a dichroic dye and a fluorescent dye. By polymerizing this polymerizable liquid crystal composition, a composite material with a liquid crystal compound having no polymerizable group can be obtained.

You may add an optically active compound to the composition of this invention. Suitable examples of the optically active compound are compounds represented by formulas (Op-1) to (Op-25). In these formulas, Ak represents alkyl having 1 to 15 carbon atoms or alkoxy having 1 to 15 carbon atoms, and Me, Et and Ph represent methyl, ethyl and phenyl, respectively. P ² is a polymerizable group and is preferably a group containing (meth) acryloyloxy, vinyloxy, oxiranyl, or oxetanyl. The composition of this invention may be used as a raw material of the polymer demonstrated below, and may also use the liquid crystal which is a component of a liquid crystal display element.

As a specific example, Paragraph 0159 of p.70 of Unexamined-Japanese-Patent No. 2011-148762-paragraph 0170 of p.81 are mentioned.

A spiral structure (twisted structure) is obtained by applying and polymerizing a polymerizable liquid crystal composition containing an appropriate amount of a compound having an optical activity or a polymerizable liquid crystal composition containing an appropriate amount of a polymerizable compound having an optical activity on a substrate subjected to an alignment treatment. The retardation film shown can be obtained. This spiral structure is fixed by superposition | polymerization of a polymeric liquid crystal composition. The characteristic of the obtained liquid crystal film depends on the spiral pitch of the obtained spiral structure. This spiral pitch length can be adjusted with the kind and addition amount of an optically active compound. Although one optically active compound may be added, a plurality of optically active compounds may be used for the purpose of canceling the temperature dependency of the spiral pitch. In addition to the optically active compound, other polymerizable compounds may be included in the polymerizable liquid crystal composition.

Selective reflection of visible light which is a characteristic of the liquid crystal film as described above is that the helical structure acts on incident light to reflect circularly polarized light or elliptically polarized light. The selective reflection characteristic is represented by λ = nPitch (λ is the center wavelength of the selective reflection, n is the average refractive index, and Pitch is the spiral pitch, so that the center wavelength (λ) and the wavelength width (Δλ) are appropriately changed by changing n or Pitch). In order to improve color purity, the wavelength width Δλ may be reduced, and when the broadband reflection is desired, the wavelength width Δλ may be increased. In order to maintain the color purity, the thickness must be made too small, in order to maintain uniform orientation, the thickness must be made too large. It is preferable and 1-10 micrometers is more preferable.

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

A liquid crystal film can be used for the reflective film which set the reflection wavelength area | region described in Unexamined-Japanese-Patent No. 2004-333671 to near infrared (wavelength 800-2500 nm) by making spiral pitch longer than visible light. In order to lengthen a spiral pitch, it can achieve by using the optically active compound with a small torsion force, or reducing the addition amount of an optically active compound.

What kind of optically active compound may be used for the said optically active compound as long as it has a spiral structure and can mix suitably with the polymeric liquid crystal composition used as a base. Moreover, it may be a polymeric compound or a nonpolymerizable compound, and an optimal compound can be added according to the objective. In view of heat resistance and solvent resistance, polymerizable compounds are very suitable.

In addition, among the above-mentioned optically active compounds, a large torsional force (HTP: helical twisting power) is very suitable for shortening the spiral pitch. Representative examples of compounds with high torsional force are disclosed in GB2298202 and DE10221751.

The thickness (film thickness) of the liquid crystal film differs in appropriate thickness depending on the retardation according to the target device and the birefringence (value of optical anisotropy) of the liquid crystal film. Therefore, the range of thickness differs according to the objective, and is 0.05-100 micrometers as a reference. More preferable ranges are 0.1-50 micrometers, and still more preferable ranges are 0.5-20 micrometers. Preferable haze value of a liquid crystal film is 1.5% or less, and preferable transmittance | permeability is 80% or more. A more preferable haze value is 1.0% or less, and a more preferable transmittance is 95% or more. About the transmittance | permeability, it is preferable to satisfy the conditions mentioned above in visible region.

As the birefringence (value of optical anisotropy) of the liquid crystal film is higher, the thickness can be made thinner. The thinner the thickness, the better the optical characteristics such as haze value and transmittance. 0.15 or more are preferable and, as for birefringence ((DELTA) n) of the liquid crystal film of this invention, 0.2 or more is more preferable.

A liquid crystal film is effective as an optical compensation element applied to a liquid crystal display element (especially an active matrix type and a passive matrix type liquid crystal display element). Examples of the type of liquid crystal display element suitable for using this liquid crystal film as an optical compensation film include IPS type (in-plane switching), OCB type (optically compensated birefringence), TN type (twisted nematic), STN type (super twisted nematic), ECB type (electrically controlled birefringence), DAP type (strain effect on alignment), CSH type (color super homeotropic), VAN / VAC type (vertically oriented) Nematic / cholesteric), OMI type (optical mode interference), and SBE type (ultra birefringent effect). Moreover, this liquid crystal film can also be used as a phase retarder for display elements, such as guest-host type, ferroelectric molding, and antiferroelectric molding. And since the optimal value of parameters, such as distribution of the tilt angle of thickness direction required for a liquid crystal film, thickness, etc. strongly depends on the kind of liquid crystal display element to compensate and its optical parameter, it changes with kinds of element.

The liquid crystal film can also be used as an optical element integrated with a polarizing plate or the like, in which case it is disposed outside the liquid crystal cell. On the other hand, since the liquid crystal film as an optical compensation element has little or no elution of impurities to the liquid crystal filled in the cell, it can also be arrange | positioned inside a liquid crystal cell. For example, if the method disclosed in Japanese Patent Application Laid-open No. 2008-01943 is applied, the function of the color filter can be further improved by forming the polymerizable liquid crystal layer of the present invention on the color filter. The liquid crystal film of the homogeneous orientation complexed with a dichroic dye can be used also as an absorption type polarizing plate. In addition, the homogeneous orientation liquid crystal film complexed with the fluorescent dye can be used also as a polarization light-emitting film.

[Example]

Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these Examples. The evaluation method in an Example is shown next.

<Polymerization condition>

Under a nitrogen atmosphere, light having an intensity of 30 mW / cm ² (365 nm) was irradiated for 30 seconds using a 250 W ultra-high pressure mercury lamp (manufactured by Ushio Electric Co., Ltd., Multilite-250) at room temperature.

<Evaluation of orientation>

(1) Preparation of a glass substrate having a rubbed treated alignment film

On a 1.1 mm thick glass substrate, spin-coated a polyamic acid (Lixon Aligner (LIXON Aligner): manufactured by PIA-5370 JNC Co., Ltd.) for a low pretilt angle (horizontal alignment mode), and the solvent was a hot plate at 80 ° C. After drying over, the thing baked in 230 degreeC for 30 minutes was subjected to the rubbing process using a rayon cloth.

(2) Observation method by visual observation

The board | substrate with which the retardation film was formed was observed between two polarizing plates arrange | positioned by cross nicol, the board | substrate was rotated in the horizontal plane, and the contrast state was confirmed. The board | substrate with which the retardation film was formed was observed with the polarization microscope, and the presence or absence of the orientation defect was confirmed.

(3) Measurement by polarization analyzer

Light of wavelength 550 nm was irradiated to the board | substrate with which the retardation film was formed using the OPTIPRO polarization analyzer manufactured by Syntec. The retardation was measured while reducing the incident angle of this light from 90 degrees with respect to the film surface. Retardation (retardation; also referred to as retardation) is represented by Δn × d. The symbol Δn is the optical anisotropy value, and the symbol d is the thickness of the polymer film.

&Lt; Measurement of film thickness &

The layer of the liquid crystal film of the glass substrate with a liquid crystal film was scraped off, and the step was measured using the fine shape measuring apparatus (manufactured by KLATENCOR Co., Ltd., alpha step IQ).

<Evaluation of Optical Anisotropy (Δn)>

It was computed as retardation / film thickness from the retardation and film thickness value calculated | required about the liquid crystal film which has homogeneous orientation.

The compounds used in Examples and Comparative Examples are shown below.

[Synthesis Example 1]

Compound (1-1-a-1) was synthesized by the following method.

(First step)

100 g of 2-fluoro-4-hydroxybenzoic acid and 55.8 g of pyridine were added to 400 mL of tetrahydrofuran (THF), and the mixture was stirred at 10 ° C. or lower under a nitrogen atmosphere. 78.5g of acetic anhydride was dripped there. After dripping, it stirred at room temperature for 4 hours. Ethyl acetate and water were added for extraction. The organic layer was washed with saturated brine and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the obtained residue was recrystallized with ethyl acetate, and 94.0 g of compound (ex-1) was obtained.

(Second step)

30 g of compound (ex-1) and 0.1 g of pyridine were added to 150 mL of toluene and stirred at 60 ° C under a nitrogen atmosphere. 19.9 g of thionyl chlorides were dripped there. After dripping, it stirred at 60 degreeC for 4 hours, and distilled off the solvent under reduced pressure. Toluene 300mL was added to the obtained residue, and it stirred at 10 degrees C or less under nitrogen atmosphere. 50 mL of the toluene solution of 25 g of 4-amyl phenol was dripped there, and 23.1 g of triethylamines were dripped thereafter. After dripping, it stirred at room temperature for 4 hours. The mixture was extracted by addition of water, and the organic layer was washed with 1N aqueous sodium hydroxide solution and water. It dried with anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. It was added to 100 mL of THF and 50 mL of methanol to the obtained residue, and it stirred at 10 degrees C or less under nitrogen atmosphere. 18 mL of 28% aqueous ammonia solution was dripped there, and it stirred at room temperature for 8 hours. Ethyl acetate and water were added for extraction, and the organic layer was washed with saturated brine and dried over anhydrous magnesium sulfate. 39.2 g of compounds (ex-2) were obtained by distilling a solvent off under reduced pressure and recrystallizing the obtained residue with toluene.

(Third step)

39.2 g of compound (ex-2) and 19.7 g of triethylamine were added to 400 mL of dichloromethane, and the mixture was stirred at 10 ° C. or lower under a nitrogen atmosphere. 12.9 g of acrylic acid chlorides were dripped there, and it stirred at room temperature for 8 hours. The mixture was extracted by addition of water, and the organic layer was washed with 1N aqueous sodium hydroxide solution and water. It dried with anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography and recrystallized with methanol to give 27.3 g of the compound (1-1-a-1). The phase transition temperature of the obtained compound (1-1-a-1) is as follows.

Phase transition temperature: C 30 N 48 I

¹ H-NMR (500 MHz, CDCl ₃ ; δ ppm): 8.15 (t, 1H), 7.24 (d, 2H), 7.15-7.07 (m, 4H), 6.65 (d, 1H), 6.36-6.28 (m, 1H), 6.09 (d, 1H), 2.62 (t, 2H), 1.67-1.59 (m, 2H), 1.39-1.28 (m, 4H), 0.90 (t, 3H).

¹⁹ F-NMR (500 MHz, CDCl ₃ ; δ ppm): -104.98.

[Synthesis Example 2]

Compound (1-1-a-3) was synthesized by the following method.

(First step)

30 g of compound (ex-1) and 0.1 g of pyridine were added to 150 mL of toluene and stirred at 60 ° C under a nitrogen atmosphere. 19.9 g of thionyl chlorides were dripped there. After dripping, it stirred at 60 degreeC for 4 hours, and distilled off the solvent under reduced pressure. Toluene 300mL was added to the obtained residue, and it stirred at 10 degrees C or less under nitrogen atmosphere. 50 mL of the toluene solution of 23 g of 4- (2-methoxyethyl) phenol was dripped there, and then 23.1 g of triethylamine was dripped. After dripping, it stirred at room temperature for 4 hours. The mixture was extracted by addition of water, and the organic layer was washed with 1N aqueous sodium hydroxide solution and water. It dried with anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. THF100mL and methanol 50mL were added to the obtained residue, and it stirred at 10 degrees C or less under nitrogen atmosphere. 18 mL of 28% aqueous ammonia solution was dripped there, and it stirred at room temperature for 8 hours. Ethyl acetate and water were added for extraction, and the organic layer was washed with saturated brine and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the obtained residue was recrystallized with toluene, and 37.2 g of compound (ex-3) was obtained.

(Second step)

37.2 g of compound (ex-3) and 19.4 g of triethylamine were added to 400 mL of dichloromethane, and the mixture was stirred at 10 ° C. or lower under a nitrogen atmosphere. 12.8 g of acrylic acid chlorides were dropped therein, followed by stirring at room temperature for 8 hours. The mixture was extracted by addition of water, and the organic layer was washed with 1N aqueous sodium hydroxide solution and water. It dried with anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography and recrystallized with methanol to give 25.6 g of the compound (1-1-a-3). The phase transition temperature of the obtained compound (1-1-a-3) is as follows.

Phase transition temperature: C 34 (N-19) I

¹ H-NMR (500 MHz, CDCl ₃ ; δ ppm): 8.15 (t, 1H), 7.27 (d, 2H), 7.16 (d, 2H), 7.11 (d, 2H), 6.66 (d, 1H), 6.36 -6.28 (m, 1H), 6.09 (d, 1H), 3.61 (t, 2H), 3.37 (s, 3H), 2.91 (t, 2H).

¹⁹ F-NMR (500 MHz, CDCl ₃ ; δ ppm): -104.95.

[Synthesis Example 3]

Compound (M2-1-4-1) was synthesized by the following method.

(First step)

400 g of trans-p-coumaric acid and 10 mL of concentrated sulfuric acid were added to 1200 mL of methanol, and the mixture was stirred for 5 hours under reflux. The solvent was distilled off under reduced pressure. The obtained residue was poured into ice water, and ethyl acetate was added and extracted. The organic layer was washed with saturated sodium bicarbonate water followed by water and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure. The residue was recrystallized from ethanol to give 384.3 g of compound (ex-3).

(Second step)

100 g of compound (ex-3), 24.7 g of sodium hydroxide and 8.4 g of sodium iodide were added to 1000 mL of N, N-dimethylformamide (DMF), and the mixture was stirred at 60 ° C under a nitrogen atmosphere. 84.3 g of 6-chlorohexanol were dripped there. After dripping, it stirred at 80 degreeC for 8 hours. Ethyl acetate and water were added and extracted to the reaction solution. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure. The obtained residue and 24.7 g of sodium hydroxide were added to the mixed solution of 500 ml of water and 500 ml of methanol, and it stirred for 3 hours under heating reflux. The solvent was distilled off under reduced pressure, and the obtained residue was poured into 3N hydrochloric acid and reprecipitated. The crystals were filtered and recrystallized with ethanol to give 94.1 g of compound (ex-4).

(Third step)

80.0 g of compound (ex-4) and 66.8 g of dimethylaniline were added to 400 mL of toluene, and the mixture was stirred at room temperature under a nitrogen atmosphere. 31.5 g of acrylic acid chlorides were dripped there. After dripping, it stirred at 50 degreeC for 4 hours. The reaction solution was poured into iced water, extracted with ethyl acetate, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure. The obtained residue was recrystallized from toluene to obtain 37.6 g of compound (ex-5).

(Step 4)

20 g of compound (ex-5), 6.6 g of 9-methyl-2,7-dihydroxyfluorene and 1.6 g of 4-dimethylaminopyridine (DMAP) were added to 200 ml of dichloromethane and stirred under a nitrogen atmosphere. 30 mL of 13.6 g of 1, 3- dicyclohexylcarbodiimide (DCC) dichloromethane solutions were dripped there. After dropwise addition, the mixture was stirred at room temperature for 8 hours. The precipitated precipitate was filtered, and the organic layer was washed with water and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, the residue was purified by column chromatography, and recrystallized with ethanol to obtain 16.3 g of the compound (M2-1-4-1). The phase transition temperature of the obtained compound (M2-1-4-1) is as follows.

Phase transition temperature: C 74 N 250 <I

¹ H-NMR (500 MHz, CDCl ₃ ; δ ppm): 7.85 (d, 2H), 7.73 (d, 2H), 7.55 (d, 4H), 7.31 (s, 2H), 7.16 (d, 2H), 6.93 (d, 4H), 6.53 (d, 2H), 6.41 (d, 2H), 6.16-6.09 (m, 2H), 5.83 (d, 2H), 4.18 (t, 4H), 4.04-3.96 (m, 5H ), 1.87-1.80 (m, 4H), 1.76-1.69 (m, 4H), 1.57-1.43 (m, 11H).

Compound (M2-1-1-1) was synthesized according to the methods described in Japanese Patent Application Laid-open No. 2003-238491 and Japanese Patent Application Laid-open No. 2006-307150.

Compound (M2-2-2-1) is Makromol. Synthesis was carried out by the method described in Chem., 190, 2255-2268 (1989).

Compound (M2-2-2-2) is Makromol. Synthesis was carried out by the method described in Chem., 192, 59-74 (1991).

Compound (M2-2-7-1) was synthesized by the method described in 4063873.

Compound (M1-7-1) was synthesized by the method described in Macromolecules, 3938-3943, (23), 1990.

Compound (M1-2-1) is Makromol. Chem. 183, 2311-2321, (1982).

Compound (C-1) is Mol. Cryst. Liq. Synthesis was carried out by the method described in Cryst., 261, 593-603 (1995).

Compound (C-2) was synthesize | combined by the method of Unexamined-Japanese-Patent No. 9-316032.

Example 1

[Preparation of Polymerizable Liquid Crystal Composition (1)]

Compound (1-1-a-1): Compound (M2-1-1-1): Compound (M2-2-2-2): Compound (M2-1-4-1) = 25: 25: 25: These compounds were mixed in a weight ratio of 25. In this composition, a polymerization initiator Irgacure Oxe01 (manufactured by BASF Japan) with a weight ratio of 0.06, and a fluorine-based nonionic surfactant FTX-218 (manufactured by Neos) having a weight ratio of 0.005, and a polymerization inhibitor 2,5-di having a weight ratio of 0.005 (tert-butyl) hydroxytoluene (BHT) was added. The composition was heated to 60 ° C. and uniformly mixed to obtain a polymerizable liquid crystal composition (1). The polymerizable liquid crystal composition (1) maintained its fluidity even when left at room temperature for one day, and was determined to be a room temperature liquid crystal composition.

Next, the polymeric liquid crystal composition 1 was apply | coated by spin coating on the glass substrate which has a rubbing process complete alignment film. This board | substrate was heated at 80 degreeC for 5 minutes, it cooled at room temperature for 2 minutes, and the coating film was superposed | polymerized by the ultraviolet stream under nitrogen stream, and the liquid crystal film was obtained. The board | substrate with the obtained liquid crystal film was put between two polarizing plates arrange | positioned by cross nicol, the board | substrate was put in the dark field state, and it checked that there was no leakage of light, and it was that the orientation was uniform and had homogeneous orientation Judged. When the retardation of the board | substrate with this liquid crystal film was measured, 90 degree of retardation measurement value was 621 nm with respect to the film surface, and since film thickness is 3.45 micrometers, (DELTA) n was computed as 0.18.

[Example 2]

[Preparation of Polymerizable Liquid Crystal Composition (2)]

Compound (1-1-a-1): Compound (M2-1-1-1): Compound (M1-7-1): Compound (M2-1-4-1) = 25: 25: 25: 25 These compounds were mixed by weight. In this composition, a polymerization initiator Irgacure Oxe01 (manufactured by BASF Japan) with a weight ratio of 0.06, and a fluorine-based nonionic surfactant FTX-218 (manufactured by Neos) having a weight ratio of 0.002, and a polymerization inhibitor 2,5-di having a weight ratio of 0.005 (tert-butyl) hydroxytoluene (BHT) was added. The composition was heated to 60 ° C. and uniformly mixed to obtain a polymerizable liquid crystal composition (2). The polymerizable liquid crystal composition (2) maintained its fluidity even when left at room temperature for one day, and was determined to be a room temperature liquid crystal composition.

Next, the polymeric liquid crystal composition 2 was apply | coated by spin coating on the glass substrate which has a rubbing process complete alignment film. This board | substrate was heated at 80 degreeC for 5 minutes, it cooled at room temperature for 2 minutes, and the coating film was superposed | polymerized by the ultraviolet stream under nitrogen stream, and the liquid crystal film was obtained. The board | substrate with the obtained liquid crystal film was sandwiched between two polarizing plates arrange | positioned by cross nicol, and it confirmed that there was no light leakage in the dark field state, and it judged that the orientation was uniform and had homogeneous orientation. When the retardation of the board | substrate with this liquid crystal film was measured, 90 degrees of retardation measured value was 894 nm with respect to the film surface, and since film thickness is 3.44 micrometers, (DELTA) n was computed as 0.26.

[Example 3]

[Preparation of Polymerizable Liquid Crystal Composition (3)]

These compounds were mixed in the weight ratio of compound (1-1-a-1): compound (M1-2-1): compound (M2-2-2-1) = 20:30:50. In this composition, a polymerization initiator Irgacure Oxe01 (manufactured by BASF Japan) with a weight ratio of 0.06, and a fluorine-based nonionic surfactant FTX-218 (manufactured by Neos) having a weight ratio of 0.002, and a polymerization inhibitor 2,5-di having a weight ratio of 0.005 (tert-butyl) hydroxytoluene (BHT) was added. The composition was heated to 60 ° C. and uniformly mixed to obtain a polymerizable liquid crystal composition (3). The polymerizable liquid crystal composition (3) remained in fluidity even when left at room temperature for one day, and was determined to be a room temperature liquid crystal composition.

Next, the polymeric liquid crystal composition 3 was apply | coated by the spin coat on the glass substrate which has a rubbing process complete alignment film. This board | substrate was heated at 80 degreeC for 5 minutes, it cooled at room temperature for 2 minutes, and the coating film was superposed | polymerized by the ultraviolet stream under nitrogen stream, and the liquid crystal film was obtained. The board | substrate with the obtained liquid crystal film was sandwiched between two polarizing plates arrange | positioned by cross nicol, and it confirmed that there was no light leakage in the dark field state, and it judged that the orientation was uniform and had homogeneous orientation. When the retardation of the board | substrate with this liquid crystal film was measured, 90 degrees of retardation measured values were 504 nm with respect to the film surface, and since film thickness is 3.15 micrometers, (DELTA) n was computed as 0.16.

Example 4

[Preparation of Polymerizable Liquid Crystal Composition (4)]

These compounds were mixed in the weight ratio of compound (1-1-a-1): compound (M2-2-7-1): compound (M2-1-1-1) = 50:20:30. In this composition, a polymerization initiator Irgacure Oxe01 (manufactured by BASF Japan) with a weight ratio of 0.06, and a fluorine-based nonionic surfactant FTX-218 (manufactured by Neos) having a weight ratio of 0.002, and a polymerization inhibitor 2,5-di having a weight ratio of 0.005 (tert-butyl) hydroxytoluene (BHT) was added. The composition was heated to 60 ° C. and uniformly mixed to obtain a polymerizable liquid crystal composition (4). The polymerizable liquid crystal composition 4 was in a state of maintaining fluidity even when left at room temperature for one day, and was determined to be a room temperature liquid crystal composition.

Next, the polymeric liquid crystal composition 4 was apply | coated by spin coating on the glass substrate which has a rubbing process complete alignment film. This board | substrate was heated at 80 degreeC for 5 minutes, it cooled at room temperature for 2 minutes, and the coating film was superposed | polymerized by the ultraviolet stream under nitrogen stream, and the liquid crystal film was obtained. The board | substrate with the obtained liquid crystal film was sandwiched between two polarizing plates arrange | positioned by cross nicol, and it confirmed that there was no light leakage in the dark field state, and it judged that the orientation was uniform and had homogeneous orientation. When the retardation of the board | substrate with this liquid crystal film was measured, 90 degrees of retardation measured values were 700 nm with respect to the film surface, and since film thickness is 3.89 micrometers, (DELTA) n was computed as 0.18.

[Example 5]

[Preparation of Polymerizable Liquid Crystal Composition (5)]

These compounds were mixed in the weight ratio of compound (1-1-a-1): compound (1-1-a-3): compound (M2-1-4-1) = 30:20:50. In this composition, a polymerization initiator Irgacure Oxe01 (manufactured by BASF Japan) with a weight ratio of 0.06, and a hydrocarbon-based nonionic surfactant BYK-361N (manufactured by Bigchem Japan) with a weight ratio of 0.002, and a polymerization inhibitor 2,5- having a weight ratio of 0.005 Di (tert-butyl) hydroxytoluene (BHT) was added. The composition was heated to 60 ° C. and uniformly mixed to obtain a polymerizable liquid crystal composition (5). The polymerizable liquid crystal composition 5 was in a state of maintaining fluidity even when left at room temperature for one day, and was determined to be a room temperature liquid crystal composition.

Next, the polymeric liquid crystal composition 5 was apply | coated by spin coating on the glass substrate which has a rubbing process complete alignment film. This board | substrate was heated at 80 degreeC for 5 minutes, it cooled at room temperature for 2 minutes, and the coating film was superposed | polymerized by the ultraviolet stream under nitrogen stream, and the liquid crystal film was obtained. The board | substrate with the obtained liquid crystal film was sandwiched between two polarizing plates arrange | positioned by cross nicol, and it confirmed that there was no light leakage in the dark field state, and it judged that the orientation was uniform and had homogeneous orientation. When the retardation of the board | substrate with this liquid crystal film was measured, 90 degrees of retardation measured values were 568 nm with respect to the film surface, and since film thickness is 3.55 micrometers, (DELTA) n was computed as 0.16.

Comparative Example 1

Compound (C-1): Compound (M2-1-1-1): Compound (M2-2-2-2): Compound (M2-1-4-1) = 25: 25: 25: 25 in weight ratio The compounds were mixed in the same manner as in Example 1 except that these compounds were mixed. The polymerizable liquid crystal composition (6) was prepared in the same manner as in Example 1 with this composition. When the polymerizable liquid crystal composition 6 was left at room temperature for one day, crystallization progressed and fluidity was lost. Moreover, even if it heated up at 40 degreeC, fluidity | liquidity could not be obtained and a liquid crystal film could not be formed.

[Comparative Example 2]

Compound (C-2): Compound (M2-2-7-1): Compound (M2-1-1-1) = Same as Example 4 except for mixing these compounds in a weight ratio of 50:20:30 The compound was mixed by the method. The polymerizable liquid crystal composition (7) was prepared in the same manner as in Example 4 with this composition. The polymerizable liquid crystal composition 7 remained in fluidity even when left at room temperature for one day, and was a room temperature liquid crystal composition.

Next, the polymeric liquid crystal composition 7 was apply | coated by spin coating on the glass substrate which has a rubbing process complete alignment film. This board | substrate was heated at 80 degreeC for 5 minutes, it cooled at room temperature for 2 minutes, and the coating film was superposed | polymerized by the ultraviolet stream under nitrogen stream, and the liquid crystal film was obtained. When the retardation of the board | substrate with this liquid crystal film was measured, 90 degrees of retardation measured value was 536 nm with respect to the film surface, and since film thickness is 4.12 micrometers, (DELTA) n was computed as 0.13.

By using the polymeric liquid crystal composition of this invention, the liquid crystal film which has a uniform orientation form can be obtained without using a solvent, and the refractive index anisotropy of the liquid crystal film obtained becomes comparatively large.

Claims (11)

A polymeric liquid crystal composition containing the compound represented by following formula (1):

[In Formula (1), R <^1> is hydrogen or methyl; Z <^1> is -COO- or -OCO-; W <^1> and W <^2> are independently hydrogen, halogen, C1-C5 alkyl, or C1-C5 Alkoxy of 5; R ² is alkyl having 1 to 20 carbon atoms or alkoxy having 1 to 20 carbon atoms, at least one of -CH ² -in the alkyl and alkoxy may be substituted with -O-; n is 1 Or 2; The method of claim 1,
A polymerizable liquid crystal composition, wherein the formula (1) is a compound of the formula (1-1):

[In Formula (1-1), R ¹ is hydrogen or methyl; W ¹ and W ² are independently hydrogen, fluorine, methyl or methoxy; R ² is alkyl having 1 to 10 carbons or 1 to 10 carbon atoms. Alkoxy, and at least one -CH ² -in the alkyl and the alkoxy may be substituted with -O-. The method of claim 1,
A polymerizable liquid crystal composition containing at least one compound selected from the compounds represented by the following formulas (M1), (M2) and (M3):

[In the formulas (M1), (M2) and (M3), R ¹ is hydrogen or methyl; A ¹ is each independently 1,4-phenylene, 1,4-cyclohexylene or naphthalene-2,6. -Diyl, in the 1,4-phenylene, at least one hydrogen may be substituted with fluorine, alkyl having 1 to 5 carbon atoms or alkoxy having 1 to 5 carbon atoms; A ² is 1,4-phenylene, 1,4-cyclohexylene, naphthalene-2,6-diyl or fluorene-2,7-diyl, in which 1,4-phenylene, at least one hydrogen is fluorine, chlorine, cyano, hydroxy , Formyl, acetoxy, acetyl, trifluoromethyl, alkyl of 1 to 5 carbon atoms, alkoxy of 1 to 5 carbon atoms, or alkyl ester of 1 to 5 carbon atoms, and may be substituted with fluorene-2,7-diyl. And hydrogen at position 9 may be substituted with alkyl having 1 to 5 carbon atoms; Z ² is each independently a single bond, -C ₂ H _4- , -COO-, -OCO-, -C≡C-, -CH = CHCOO-, -OCOCH = CH-, -COOC ₂ H _4- , -C ₂ H ₄ OCO-, -C ₂ H ₄ COO- or -OCOC ₂ H _4- ; W ¹ and W ² are each independently hydrogen, fluorine, methyl or methoxy; Y is cyano, alkyl having 1 to 10 carbon atoms or Alkoxy having 1 to 10 carbon atoms, and at least one CH ² -in the alkyl and alkoxy may be substituted with -O-; Q is a single bond, -O-, -COO-, -OCO- or -OCOO P is an integer of 1 to 12; r is each independently an integer of 0 to 12; a is 1 or 2; b is an integer of 0 to 2, and c and d are independently 0 to 2; Integer and satisfies 1 ≦ c + d ≦ 3]. The method of claim 1,
A polymeric liquid crystal composition containing the compound represented by said formula (1), and at least 1 compound chosen from the compound represented by following formula (M2-1):

[In Formula (M2-1), R ¹ is hydrogen or methyl; Z ² is each independently a single bond, -COO-, -OCO-, -C≡C-, -CH = CHCOO-, -OCOCH = CH-, -C ₂ H ₄ COO- or -OCOC ₂ H _4- ; W ¹ and W ² are each independently hydrogen, fluorine, methyl or methoxy; W ³ is independently hydrogen or of 1 to 5 carbon atoms Alkyl; Q is -O-, -COO-, -OCO-, or -OCOO-; r is an integer from 1 to 12. The method of claim 1,
A polymerizable liquid crystal composition, wherein the compound represented by the formula (1) is a compound represented by the following formula (1-1-a):

[In Formula (1-1-a), R ² is alkyl having 2 to 10 carbon atoms, and at least one CH ² -in the alkyl may be substituted with -O-. The method of claim 1,
A polymerizable liquid crystal composition which is nematic at room temperature. The method of claim 3,
10-50 weight% of the compound represented by said Formula (1) with respect to 100 weight% of total amounts of the compound represented by said Formula (1), Formula (M1), Formula (M2), and Formula (M3), said Formula A polymerizable liquid crystal composition containing 50 to 90% by weight of the compound represented by (M1) and the formula (M2). The method of claim 1,
A polymerizable liquid crystal composition which can be applied to a substrate without using a solvent. The optically anisotropic film obtained by superposing | polymerizing the polymeric liquid crystal composition of Claim 1. 10. The method of claim 9,
Optically anisotropic film whose refractive index anisotropy is 0.15 or more. The liquid crystal display element which has the optically anisotropic film of Claim 9.