WO2014192657A1 - Polymerisable liquid crystal composition, phase difference film, phase difference patterning film, and homogeneously aligned liquid crystal film - Google Patents

Abstract

Provided are: a polymerisable liquid crystal composition which has excellent storage stability, and in which disordering of alignment does not occur when polymerised; and a phase difference film, a phase difference patterning film, and a homogeneously aligned (horizontally aligned) liquid crystal film which are formed using the polymerisable liquid crystal composition. The polymerisable liquid crystal composition is characterised by: including two or more polymerisable compounds represented by general formula (I), and an organic solvent; and satisfying |SA-SB|=1,2, and SA+SB ≤ 10, where SA and SB are, respectively, m of any two polymerisable compounds from among the polymerisable compounds (in the formula, P¹ and P² represent reactive functional groups, MG represents a mesogenic group or a mesogenity-supporting group, and the two m represent the same numerical value from 1-6).

Description

Polymerizable liquid crystal composition, retardation film, retardation patterning film, and homogeneous alignment liquid crystal film

The present invention relates to a polymerizable liquid crystal composition, a retardation film, a retardation patterning film, and a homogeneous alignment liquid crystal film.

In recent years, development of polarizing plates, retardation plates, etc. using polymerizable liquid crystal materials has been actively conducted. These are applied to a base material that has been subjected to rubbing treatment or a base material on which a photo-alignment photo-alignment film has been formed, and after applying a solution containing a polymerizable liquid crystal material, drying the solvent, and then polymerizing by ultraviolet rays or heat. To obtain. Since these polymerizable liquid crystal materials are generally used in a form diluted with a solvent, solubility in a solvent and storage stability are required.

Generally, in order to improve the storage stability of a liquid crystal composition obtained by dissolving a polymerizable liquid crystal compound in an organic solvent, the molecular shape is made bulky (made bulky). In Patent Documents 1 and 2, the polymerizable liquid crystal compound is made asymmetrical, which not only leads to an increase in cost, but also reduces the liquid crystallinity and causes a phenomenon in which the alignment is disturbed when polymerized. There is a problem. Addition of a non-liquid crystalline compound also improves the solubility and storage stability, but the liquid crystallinity deteriorates and the orientation deteriorates. Many chiral compounds are non-liquid crystalline by themselves. Even when these chiral compounds are added, the storage stability is improved, but there is a problem that they can be used only for polymerizable cholesteric liquid crystal materials.

JP 2008-127336 A JP 2010-159324 A

The present invention has been made in view of the above circumstances, is a polymerizable liquid crystal composition that is excellent in storage stability and does not cause disorder in alignment when polymerized, and a position formed using the polymerizable liquid crystal composition. An object is to provide a phase difference film, a phase difference patterning film, and a homogeneous alignment (horizontal alignment) liquid crystal film.

As a result of intensive studies by the present inventors, the length of a linking group connecting a reactive functional group (polymerizable group) and a mesogenic group or mesogenic indicator group in two or more polymerizable compounds contained in the composition. However, it has been found that the storage stability of the composition is improved by satisfying predetermined conditions, and the present invention has been completed.

The first aspect of the present invention includes two or more polymerizable compounds represented by the following general formula (I) and an organic solvent, and m of any two polymerizable compounds among the polymerizable compounds is A polymerizable liquid crystal composition characterized by satisfying | SA−SB | = 1 or 2 when SA and SB are satisfied, and satisfying SA + SB ≦ 10.

In the above formula, P ¹ and P ² represent a reactive functional group, MG represents a mesogenic group or a mesogenic support group, and two m represent the same numerical value of 1 to 6.

The second aspect of the present invention is a retardation film using the polymerizable liquid crystal composition of the first aspect.
The third aspect of the present invention is a retardation patterning film using the polymerizable liquid crystal composition of the first aspect.
A fourth aspect of the present invention is a homogeneously aligned liquid crystal film using the polymerizable liquid crystal composition of the first aspect.

The liquid crystal composition according to the present invention has excellent storage stability and excellent orientation when polymerized. By using this liquid crystal composition, it is possible to produce a retardation film, a retardation patterning film, and a homogeneous alignment liquid crystal film excellent in orientation.

Hereinafter, although the present invention will be described based on preferred embodiments, the present invention is not limited to such embodiments.

<< Polymerizable liquid crystal composition >>
The polymerizable liquid crystal composition of the first embodiment of the present invention includes two or more polymerizable compounds (polymerizable liquid crystal compounds) represented by the following general formula (I) and an organic solvent, and among the polymerizable compounds: When m of any two polymerizable compounds is SA and SB, respectively, | SA−SB | = 1 or 2, and SA + SB ≦ 10 is satisfied.

In general formula (I), P ¹ and P ² represent reactive functional groups, MG represents a mesogenic group or a mesogenic supporting group, and two m represent the same numerical value of 1 to 6.

Examples of the reactive functional group represented by P ¹ and P ² in the general formula (I) include the following general formula (II-c), general formula (II-d), and general formula (II-e). Represents a substituent selected from the group consisting of the substituents represented. P ¹ and P ² in a single molecule are preferably the same.

In the general formula (II-c), formula (II-d) and formula ^{(II-e), R 21} , R 22, R 23, R 31, R 32, R 33, R 41, R 42 and R Each of ⁴³ independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 5 carbon atoms, and n represents 0 or 1.
R ³¹ in the general formula (II-d) represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms.
The left end of the substituent (reactive functional group) represented by the above general formula is bonded to the carbon atom of the methylene group of the general formula (I).
The alkyl group is preferably a linear or branched alkyl group, and more preferably a linear alkyl group. Some or all of the hydrogen atoms bonded to the alkyl group may be substituted with halogen atoms.

Examples of the reactive group represented by the general formula (II-c), general formula (II-d) or general formula (II-e) include the following reactive groups (P-1) and (P-2). , (P-3), (P-5), (P-6), (P-9), and (P-10). Of these reactive functional groups, the following (P-1) or (P-2) is preferred, and the following (P-1) is more preferred from the viewpoint of enhancing the polymerizability and storage stability.

Examples of the mesogenic group or mesogenic support group represented by MG in the general formula (I) include groups represented by the following general formula (II-b).

In general formula (II-b), A1, A2 and A3 are each independently 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5- Diyl group, 1,3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene-2,6- Diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 2, 6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4,4a, 9,10a-octahydrophenanthrene 2,7-diyl Group or a fluorene 2,7-diyl group,
The 1,4-phenylene group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2 , 7-diyl group, 1,2,3,4,4a, 9,10a-octahydrophenanthrene 2,7-diyl group and one or more hydrogen atoms bonded to fluorene 2,7-diyl group are F, Cl, CF ₃ , OCF ₃ , cyano group, alkyl group having 1 to 8 carbon atoms, alkoxy group, alkanoyl group, alkanoyloxy group, alkenyl group having 2 to 8 carbon atoms, alkenyloxy group, alkenoyl group or alkenoyl May be substituted by an oxy group,
Z0 and Z3 are each independently —COO—, —OCO—, —CH═CH—, —C≡C—, —CH═CHCOO—, —OCOCH═CH—, —CONH—, —NHCO—, — O—, —S—, —NH—, —N (CH ₃ ) —, —CO—, —OCOO—, —SCO—, —COS— or a single bond,
Z1 and Z2 are each independently —COO—, —OCO—, —CH ₂ CH ₂ —, —OCH ₂ —, —CH ₂ O—, —CH═CH—, —C≡C—, —CH═ CHCOO—, —OCOCH═CH—, —CH ₂ CH ₂ COO—, —CH ₂ CH ₂ OCO—, —COOCH ₂ CH ₂ —, —OCOCH ₂ CH ₂ —, —CONH—, —NHCO—, —O— _{, -S -, - NH -,} - n (CH 3) -, - CO -, - OCOO -, - SCO -, - COS- or a single bond, ^{n b} represents 0, 1 or 2.

The polymerizable liquid crystal composition of this embodiment contains two or more polymerizable compounds represented by the general formula (I). Of the polymerizable compounds represented by the general formula (I) contained in the polymerizable liquid crystal composition, “m” in the general formula (I) representing the first polymerizable compound is “SA”. And when “m” in the general formula (I) representing the second polymerizable compound is represented as “SB”, at least one set satisfying | SA−SB | = 1 or 2 and satisfying SA + SB ≦ 10 There are combinations of two polymerizable compounds.

The polymerizable liquid crystal composition of the present embodiment preferably contains 2 to 4 polymerizable compounds represented by the general formula (I), more preferably 2 to 3 types, more preferably 2 types. More preferably. When 3 or 4 polymerizable compounds represented by the general formula (I) are contained, the relationship between SA and SB is established in any combination of the polymerizable compounds. If you do.

The polymerizable compound represented by the general formula (I) contained in the polymerizable liquid crystal composition of the present embodiment is preferably a polymerizable compound represented by the following general formula (I-1).

Hereinafter, the general formula (I-1) will be described.
Y ²¹ represents a hydrogen atom or a methyl group.
E ²¹ represents an alkylene group having 1 to 8 carbon atoms.
Z ²¹ and Z ²² are each independently —COO—, —OCO—, —CH ₂ CH ₂ COO—, —CH ₂ CH ₂ OCO—, —COOCH ₂ CH ₂ —, —OCOCH ₂ CH ₂ —, Or it represents a single bond.
X ¹³ to X ²⁴ each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, a methoxy group, a CF ₃ group, or an OCF ₃ group, and 1 to 3 of X ¹³ to X ²⁴ Represents a fluorine atom, a chlorine atom, a methyl group, a methoxy group, a CF ₃ group, or an OCF ₃ group.
n ¹ is 0, 1 or 2. When n ¹ is 2 and a plurality of Z ²¹ are present, they may be the same or different, and when there are a plurality of 1,4-phenylene groups having substituents X17 to X20, they are the same. May be different.

Z ²¹ and Z ²² are preferably each independently —COO— or —OCO—.

Preferable specific examples represented by the general formula (I-1) include polymerizable compounds represented by the following general formulas (I-1-1) to (I-1-5).

In the formulas (I-1-1) to (I-1-5), Y ²² represents a hydrogen atom or a methyl group, and RI ¹ to RI ¹⁴ each independently represents a fluorine atom, a chlorine atom, a methyl group or a methoxy group. Nr ¹ to nr ¹⁴ are each independently an integer of 0 to 2, and when nr ¹ to nr ¹⁴ is 2 and there are a plurality of RI ¹ to RI ^14, they may be the same or different In general, m represents an integer of 1 to 8.
m is preferably from 2 to 7, and more preferably from 3 to 6.

In the general formulas (I-1-1), (I-1-3) to (I-1-5), the bonding positions of RI ¹ to RI ³ and RI ⁵ to RI ¹⁴ are not particularly limited, and nr ¹ ~ ^{nr 3,} if nr 5 ~ ^{nr 14} is 1, lateral position is preferred. When nr ¹ to nr ³ and nr ⁵ to nr ¹⁴ are 2, arbitrary substitution positions can be combined.

Of the polymerizable compounds represented by the general formulas (I-1-1) to (I-1-5), those represented by any one of the general formulas (I-1-1) to (I-1-4) A polymerizable compound represented by any one of the general formulas (I-1-2) to (I-1-4) is more preferable.

Among these polymerizable compounds, as a more preferable compound,
In the general formula (I-1-2), a compound in which Y ²² is a hydrogen atom, RI ⁴ is a hydrogen atom or a methyl group, and nr ⁴ is 0 or 1 is preferable.
In the general formula (I-1-3) or (I-1-4), a compound in which Y ²² is a hydrogen atom and nr ⁵ to nr ¹¹ are 0 is preferable.

Specific examples of the polymerizable compounds represented by the general formulas (I-1-1) to (I-1-5) are shown below.

As exemplified above, when the polymerizable compound represented by the general formula (I) has three ring structures, if the lateral hydrogen atom of the ring structure is substituted with a substituent, the polymerizable compound The solubility of the compound in the solvent is improved, and the storage stability of the polymerizable liquid crystal composition of this embodiment is improved, which is preferable. Furthermore, in order to further improve the storage stability, it is preferable to increase the solubility (compatibility) between a plurality of polymerizable compounds.

From the viewpoint of increasing the compatibility, it is preferable that the skeleton structures of the plurality of polymerizable compounds are approximated or the same. That is, the polymerizable liquid crystal composition of the present embodiment includes the above general formulas (I-1-1) to (I-1-4) as the two or more polymerizable compounds represented by the general formula (I). Any two or more polymerizable compounds selected from the group consisting of the polymerizable compounds represented by formula (I) are preferred, and the polymerizable compounds represented by the above general formulas (I-1-2) to (I-1-4) Any two or more polymerizable compounds selected from the group consisting of are more preferred.
Further, two or more compounds represented by the above general formula (I-1-2), two or more compounds represented by the above general formula (I-1-3), and the above general formula (I-1-) It is more preferable to contain two or more compounds represented by 4).

When the total weight of the polymerizable compounds (including monofunctional compounds described later) contained in the polymerizable liquid crystal composition of the present embodiment is 100 parts by weight, the total of the polymerizable compounds represented by the general formula (I) The content of is preferably more than 30% by weight and less than 95% by weight, more preferably 50 to 95% by weight, still more preferably 60 to 90% by weight.

In the polymerizable liquid crystal composition of the present embodiment, when two kinds of polymerizable compounds represented by the general formula (I) are included, the total weight of the polymerizable compounds contained in the polymerizable liquid crystal composition is 100 parts by weight, The content of each polymerizable compound represented by the general formula (I) is independently preferably more than 30 and 60% by weight or less, more preferably more than 30 and 50% by weight or less, more than 30 and 45% by weight. The following is more preferable. When the content is in these preferred ranges, the storage stability of the polymerizable liquid crystal composition of the present embodiment is further improved.

In the polymerizable liquid crystal composition of the present embodiment, when two kinds of polymerizable compounds represented by the general formula (I) are included, the first polymerizable compound represented by the general formula (I) and the second polymerizable compound. The difference in the compound content is preferably 0 to 30 parts by weight, more preferably 0 to 20 parts by weight, and still more preferably 0 to 10 parts by weight. Thus, the storage stability of the polymerizable liquid crystal composition of the present embodiment is further improved when the contents of the two polymerizable compounds are equal.

In addition, the liquid crystal composition of the present embodiment preferably includes a monofunctional compound having one reactive functional group in the molecule. By containing a monofunctional compound, the storage stability of the polymerizable liquid crystal composition of the present embodiment is further improved, and the use of polymer base material lamination (for example, retardation film and retardation patterning in the field of liquid crystal display) When used for a film and a homogeneous alignment (horizontal alignment) liquid crystal film, etc., properties such as excellent alignment can be imparted.

The substrate on which the solution containing the polymerizable liquid crystal composition of the present invention is applied is a substrate that is usually used for liquid crystal devices, displays, optical components and optical films, and after the application of the polymerizable liquid crystal composition of the present invention. There is no particular limitation as long as it is a material having heat resistance that can withstand heating during the drying of the liquid crystal or during the manufacture of the liquid crystal device. Examples of such a substrate include organic materials such as a glass substrate, a metal substrate, a ceramic substrate, and a polymer substrate. Among these, the polymer base material is preferable because it can be produced by roll-to-roll and is easy to handle as compared with a glass substrate or the like.

Furthermore, the base material (polymer base material) made of a polymer compound has excellent affinity with the polymerizable compound of the present embodiment, and after applying and drying a solution containing the polymerizable compound to the polymer base material, The polymerizable compound of the present embodiment is also suitable for applications that are laminated on a polymer substrate because it is easy to impart excellent orientation. Examples of the polymer compound constituting such a preferable polymer substrate include cellulose derivatives, polyolefin-based, polyester-based, polyethylene terephthalate, polycarbonate, polyacrylate-based, polyarylate, polyethersulfone, polyimide, polyphenylene sulfide, and polyphenylene ether. , Nylon, or polystyrene. Particularly preferred are cycloolefin polymer, triacetyl cellulose, and polymethyl methacrylate resin.

Further, the substrate may be subjected to an alignment treatment so that the polymerizable liquid crystal composition is easily aligned when the polymerizable liquid crystal composition of the present invention is applied and dried. As the alignment treatment, in addition to the method of directly rubbing the substrate, an alignment film used in a general liquid crystal device may be applied and the rubbing treatment may be performed. A particularly preferable method is a publicly known method using a photo-alignment film. When the photo-alignment film is used, a patterned retardation film can be produced.

Hereinafter, with respect to the “bifunctional compound”, the polymerizable compound represented by the following general formula (X) may be referred to as a “monofunctional compound”.
Examples of the monofunctional compound include polymerizable compounds represented by the following general formula (X).

<Monofunctional compound>
The polymerizable liquid crystal composition of the present embodiment has a polymerizable compound (monofunctional compound) represented by the following general formula (X) from the viewpoint of improving storage stability and improving alignment when polymerized. It is preferable to include one or more types, and it is more preferable to include two or more types.

In the case where the polymerizable liquid crystal composition of this embodiment contains two or more monofunctional compounds represented by the general formula (X), m ^x of any two monofunctional compounds is respectively SAx and SBx. In this case, it is preferable that 1 ≦ | SAx−SBx | ≦ 3 and 3 ≦ SAx + SBx ≦ 10.

(In the general formula (X), P ^x represents a reactive functional group, m ^x represents an integer of 1 to 8, MG represents a mesogenic group or a mesogenic supporting group, R ¹ represents a hydrogen atom, a halogen atom, A cyano group or an alkyl group having 1 to 25 carbon atoms, wherein one or more hydrogen atoms bonded to the alkyl group may be substituted with a halogen atom or CN, and one CH present in the group; _Two groups or two or more CH ₂ groups that are not adjacent to each other are independently of each other in a form in which oxygen atoms, sulfur atoms, and oxygen atoms and sulfur atoms are not directly bonded to each other. S—, —NH—, —N (CH ₃ ) —, —CO—, —COO—, —OCO—, —OCOO—, —SCO—, —COS—, —CH═CH—, or —C≡C. - may be replaced by (wherein, R ¹ is the reactivity Except for the case of a functional group).)
R ¹ is an alkyl group having 1 to 8 carbon atoms (one CH ₂ group present in this group or two or more non-adjacent CH ₂ groups are independently of each other, And may be replaced by —O—, —CO—, —COO—, —OCO—, —OCOO—, —CH═CH—, or —C≡C— in a form that is not directly bonded to each other. It is preferable.

Examples of the reactive functional group represented by P ^x in the general formula (X) include a substituent represented by the general formula (II-c), (II-d), or (II-e). And substituents selected from the group.

Examples of the mesogenic group or mesogenic supporting group represented by MG in the general formula (X) include the same groups as MG in the general formula (II-b).

The polymerizable liquid crystal composition of the present embodiment may contain two or more polymerizable compounds represented by the general formula (X). Of the polymerizable compounds represented by the general formula (X) contained in the polymerizable liquid crystal composition, “m ^x ” in the general formula (X) representing the first polymerizable compound is changed to “SA _x. represents a ", if the formula representing the second polymerizable compound" ^{m x} "in (X) represented as" SB _{x ", 1 ≦ | SA x -SB x} | a ≦ 3, and, 3 ≦ It is preferable that SA _x + SB _x ≦ 10 is satisfied.

In the polymerizable liquid crystal composition of the present embodiment, it is preferable to contain 2 to 4 types of polymerizable compounds represented by the general formula (X), more preferably 2 to 3 types, and more preferably 2 types. More preferably. When three or four polymerizable compounds represented by the general formula (X) are contained, the relationship between SA and SB is established in any combination of the polymerizable compounds. If you do.

Examples of the two or more polymerizable compounds represented by the general formula (X) contained in the polymerizable liquid crystal composition of the present embodiment include the following general formulas (X-1) to (X-4) and the following general formulas: Any two or more polymerizable compounds selected from the group consisting of polymerizable compounds represented by (X-31) to (X-32) are preferred,
Two or more compounds represented by the following general formula (X-1), two or more compounds represented by the following general formula (X-2), and a compound represented by the following general formula (X-3) Two or more compounds, two or more compounds represented by the following general formula (X-4), two or more compounds represented by the following general formula (X-31), or the following general formula (X-32) It is more preferable that 2 or more types of compounds represented by these are contained.

The general formulas (X-1) to (X-4) will be described below.
Y ²¹ , Y ³¹ , Y ⁴¹ , and Y ⁵¹ each independently represent a hydrogen atom or a methyl group.
E ²¹ , E ³¹ , E ⁴¹ , and E ⁵¹ each independently represent an alkylene group having 1 to 8 carbon atoms.
Z ²¹ , Z ²² , Z ³¹ , Z ³² , Z ⁴¹ , Z ⁴² , Z ⁵¹ , and Z ⁵² are each independently —COO—, —OCO—, —C≡C—, —CH═CH—. , —CH ₂ —CH ₂ —, —CH═CH—COO—, —OCO—CH═CH—, or a single bond.
X ¹³ to X ²⁴ each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, a methoxy group, a CF ₃ group, or an OCF ₃ group, and 1 to 3 of X ¹³ to X ²⁴ Preferably represents a fluorine atom, a chlorine atom, a methyl group, a methoxy group, a CF ₃ group, or an OCF ₃ group.
X ²⁵ to X ³⁹ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, a methoxy group, a CF ₃ group, or an OCF ₃ group, and 1 to 3 of X ²⁵ to X ³⁹ Preferably represents a fluorine atom, a chlorine atom, a methyl group, a methoxy group, a CF ₃ group, or an OCF ₃ group.
X ⁴⁰ to X ⁵³ each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, a methoxy group, a CF ₃ group, or an OCF ₃ group, and 1 to 3 of X ⁴⁰ to X ⁵³ Preferably represents a fluorine atom, a chlorine atom, a methyl group, a methoxy group, a CF ₃ group, or an OCF ₃ group.
X ⁵⁴ to X ⁶⁸ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, a methoxy group, a CF ₃ group, or an OCF ₃ group, and 1 to 3 of X ⁵⁴ to X ⁶⁸ Preferably represents a fluorine atom, a chlorine atom, a methyl group, a methoxy group, a CF ₃ group, or an OCF ₃ group.
R ² to R ⁵ each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, or an alkyl group having 1 to 15 carbon atoms, and one or two or more present in the alkyl group The methylene group is substituted with an oxygen atom (—O—), —CO—, —OCO—, —COO—, —C≡C—, or —CH═CH—, assuming that the oxygen atoms are not directly bonded to each other. (Except when R ² to R ⁵ are the reactive functional group).

Z ²¹ , Z ²² , Z ³¹ , Z ³² , Z ⁴¹ , Z ⁴² , Z ⁵¹ , and Z ⁵² are each independently a single bond, —COO—, or —OCO—, and R ² to R ^More preferably, each of ⁵ is independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.

As more preferred specific examples of the polymerizable compounds represented by the general formulas (X-1) to (X-4), polymerizable compounds represented by the following general formulas (X-5) to (X-21) Is mentioned.

In the general formulas (X-5) to (X-21), Y ²² represents a hydrogen atom or a methyl group, R ²¹ represents an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. R ²³ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, R ²² represents a fluorine atom, a chlorine atom, a methyl group, or a methoxy group, n ²¹ represents an integer of 1 to 8.

Of the polymerizable compounds represented by the general formulas (X-5) to (X-21), the general formulas (X-5), (X-7), (X-10), (X-12), (X X-14) and (X-19) are preferred, and in general formulas (X-5), (X-10), (X-12), (X-14) and (X-19) The compounds represented by formulas (X-5), (X-10), and (X-14) are even more preferred. The compound represented by the general formula (X-5) is most preferable.

Among these polymerizable compounds, as a more preferable compound,
In the general formula (X-5), compounds wherein R ²¹ and R ²² are methyl groups,
In the general formula (X-7), a compound wherein R ²¹ is a methyl group, an ethyl group or a propyl group, and R ²² is a methoxy group or a chlorine atom,
In the general formula (X-10), compounds wherein R ²¹ and R ²² are methyl groups,
In the general formula (X-12), a compound wherein R ²¹ is a methyl group, an ethyl group or a propyl group, and R ²² is a methoxy group or a chlorine atom,
In the general formula (X-14), a compound wherein R ²¹ and R ²² are methyl groups, and
In the general formula (X-19), a compound in which R ²¹ is a hydrogen atom, a methyl group, an ethyl group, or a propyl group, and R ²² is a methoxy group or a chlorine atom can be given.

Among these polymerizable compounds, as a more preferable compound,
In the general formula (X-5), compounds wherein R ²¹ and R ²² are methyl groups,
In the general formula (X-12), a compound wherein R ²¹ is a methyl group and R ²² is a methoxy group,
In the general formula (X-14), compounds in which R ²¹ and R ²² are methyl groups can be given.

The general formulas (X-31) to (X-32) will be described below.
Y ⁶¹ and Y ⁷¹ each independently represent a hydrogen atom or a methyl group.
E ⁶¹ and E ⁷¹ each independently represents an alkylene group having 1 to 8 carbon atoms.
Z ⁶¹ represents —COO—, —OCO—, or a single bond.
Z ⁶² represents —C≡C—.
Z ⁷¹ and Z ⁷² each independently represent —COO—, —OCO—, or a single bond.

X ⁷¹ to X ⁸² each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, a methoxy group, a CF ₃ group, or an OCF ₃ group, and 1 to 3 of X ⁷¹ to X ⁸² Preferably represents a fluorine atom, a chlorine atom, a methyl group, a methoxy group, a CF ₃ group, or an OCF ₃ group.
X ⁸⁵ to X ⁹⁶ each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, a methoxy group, a CF ₃ group, or an OCF ₃ group.

R ⁷ to R ⁸ each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, or an alkyl group having 1 to 15 carbon atoms, and one or two or more present in the alkyl group The methylene group may be substituted with an oxygen atom (—O—), —CO—, —OCO—, —COO—, or —CH═CH—, provided that the oxygen atoms are not directly bonded to each other (provided that R ⁷ to R ⁸ are the reactive functional groups).

Among the polymerizable compounds represented by the general formula (X-31), Z ⁶¹ is —COO— or —OCO—, Z ⁶² is —C≡C—, and R ⁷ has 1 to 10 carbon atoms. Of these, a compound having an alkyl group or an alkoxy group having 1 to 10 carbon atoms is more preferred.

Among the polymerizable compounds represented by the general formula (X-32), Z ⁷¹ is —COO— or —OCO—, Z ⁷² is a single bond, and R ⁸ is an alkyl group having 1 to 10 carbon atoms. Or a compound which is an alkoxy group having 1 to 10 carbon atoms is more preferable.

More preferred specific examples of the polymerizable compounds represented by the general formulas (X-31) to (X-32) include polymerizable compounds represented by the following general formulas (X-33) to (X-44). Can be mentioned.

In the general formulas (X-33) to (X-44), Y ⁶² and Y ⁷² represent a hydrogen atom or a methyl group, and R ⁶¹ and R ⁶³ represent an alkyl group having 1 to 10 carbon atoms or a carbon atom number of 1 to 10 represents an alkoxy group, R ⁶² and R ⁶⁴ represent a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group or a methoxy group, and n ⁶¹ represents an integer of 1 to 8.

Of the polymerizable compounds represented by the general formulas (X-33) to (X-44), those represented by the general formulas (X-33), (X-34), (X-39) and (X-40) Are preferred.

Among these polymerizable compounds, as a more preferable compound,
In the general formulas (X-33) and (X-34), a compound in which R ⁶¹ is a methoxy group or an ethoxy group, and R ⁶² is a chlorine atom or a fluorine atom,
In the general formulas (X-39) and (X-40), compounds in which R ⁶³ is a linear alkyl group having 2 to 5 carbon atoms and R ⁶⁴ is a hydrogen atom or a methyl group can be mentioned.

Among these polymerizable compounds, as a more preferable compound,
In the general formula (X-33), a compound wherein R ⁶¹ is a methoxy group and R ⁶² is a chlorine atom,
In the general formula (X-39), a compound in which R ⁶³ is a propyl group and R ⁶⁴ is a hydrogen atom can be given.

The polymerizable compound represented by the general formula (X) is preferably a compound represented by the following general formula (X-50).

In General Formula (X-50), Y ⁸² represents a hydrogen atom or a methyl group, n ⁸¹ is an integer of 0 to 8, n ⁸² is 1 or 2, and Z ⁸³ is —COO— or —OCO—. , —C≡C—, or a single bond, A ⁸³ represents a 1,4-phenylene group or a 1,4-cyclohexylene group, and R ⁸³ represents an alkyl group having 1 to 5 carbon atoms or an alkoxyl group. Z ⁸³ is preferably a single bond, A ⁸³ is a 1,4-phenylene group, and R ⁸³ is a cyano group, a methyl group, an ethyl group, or a methoxy group.
When n ⁸² is 2 and a plurality of Z ⁸³ are present, they may be the same or different, and when a plurality of A ⁸³ are present, they may be the same or different.
The compound of the general formula (X-50) is an effective compound when it is desired to reduce the viscosity. However, if too much is added, the orientation deteriorates. The addition amount is preferably 0 to 30% by mass, and more preferably 0 to 10% by mass, when the total amount of the polymerizable compound is 100% by mass.

As exemplified above, when the polymerizable compound represented by the general formula (X) has three ring structures, when the lateral hydrogen atom of the ring structure is substituted with a substituent, the polymerizable compound The solubility of the compound in the solvent is improved, and the storage stability of the polymerizable liquid crystal composition of this embodiment is improved, which is preferable. Furthermore, in order to further improve the storage stability, it is preferable to increase the solubility (compatibility) between a plurality of polymerizable compounds.

From the viewpoint of increasing the compatibility, it is preferable that the skeleton structures of the plurality of polymerizable compounds are approximated or the same. For example, the polymerizable liquid crystal composition of the present embodiment contains two or more polymerizable compounds represented by the general formula (X-5), and the polymerizable property represented by the general formula (X-12). A compound containing two or more compounds, two or more polymerizable compounds represented by general formula (X-14), and a polymerizable compound represented by general formula (X-33). It is more preferable to include two or more kinds, or to include two or more polymerizable compounds represented by the general formula (X-39).

When the total weight of the polymerizable compounds (including the bifunctional compound described above) contained in the polymerizable liquid crystal composition of the present embodiment is 100 parts by weight, the total of the polymerizable compounds represented by the general formula (X) The content of is preferably 5 parts by weight or more and less than 70 parts by weight, more preferably 5 to 50 parts by weight, still more preferably 10 to 40 parts by weight.

In the polymerizable liquid crystal composition of the present embodiment, when two kinds of polymerizable compounds represented by the general formula (X) are included, the total weight of the polymerizable compounds contained in the polymerizable liquid crystal composition is 100 parts by weight, The content of each polymerizable compound represented by the general formula (X) is preferably 5 to 70% by weight, more preferably 5 to 50% by weight, and still more preferably 10 to 40% by weight.
When the content is in these preferred ranges, the storage stability of the polymerizable liquid crystal composition of the present embodiment is further improved.

In the polymerizable liquid crystal composition of the present embodiment, when two kinds of polymerizable compounds represented by the general formula (X) are included, the first polymerizable compound represented by the general formula (X) and the second polymerizable compound. The difference in the compound content is preferably 0 to 30 parts by weight, more preferably 0 to 20 parts by weight, and still more preferably 0 to 10 parts by weight. Thus, the storage stability of the polymerizable liquid crystal composition of the present embodiment is further improved when the contents of the two polymerizable compounds are equal.

The total content of the bifunctional compound represented by the general formula (I) and the monofunctional compound represented by the general formula (X) with respect to the total weight of the polymerizable liquid crystal composition of the present embodiment is 5 to 50 wt% is preferable, 10 to 40 wt% is more preferable, and 20 to 40 wt% is still more preferable.
About these suitable ranges, the lower limit is determined from the viewpoint of improving the coating property of the composition on the substrate, and the upper limit is determined from the viewpoint of increasing the storage stability of the composition.

The polymerizable composition solution of the present invention may contain a polymerizable discotic liquid crystal compound in addition to the bifunctional compound represented by the general formula (I).
The polymerizable discotic liquid crystal compound used in the present invention preferably has one or more polymerizable functional groups. Examples of such compounds include polymerizability as described in JP-A-7-281028, JP-A-7-287120, JP-A-7-333431, and JP-A-8-27284. Examples include discotic liquid crystal compounds.
The compounding quantity of a polymerizable discotic liquid crystal compound can be suitably adjusted with a compound.

Examples of the general formula of the polymerizable discotic liquid crystal compound include general formulas (4-1) to (4-3), but are not limited to the following general formula.

In the formula, Sp ⁴ represents an alkylene group having 0 to 18 carbon atoms, and the alkylene group is substituted with one or more halogen atoms, CN group, or an alkyl group having 1 to 8 carbon atoms having a polymerizable functional group. may be, independently each two or more CH ₂ groups not one CH ₂ group or adjacent present in this group to each other, in a manner that oxygen atoms are not directly bonded to each other, -O Replaced by —, —S—, —NH—, —N (CH ₃ ) —, —CO—, —COO—, —OCO—, —OCOO—, —SCO—, —COS— or —C≡C—. You may,
A ⁴ represents 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group, 1,3-dioxane-2,5-diyl group, tetrahydro Thiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene-2,6-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5 -Diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group-, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene- 2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4,4a, 9,10a-octahydrophenanthrene-2,7-diyl group, 1,4- Naphthile Benzo [1,2-b: 4,5-b ′] dithiophene-2,6-diyl group, benzo [1,2-b: 4,5-b ′] diselenophen-2,6-diyl group [1] benzothieno [3,2-b] thiophene-2,7-diyl group, [1] benzoselenopheno [3,2-b] selenophene-2,7-diyl group, or fluorene-2,7- Represents a diyl group,
n5 represents 0 or 1,
Z ^4a represents —CO—, —CH ₂ CH ₂ —, —CH ₂ O—, —CH═CH—, —CH═CHCOO—, —CH ₂ CH ₂ COO—, —CH ₂ CH ₂ OCO—, — COCH ₂ CH ₂ — represents an alkyl group which may have a halogen atom having 2 to 10 carbon atoms or a single bond,
Z ^4b is —COO—, —OCO—, —OCH ₂ —, —CH ₂ O—, —CH═CH—, —C≡C—, —CH═CHCOO—, —OCOCH═CH—, —CH ₂ CH _{2 COO -, - CH 2 CH} 2 OCO -, - COOCH 2 CH 2 -, - OCOCH 2 CH 2 -, - CONH -, - NHCO -, - OCOO-, a halogen atom having 2 to 10 carbon atoms Represents a good alkyl group or a single bond,
R ⁶ represents a hydrogen atom, a halogen atom, a cyano group or an alkyl group having 1 to 18 carbon atoms, and the alkyl group may be substituted with one or more halogen atoms or CN, One CH ₂ group present or two or more non-adjacent CH ₂ groups are each independently of each other in a form in which oxygen atoms are not directly bonded to each other, —O—, —S—, —NH—, May be replaced by —N (CH ₃ ) —, —CO—, —COO—, —OCO—, —OCOO—, —SCO—, —COS— or —C≡C—,
Or R ⁶ represents the general formula (4-a)

(In the formula, P ^4a represents a polymerizable functional group, and Sp ^3a represents the same meaning as Sp ¹ ).
P ^4a preferably represents a substituent selected from the polymerizable groups represented by the following formulas (P-1) to (P-20).

Among these polymerizable functional groups, from the viewpoint of enhancing the polymerizability and storage stability, the formula (P-1) or the formulas (P-2), (P-7), (P-12), (P-13) ) Are preferred, and formulas (P-1), (P-7), and (P-12) are more preferred.
Specific examples of the polymerizable discotic liquid crystal compound include compounds (4-4) to (4-8), but are not limited to the following compounds.

In the formula, q represents an integer of 1 to 18.

<Organic solvent>
The organic solvent constituting the polymerizable liquid crystal composition of the present embodiment is not particularly limited as long as it can dissolve the general formula (I), but is a solvent that can be evaporated at a temperature of 100 ° C. or lower and dried. It is preferable that it is present, and it is preferable that the substrate used is not eroded. Examples of such solvents include aromatic hydrocarbons such as toluene, xylene, cumene, and mesitylene, ester solvents such as methyl acetate, ethyl acetate, propyl acetate, and butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclohexane, and the like. Ketone solvents such as pentanone, ether solvents such as tetrahydrofuran, 1,2-dimethoxyethane and anisole, amide solvents such as N, N-dimethylformamide and N-methyl-2-pyrrolidone, propylene glycol monomethyl ether acetate, Examples include diethylene glycol monomethyl ether acetate, γ-butyrolactone, and chlorobenzene. These organic solvents can be used alone or in combination of two or more.

Among the exemplified organic solvents, the solubility of the polymerizable compound represented by the general formula (I) is excellent, the orientation of the film obtained by polymerizing the composition is also excellent, and it is easy to dry at 100 ° C. or less. More preferred are toluene, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, propylene glycol monomethyl ether acetate, and N-methyl-2-pyrrolidone and combinations thereof.

The content of the organic solvent relative to the total weight of the polymerizable liquid crystal composition of the present embodiment is preferably a content that facilitates application of the composition to a substrate, for example, 40 to 90% by weight. Preferably, it is 50 to 80% by weight.

<Polymerization initiator>
The polymerizable liquid crystal composition of the present embodiment preferably contains at least one polymerization initiator.
The polymerization initiator is a useful compound for efficiently polymerizing the polymerizable liquid crystal composition. As the polymerization initiator, a photopolymerization initiator is preferable, and specifically, the following compounds are preferable.
Irgacure 651, Irgacure 184, Irgacure 907, Irgacure 127, Irgacure 369, Irgacure 379, Irgacure 819, Irgacure OXE01, Irgacure OXE02, Lucyrin TPO, Darocur 1173 manufactured by BASF. LAMBSON's Esacure 1001M, Esacure KIP150, Speed Cure BEM, Speed Cure BMS, Speed Cure PBZ, Benzophenone.
These polymerization initiators may be used alone or in combination of two or more, and a sensitizer or the like may be added.
The content of the polymerization initiator with respect to the total weight of the polymerizable liquid crystal composition of the present embodiment is, for example, preferably 0.1 to 10% by weight, more preferably 1 to 7% by weight, and still more preferably 3 to 7% by weight. .

<Surfactants>
The polymerizable liquid crystal composition of this embodiment preferably contains a surfactant or a compound having a repeating unit represented by the following general formula (3) and having a weight average molecular weight of 100 or more.

(Wherein R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and one or more hydrogen atoms in the hydrocarbon group) The atom may be substituted with a halogen atom.)
The surfactant and the compound represented by the general formula (3) impart an effect of reducing the tilt angle of the liquid crystal compound at the air interface. Examples of the surfactant include alkyl carboxylates, alkyl phosphates, alkyl sulfonates, fluoroalkyl carboxylates, fluoroalkyl phosphates, fluoroalkyl sulfonates, polyoxyethylene derivatives, fluoroalkylethylene oxide derivatives, Examples include polyethylene glycol derivatives, alkyl ammonium salts, fluoroalkyl ammonium salts, silicone derivatives, and the like. Of these, fluorine-containing surfactants and silicone derivatives are particularly preferable.

More specifically, “MEGAFAC F-110”, “MEGAFACCF-113”, “MEGAFAC F-120”, “MEGAFAC F-812”, “MEGAFAC F-142D”, “MEGAFAC F-144D”, “MEGAFAC F-” 150 "," MEGAFAC F-171 "," MEGAFACF-173 "," MEGAFAC F-177 "," MEGAFAC F-183 "," MEGAFAC F-195 "," MEGAFAC F-824 "," MEGAFAC F-833 " , “MEGAFAC F-114”, “MEGAFAC F-410”, “MEGAFAC F-493”, “MEGAFAC F-494”, “MEGAFAC F-443”, “MEGAFAC F-444”, “MEGAFAC F-445”, "ME “GAFAC F-446”, “MEGAFAC F-470”, “MEGAFAC F-471”, “MEGAFAC F-474”, “MEGAFAC F-475”, “MEGAFAC F-477”, “MEGAFAC F-478”, “MEGAFAC” F-479, MEGAFAC F-480SF, MEGAFAC F-482, MEGAFAC F-484, MEGAFAC F-484, MEGAFAC F-486, MEGAFAC F-487, MEGAFAC F -489, MEGAFAC F-172D, MEGAFAC F-178K, MEGAFAC F-178RM, MEGAFAC R-08, MEGAFAC R-30, MEGAFAC F-472SF, MEGAFAC “BL-20”, “MEGAFAC R-61”, “MEGAFAC R-90”, “MEGAFAC ESM-1”, “MEGAFAC MCF-350SF” (manufactured by DIC Corporation),
“Furgent 100”, “Furgent 100C”, “Furgent 110”, “Furgent 150”, “Furgent 150CH”, “Furgent A”, “Furgent 100A-K”, “Furgent 501”, "Factent 300", "Factent 310", "Factent 320", "Factent 400SW", "FTX-400P", "Factent 251", "Factent 215M", "Factent 212MH", "Footer Gent 250, Fategent 222F, Fategent 212D, FTX-218, FTX-209F, FTX-213F, FTX-233F, Fate 245F, FTX-208G ”,“ FTX-240G ”,“ FT -206D "," FTX-220D "," FTX-230D "," FTX-240D "," FTX-207S "," FTX-211S "," FTX-220S "," FTX-230S "," FTX-750FM " ”,“ FTX-730FM ”,“ FTX-730FL ”,“ FTX-710FS ”,“ FTX-710FM ”,“ FTX-710FL ”,“ FTX-750LL ”,“ FTX-730LS ”,“ FTX-730LM ”, "FTX-730LL", "FTX-710LL" (above, manufactured by Neos),
“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-340 "," BYK-344 "," BYK-370 " ”,“ BYK-375 ”,“ BYK-377 ”,“ BYK-350 ”,“ BYK-352 ”,“ BYK-354 ”,“ BYK-355 ”,“ BYK-356 ”,“ BYK-358N ”, “BYK-361N”, “BYK-357”, “BYK-390”, “BYK-392”, “BYK-UV3500”, “BYK-UV3510”, “BYK-UV3570”, “B K-Silclean3700 "(manufactured by BYK Japan KK),
Examples include “TEGO Rad2100”, “TEGO Rad2200N”, “TEGO Rad2250”, “TEGO Rad2300”, “TEGO Rad2500”, “TEGO Rad2600”, “TEGO Rad2700” (manufactured by TEGO).

The weight average molecular weight of the compound represented by the general formula (3) is preferably 200 to 100,000, more preferably 300 to 10,000, and further preferably 500 to 5,000.

The surfactant and the compound represented by the general formula (3) may be used singly or in combination of two or more. Moreover, you may use combining the said surfactant and the compound represented by the said General formula (3).

The total content of the surfactant and the compound represented by the general formula (3) with respect to the total weight of the polymerizable liquid crystal composition of the present embodiment is preferably 0.01 to 1% by weight, More preferably, it is 0.05 to 0.6% by weight.

<Other ingredients>
A chain transfer agent is preferably added to the polymerizable liquid crystal composition of the present embodiment as another component in order to further improve the adhesion to the substrate. The chain transfer agent is preferably a thiol compound, more preferably a monothiol, dithiol, trithiol, or tetrathiol compound, and even more preferably a trithiol compound. Specifically, compounds represented by the following general formulas (5-1) to (5-12) are preferable.
The content of these thiol compounds is preferably 0.5 to 5.0% by weight, more preferably 1.0 to 3.0% by weight, based on the total weight of the composition. .

Wherein R ⁶⁵ represents an alkyl group having 2 to 18 carbon atoms, and the alkyl group may be linear or branched, and one or more methylene groups in the alkyl group are oxygen atoms, and assuming that the sulfur atoms are not linked directly to one another, an oxygen atom, a sulfur atom, -CO -, - OCO -, - COO-, or -CH = CH- may be substituted ^{by, R 66} is a carbon Represents an alkylene group having 2 to 18 atoms, and one or more methylene groups in the alkylene group are oxygen atoms, sulfur atoms, —CO—, —OCO on the assumption that an oxygen atom and a sulfur atom are not directly bonded to each other. It may be substituted with —, —COO—, or —CH═CH—.

In the polymerizable liquid crystal composition of the present embodiment, it is preferable to add a polymerization inhibitor, an antioxidant or the like in order to improve storage stability. Examples of such compounds include hydroquinone derivatives and hindered phenol antioxidants. More specifically, p-methoxyphenol, IRGANOX1010, IRGANOX1035, IRGANOX1076, IRGANOX1098, IRGANOX1135, IRGANOX1325, IRGANOX1520, IRGANOX2457, IRGANOX3957, IRGANOX3590, IRGANOX3590, IRGANOX3590, IRGANOX3590

The content of the polymerization inhibitor and the antioxidant is preferably 0.01 to 1.0% by mass, and 0.05 to 0.2% by mass with respect to the total weight of the composition. It is more preferable.

Furthermore, in order to adjust the physical properties of the polymerizable liquid crystal composition of the present embodiment, a non-polymerizable liquid crystal compound, a non-liquid crystal polymerizable compound, or the like can be added as necessary.
The content of these compounds is preferably 20% by weight or less, more preferably 10% by weight or less, and still more preferably 5% by weight or less based on the total weight of the composition.

(Optical anisotropic body manufacturing method)
(Optical anisotropic)
The optical anisotropic body of the present invention is obtained by sequentially laminating a base material, an orientation film as necessary, and a polymer of a polymerizable composition solution. Alternatively, a base material, an orientation film as necessary, and a polymerization composition solution of a polymerizable composition solution are sequentially laminated, and an orientation film and a polymerizable composition that may be different from the above or above as necessary. A product solution is sequentially laminated. Furthermore, an alignment film and a polymerizable composition solution that may be different from the above or the above may be sequentially laminated thereon as necessary.
The base material used for the optical anisotropic body of the present invention is a base material usually used for liquid crystal devices, displays, optical elements, optical components, colorants, security markings, laser emission members, and optical films. The material is not particularly limited as long as it is a material having heat resistance capable of withstanding heating during drying after the application of the polymerizable composition solution of the present invention. Examples of such a substrate include organic materials such as a glass substrate, a metal substrate, a ceramic substrate, and a plastic substrate. In particular, when the substrate is an organic material, examples thereof include cellulose derivatives, polyolefins, polyesters, polyolefins, polycarbonates, polyacrylates, polyarylates, polyether sulfones, polyimides, polyphenylene sulfides, polyphenylene ethers, nylons, and polystyrenes. Of these, plastic substrates such as polyester, polystyrene, polyolefin, cellulose derivatives, polyarylate, and polycarbonate are preferable.
In order to improve the applicability and adhesion of the polymerizable composition solution of the present invention, surface treatment of these substrates may be performed. Examples of the surface treatment include ozone treatment, plasma treatment, corona treatment, silane coupling treatment, and the like. In addition, in order to adjust the light transmittance and reflectance, an organic thin film, an inorganic oxide thin film, a metal thin film, etc. are provided on the surface of the substrate by a method such as vapor deposition, or in order to add optical added value. The material may be a pickup lens, a rod lens, an optical disk, a retardation film, a light diffusion film, a color filter, or the like. Among these, a pickup lens, a retardation film, a light diffusion film, and a color filter that have higher added value are preferable.

Moreover, even if the said base material is normally orientated or the orientation film | membrane is provided so that polymeric composition may orientate when the polymeric composition solution of this invention is apply | coated and dried. good. Examples of the alignment treatment include stretching treatment, rubbing treatment, polarized ultraviolet visible light irradiation treatment, ion beam treatment, and the like. When the alignment film is used, a known and conventional alignment film is used. Such alignment films include polyimide, polysiloxane, polyamide, polyvinyl alcohol, polycarbonate, polystyrene, polyphenylene ether, polyarylate, polyethylene terephthalate, polyether sulfone, epoxy resin, epoxy acrylate resin, acrylic resin, coumarin compound, chalcone. Examples of the compound include compounds, cinnamate compounds, fulgide compounds, anthraquinone compounds, azo compounds, and arylethene compounds. The compound subjected to the alignment treatment by rubbing is preferably an alignment treatment or a compound in which crystallization of the material is promoted by inserting a heating step after the alignment treatment. Among the compounds that perform alignment treatment other than rubbing, it is preferable to use a photo-alignment material.

(Application)
As an application method for obtaining the optical anisotropic body of the present invention, an applicator method, a bar coating method, a spin coating method, a gravure printing method, a flexographic printing method, an ink jet method, a die coating method, a cap coating method, dipping, etc. are known. Conventional methods can be performed. The polymerizable composition solution is applied and then dried.

(Polymerization process)
The polymerization treatment of the dried polymerizable composition is generally performed by irradiation with light such as ultraviolet rays or heating in a state where the polymerizable compound represented by the general formula (1) in the polymerizable composition is planarly aligned. When the polymerization is performed by light irradiation, specifically, it is preferable to irradiate ultraviolet light having a wavelength of 390 nm or less, and most preferable to irradiate light having a wavelength of 250 to 370 nm. However, when the polymerizable composition causes decomposition or the like due to ultraviolet light of 390 nm or less, it may be preferable to perform polymerization treatment with ultraviolet light of 390 nm or more. This light is preferably diffused light and unpolarized light.

(Retardation film)
The retardation film of the present invention is prepared in the same manner as the optical anisotropic body of the present invention. When the polymerizable compound represented by the general formula (1) in the polymerizable composition is polymerized in a planar alignment state, a retardation film having in-plane birefringence with respect to the substrate is obtained. The retardation film can be used as a homogeneous liquid crystal film. When the polymerizable compound represented by the general formula (1) in the polymerizable composition and the polymerizable chiral compound are polymerized in a planar alignment state, the birefringence is out of plane with respect to the substrate. A phase difference film is obtained. When the polymerizable compound represented by the general formula (1) in the polymerizable composition containing a polymerizable discotic compound is polymerized in a planar orientation state, it is compounded both in-plane and out-of-plane with respect to the substrate. A retardation film having refractive properties can be obtained.
When the substrate has a retardation, a retardation film having birefringence obtained by adding the birefringence of the substrate and the birefringence of the retardation film of the present invention can be obtained. In the retardation film, the birefringence of the base material and the birefringence of the retardation film may be in the same direction or different directions in the plane of the base material. The liquid crystal device, the display, the optical element, the optical component, the colorant, the marking for security, the member for laser emission, the optical film, and the compensation film are applied in a form suitable for the application.

(Phase difference patterning film)
The retardation patterning film of the present invention is obtained by sequentially laminating a base material, an alignment film, and a polymer of a polymerizable composition solution in the same manner as the optical anisotropic body of the present invention. Are patterned so as to obtain different phase differences. The patterning may be in different directions, such as linear patterning, lattice patterning, circular patterning, polygonal patterning, and the like. The liquid crystal device, display, optical element, optical component, colorant, security marking, laser emission member, optical film, compensation film, and the like are used.
As a method of obtaining a partially different phase difference, an alignment film is provided on the substrate, and the polymerizable composition solution of the present invention is applied and dried during the alignment treatment so that the polymerizable composition is patterned and aligned. To do. Examples of such an alignment treatment include a fine rubbing treatment, a polarized ultraviolet visible light irradiation treatment through a photomask, and a fine shape processing treatment. As the alignment film, known and conventional ones are used. Such alignment films include polyimide, polysiloxane, polyamide, polyvinyl alcohol, polycarbonate, polystyrene, polyphenylene ether, polyarylate, polyethylene terephthalate, polyether sulfone, epoxy resin, epoxy acrylate resin, acrylic resin, coumarin compound, chalcone. Examples of the compound include compounds, cinnamate compounds, fulgide compounds, anthraquinone compounds, azo compounds, and arylethene compounds. The compound subjected to the alignment treatment by fine rubbing is preferably an alignment treatment or a compound in which crystallization of the material is promoted by adding a heating step after the alignment treatment. Among the compounds that perform alignment treatment other than rubbing, it is preferable to use a photo-alignment material.

(Homogeneous orientation)
On the other hand, homogeneous alignment is achieved by appropriately selecting a polymerizable liquid crystal compound and adjusting the amount of the surfactant or the compound having a repeating unit represented by the general formula (3) and having a weight average molecular weight of 100 or more. can do.

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, “part” and “%” are based on mass.

A UCL composition was prepared by mixing each compound at the ratio shown in the following table. Each additive was further added to the UCL solution in which 30 parts by weight of the UCL composition and 70 parts by weight of each solvent were mixed to prepare sample solutions for the examples and comparative examples.

<Bifunctional compound>

<Monofunctional compound>

The solvents and additives used for the sample solutions in each table are as follows.
MEK ... Methyl ethyl ketone PGMEA ... Propylene glycol 1-monomethyl ether 2-acetate NMP ... N-methylpyrrolidone MIBK ... Methyl isobutyl ketone MEHQ ... p-methoxyphenol Irg907 ... Irgacure 907
N535 ... Fluoro rubber: TECNOFLON N535

<Production of photo-alignment film>

After dissolving 0.5 parts by weight of the compound represented by the above formula (A) in 49.5 parts by weight of 2- (2-ethoxyethoxy) ethanol, 49 parts by weight of 2-butoxyethanol is added to form a photo-alignment film. A solution of composition A was obtained. This solution was filtered through a 0.45 μm membrane filter to obtain a composition (A-1) for photo-alignment films.

The composition for photo-alignment film (A-1) was applied onto a film made of an 80 μm triacetyl cellulose derivative as a base material with a bar coater and dried at 80 ° C. for 2 minutes. The dry film thickness at this time was 15 nm. Next, the ultra-high pressure mercury lamp is passed through a wavelength cut filter, a band-pass filter, and a polarizing filter, and visible ultraviolet light having a wavelength of around 365 nm (irradiation intensity: 20 mW / cm ² ) is applied to the substrate as linearly polarized parallel light. On the other hand, the photo-alignment film was obtained by irradiating from the vertical direction. The irradiation amount was 100 mJ / cm ² .

<Production of retardation film>
The UCL sample solution of the example or the comparative example was applied on the prepared photo-alignment film, dried at 80 ° C. for 2 minutes, cooled at room temperature for 1 minute, and then irradiated with UV to prepare a target retardation film.

<Evaluation of retardation film>
The prepared retardation film was visually observed using a known polarizing film. The retardation films of the examples and comparative examples were observed, and the evaluation results are shown in Tables 1 to 10, where “◯” indicates that the result was good and “×” indicates that the result was poor.

<Evaluation of storage stability>
The UCL sample solution of the example or the comparative example was stored in a constant temperature bath (0 ° C., 10 ° C. or 20 ° C.), and the presence or absence of precipitation after 3 days was visually confirmed.
The evaluation results are shown in Tables 1 to 11, where “○” indicates that no precipitation occurred after 3 days and “×” indicates that precipitation occurred.

The configurations and combinations thereof in the embodiments described above are merely examples, and additions, omissions, substitutions, and other changes can be made without departing from the spirit of the present invention. Further, the present invention is not limited by each embodiment, and is limited only by the scope of the claims.

The polymerizable liquid crystal composition according to the present invention is widely applicable in the field of liquid crystal displays.

Claims (8)

1. Formula (I)
   

   

   (Wherein P ¹ and P ² represent a reactive functional group, MG represents a mesogenic group or a mesogenic supporting group, and two m represent the same numerical value of 1 to 6). When two or more compounds and an organic solvent are included, and m of any two polymerizable compounds among the polymerizable compounds is SA and SB, respectively, | SA−SB | = 1 or 2; A polymerizable liquid crystal composition satisfying SA + SB ≦ 10.
2. MG is represented by the general formula (II-b)
   

   

   (In the formula, A1, A2 and A3 are each independently 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group, 1, 3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene-2,6-diyl group, pyridine- 2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, Phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4,4a, 9,10a-octahydrophenanthrene 2,7-diyl group or fluorene 2, Represents a 7-diyl group, the 1,4-phenylene group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9 , 10-Dihydrophenanthrene-2,7- Yl group, 1,2,3,4,4a, 9,10a- 1 or more hydrogen atoms bonded to octahydrophenanthrene 2,7-diyl group and fluorene 2,7-diyl group, F, Cl, CF ₃ , OCF ₃ , a cyano group, an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkanoyl group, an alkanoyloxy group, an alkenyl group having 2 to 8 carbon atoms, an alkenyloxy group, an alkenoyl group or an alkenoyloxy group May be replaced,
   Z0 and Z3 are —COO—, —OCO—, —CH═CH—, —C≡C—, —CH═CHCOO—, —OCOCH═CH—, —CONH—, —NHCO—, —O—, — S—, —NH—, —N (CH ₃ ) —, —CO—, —OCOO—, —SCO—, —COS— or a single bond,
   Z1 and Z2 are each independently —COO—, —OCO—, —CH ₂ CH ₂ —, —OCH ₂ —, —CH ₂ O—, —CH═CH—, —C≡C—, —CH═ CHCOO—, —OCOCH═CH—, —CH ₂ CH ₂ COO—, —CH ₂ CH ₂ OCO—, —COOCH ₂ CH ₂ —, —OCOCH ₂ CH ₂ —, —CONH—, —NHCO—, —O— , -S-, -NH-, -N (CH ₃ )-, -CO-, -OCOO-, -SCO-, -COS- or a single bond,
   n ^b is 0, 1 or 2, if nb is located at 2 Z1 there are a plurality of them may be the same or different and if A2 there is more than one they have be the same or different May be. The polymerizable liquid crystal composition according to claim 1, which represents a structure represented by:
3. P ¹ or P ² is represented by the general formula (II-c), general formula (II-d) and general formula (II-e).
   

   

   Wherein R ²¹ , R ²² , R ²³ , R ³¹ , R ³² , R ³³ , R ⁴¹ , R ⁴² and R ⁴³ are each independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 5 carbon atoms. The polymerizable liquid crystal composition according to claim 1, wherein n represents a substituent selected from the group consisting of substituents represented by:
4. The polymerizable liquid crystal composition according to any one of claims 1 to 3, comprising a compound represented by the general formula (X).
   

   

   (In the general formula (X), P ^X represents a reactive functional group, m ^X represents an integer of 1 to 8, MG represents a mesogenic group or a mesogenic supporting group, R ¹ represents a hydrogen atom, a halogen atom, A cyano group or an alkyl group having 1 to 25 carbon atoms, wherein one or more hydrogen atoms bonded to the alkyl group may be substituted with a halogen atom or CN, and one CH present in the group; _Two groups or two or more CH ₂ groups that are not adjacent to each other are independently of each other in a form in which oxygen atoms, sulfur atoms, and oxygen atoms and sulfur atoms are not directly bonded to each other. S—, —NH—, —N (CH ₃ ) —, —CO—, —COO—, —OCO—, —OCOO—, —SCO—, —COS—, —CH═CH—, or —C≡C. -(Wherein R ¹ is the reactive functional group) Except when it is a group).)
5. The polymerizable liquid crystal composition according to any one of claims 1 to 4, comprising a polymerizable discotic liquid crystal compound.
6. A retardation film comprising the polymerizable liquid crystal composition according to any one of claims 1 to 5.
7. A retardation patterning film comprising the polymerizable liquid crystal composition according to any one of claims 1 to 5.
8. A homogeneously aligned liquid crystal film comprising the polymerizable liquid crystal composition according to any one of claims 1 to 5.