JPWO2017010560A1 - Liquid crystal composition, film, half mirror for displaying projected image, and method for producing film - Google Patents

Abstract

  According to the present invention, including a partial structure obtained by polymerizing a polymerizable liquid crystal compound, a mesogenic group derived from a rod-like liquid crystal compound or a discotic liquid crystal compound, and a mesogenic group monomer having two or more radical polymerizable double bonds, And a branched mesogen group polymer and a hydroxyl group polymer having a partial structure obtained by polymerizing a hydroxyl group monomer having one or more hydroxyl groups and two or more radical polymerizable double bonds Things are provided. The liquid crystal composition of the present invention has good liquid crystal orientation and is less likely to cause repelling when applied, and using the liquid crystal composition of the present invention, a film having desired optical characteristics, a half mirror for displaying projected images, and an advanced It is possible to provide a method for producing a film that can be optically designed.

Description

  The present invention relates to a liquid crystal composition, a film produced using the liquid crystal composition, and a half mirror for displaying projected images including the film. The present invention also relates to a method for producing a film including a layer obtained by curing a liquid crystal composition.

Currently, liquid crystal compositions containing a polymerizable liquid crystal compound are used for the production of various optical films. When coating a film using a liquid crystal composition, it is necessary to satisfy both the orientation of the liquid crystal compound and the applicability of the liquid crystal composition.
As one of methods for controlling the alignment regulating force of a liquid crystal compound in the vicinity of an interface with air of a coating film of a liquid crystal composition, for example, a polymer containing a fluoroalkyl group is disclosed in Patent Document 1 as a polymerizable liquid crystal composition. It has been proposed to add to. It is disclosed that by using such a polymer, an optical anisotropic body having no alignment defect in the vicinity of the air interface can be provided.

  On the other hand, regarding the coatability, when “repellency” of the coating solution occurs on the coated surface, it is difficult to form a good film. The repellency tends to occur because the higher the surface tension of the coating solution, the stronger the force to minimize the surface area of the coating solution. In order to reduce the surface tension of the coating solution and suppress repellency, it has a high ability to reduce the dynamic surface tension immediately after the formation of a new surface, and is also soluble in a coating solution, such as a fluorosurfactant Silicone surfactants are widely used. Examples of such a fluorosurfactant include a polymer obtained by polymerizing a fluorinated alkyl group-containing ethylenically unsaturated monomer as an essential component in Patent Document 2 and a specific amount of fluorinated alkyl group-containing ethylene. A fluorosurfactant comprising a polymerizable unsaturated monomer and a polymer obtained by polymerizing a hydrophilic structural unit-containing ethylenically unsaturated monomer as essential components has been proposed. It is described that by using the above-mentioned fluorosurfactant, excellent wettability, homogeneous coatability and recoatability, developability such as developability can be compatible.

JP 2006-16599 A JP 2000-102727 A

  By the way, in the production of a film using a liquid crystal composition, a layer formed from a liquid crystal composition may be further formed on the surface of a layer formed from the liquid crystal composition. Depending on such a manufacturing method, an advanced optical design is possible because it is not easily affected by interface reflection caused by passing through another layer. However, repellency is likely to occur on the surface of a film formed using the above-mentioned fluorine-based surfactant or silicone-based surfactant. Fluorine-based surfactants and silicone-based surfactants reduce the surface tension of the coating film and improve the coatability during coating, while the surface energy is low, so they tend to be unevenly distributed on the coating surface. This is because such a surface has high water and oil repellency.

  In view of the above, an object of the present invention is to provide a liquid crystal composition in which the orientation of a liquid crystal compound is good and repelling is less likely to occur when applied to the surface of a substrate or the like. In particular, it is an object of the present invention to provide a liquid crystal composition that is less likely to cause repelling of an upper layer forming coating liquid even after being formed as a liquid crystal layer. Another object of the present invention is to provide a film having desired optical characteristics and a half mirror for displaying projected images including the film. It is another object of the present invention to provide a method capable of advanced optical design as a film manufacturing method.

The present inventors diligently studied to solve the above problems, and found that the addition of two kinds of alignment agents results in a composition in which repelling and the like are unlikely to occur. Completed the invention.
That is, the present invention provides the following <1> to <21>.
<1> a polymerizable liquid crystal compound, a first alignment agent, and a second alignment agent,
Obtained by polymerizing a mesogenic group monomer having a mesogenic group derived from at least one liquid crystal compound selected from a rod-like liquid crystal compound and a discotic liquid crystal compound and a mesogenic group monomer having two or more radical polymerizable double bonds. A mesogenic polymer containing a branched structure and being branched,
A liquid crystal composition comprising a hydroxyl group-containing polymer containing a partial structure obtained by polymerizing a hydroxyl group-containing monomer having one or more hydroxyl groups and two or more radical polymerizable double bonds.
<2> The liquid crystal composition according to <1>, wherein the polymerizable liquid crystal compound is a rod-like liquid crystal compound.
<3> The liquid crystal composition according to <1> or <2>, wherein the mesogen-containing monomer is a compound represented by the general formula (X);

In the formula, Q ^X1 and Q ^X2 each independently represent a polymerizable group, L ^X1 and L ^X4 each independently represent a divalent linking group, and L ^X2 and L ^X3 each independently represent a single bond or divalent Cy ^X1 , Cy ^X2 and Cy ^X3 represent a divalent cyclic group, and nx represents an integer of 0 to 3.
<4> The liquid crystal composition according to <1> or <2>, wherein the mesogen-containing monomer is a compound represented by the general formula (I).

In the general formula (I), Y ¹¹ , Y ¹² and Y ¹³ each independently represent a methine or nitrogen atom which may be substituted, and L ¹ , L ² and L ³ each independently represent a single bond or two H ¹ , H ² and H ³ each independently represent the following general formula (IA) or the following general formula (IB), and R ¹ , R ² and R ³ are: Each independently represents the following general formula (IR),

In general formula (IA), YA ¹ and YA ² each independently represents a methine or nitrogen atom which may have a substituent, XA represents an oxygen atom, a sulfur atom, methylene or imino; Represents a position bonded to the L ^{1 to} L ³ side in the general formula (I), ** represents a position bonded to the R ^{1 to} R ³ side in the general formula (I),

In the general formula (IB), YB ¹ and YB ² each independently represent a methine or nitrogen atom which may have a substituent, XB represents an oxygen atom, a sulfur atom, methylene or imino, * Represents a position bonded to the L ^{1 to} L ³ side in the general formula (I), ** represents a position bonded to the R ^{1 to} R ³ side in the general formula (I),

In General Formula (I-R), ** represents a position bonded to the H ^{1 to} H ³ side in General Formula (I), L ^r1 represents a single bond or a divalent linking group, and Q ² represents at least 1 represents a divalent group having a cyclic structure, n1 represents an integer of 0 to 4, L ^r2 and L ^r3 represents a divalent linking group independently, Q ¹ is a polymerizable group or a hydrogen atom Wherein at least two of Q ¹ present in a plurality represent a polymerizable group.
<5> The liquid crystal composition according to any one of <1> to <4>, wherein the mesogen-containing polymer includes a partial structure obtained by polymerizing a compound containing fluorine.
<6> The liquid crystal composition according to <5>, wherein the partial structure obtained by polymerizing a fluorine-containing compound of the mesogen-containing polymer is represented by general formula a1;

In general formula a1, R ^a1 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R ^a2 represents an alkyl group having 1 to 20 carbon atoms or a carbon number in which at least one carbon atom has a fluorine atom as a substituent. 1-20 alkenyl groups are represented.
<7> The liquid crystal composition according to any one of <1> to <6>, wherein the hydroxyl group-containing monomer is a monomer represented by the general formula Y;

In the formula, Z ^Y1 and Z ^Y2 each independently represent a group having a radical polymerizable double bond, and L ^Y1 and L ^Y4 each independently represent a single bond or an alkylene group having a hydroxyl group, —O—, ^{-S -, - CO -, -} NR yy1 -, - C = N-, and from at least one selected from the group consisting of a divalent linking group ^{constituted, R yy1} is hydrogen Represents an atom or an alkyl group having 1 to 7 carbon atoms, L ^Y2 and L ^Y3 each independently represent a single bond, —O—, — (C═O) O—, —O (C═O) —, 2 Represents a divalent linking group composed of at least one selected from the group consisting of a valent chain group, an alkylene group having a hydroxyl group, and a divalent cyclic group, and M has a single bond or a hydroxyl group Represents a divalent to tetravalent linking group that may be present; Represents an ^{integer, L Y1, L Y2, L} Y3, L Y4, and one or more selected from the group consisting of M include a hydroxyl group.
<8> The liquid crystal composition according to any one of <1> to <6>, wherein the hydroxyl group-containing monomer is a monomer represented by the general formula Y1;

In the formula, R ^Y1 , R ^Y2 , and R ^Y3 each independently represent a hydrogen atom or a methyl group, and L ^Y11 , L ^{Y12, and} L ^Y13 each independently represent a single bond, or —O—, — (C═O ) O-, -O (C = O)-, a divalent linkage composed of at least one selected from the group consisting of a divalent chain group, an alkylene group having a hydroxyl group, and a divalent cyclic group. Represents a group, M ¹ represents a single bond or a divalent, trivalent or tetravalent linking group, and n1 represents an integer of 0 to 2.
<9> The liquid crystal composition according to any one of <1> to <8>, wherein the hydroxyl group-containing polymer includes a partial structure obtained by polymerizing a compound containing fluorine.
<10> The liquid crystal composition according to <9>, wherein the partial structure obtained by polymerizing a fluorine-containing compound of the hydroxyl group-containing polymer is represented by the following general formula a1;

In general formula a1, R ^a1 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R ^a2 represents an alkyl group having 1 to 20 carbon atoms or a carbon number in which at least one carbon atom has a fluorine atom as a substituent. 1-20 alkenyl groups are represented.
<11> The liquid crystal composition according to any one of <1> to <10>, containing a polymerization initiator.
<12> The liquid crystal composition according to any one of <1> to <11>, containing a chiral compound.
<13> A film comprising a layer obtained by curing the liquid crystal composition according to any one of <1> to <12>.
<14> A film comprising a layer obtained by curing the liquid crystal composition according to any one of <1> to <12>, and a layer obtained by curing the liquid crystal composition as a layer in direct contact with the layer.
<15> indicates selective reflection,
The film according to <13> or <14>, wherein Δλ / λ, which is a ratio between the half-value width Δλ of the selective reflection wavelength region and the central wavelength λ of the selective reflection, is 0.09 or less.
<16> The film according to any one of <13> to <15>, which reflects visible light.
<17> A film comprising at least three layers obtained by curing the liquid crystal composition according to any one of <1> to <12>,
The three layers are a layer in which a cholesteric liquid crystal phase having a central wavelength of selective reflection is fixed in a red light wavelength region, a layer in which a cholesteric liquid crystal phase having a central wavelength of selective reflection is fixed in a green light wavelength region, and a blue light wavelength region A film in which a cholesteric liquid crystal phase having a central wavelength of selective reflection is fixed.
<18> A half mirror for displaying projected images including the film according to <17>.
<19> The half mirror for displaying projected images according to <18>, including a base material made of inorganic glass or acrylic resin.
<20> The half mirror for displaying projected images according to <18> or <19>, comprising an antireflection layer on the outermost surface.
<21> Applying a liquid crystal composition containing a polymerizable liquid crystal compound to the surface of a layer obtained by curing the liquid crystal composition according to any one of <1> to <12>, and applying the applied liquid crystal composition A method for producing a film comprising curing.

  According to the present invention, a novel liquid crystal composition is provided. When the composition of the present invention is applied to the surface of a substrate or the like, the orientation of the liquid crystal compound is good and repellency is less likely to occur. Further, even after being formed as a liquid crystal layer, it is difficult to cause repellency of the coating liquid for forming the upper layer as the lower layer. Using the liquid crystal composition of the present invention, a film having desired optical properties can be produced.

Hereinafter, the present invention will be described in detail. In addition, the numerical value range represented using "to" in this specification makes the numerical value described before and behind "to" a lower limit and an upper limit.
In the present specification, the description of “(meth) acrylate” represents the meaning of “any one or both of acrylate and methacrylate”. The same applies to “(meth) acryloyl group” and the like, and “(meth) acryloyl group” means “one or both of acryloyl group and methacryloyl group”.
In this specification, the term “liquid crystal layer” means a layer formed using a liquid crystal composition containing a polymerizable liquid crystal compound, and in particular means a layer obtained by curing a liquid crystal composition containing a polymerizable liquid crystal compound. To do. In the liquid crystal layer, it is sufficient if the optical properties of the liquid crystal phase are retained in the layer, and the composition in the cured film does not necessarily have liquid crystal properties. For example, the composition may have a high molecular weight due to a curing reaction and lose liquid crystallinity.

In this specification, the term “retardation” refers to in-plane retardation, and when there is no mention of wavelength, it refers to in-plane retardation at a wavelength of 550 nm.
In the present specification, in-plane retardation is measured using a polarization phase difference analyzer AxoScan manufactured by AXOMETRIC. In-plane retardation at a wavelength of λ nm can also be measured by making light at a wavelength of λ nm incident in the normal direction of the film in KOBRA 21ADH or WR (manufactured by Oji Scientific Instruments).

<Liquid crystal composition>
The liquid crystal composition of the present invention includes a polymerizable liquid crystal compound, a first alignment agent, and a second alignment agent.
Since the liquid crystal composition of the present invention contains the first aligning agent and the second aligning agent described below, repelling hardly occurs during coating. Furthermore, when a liquid crystal layer formed using the liquid crystal composition of the present invention is used as a lower layer and an upper layer is applied and formed on the surface, repelling is less likely to occur when an upper layer forming coating solution is applied. That is, the recoatability is excellent. Furthermore, when the liquid crystal composition of the present invention is formed by coating, the alignment of the liquid crystal compound therein is good. Therefore, optical films having various functions can be produced using the liquid crystal composition of the present invention.
The liquid crystal composition of the present invention may further contain a solvent, a chiral agent, a surfactant, a polymerization initiator and the like as necessary.

[Polymerizable liquid crystal compound]
The liquid crystal composition of the present invention contains a polymerizable liquid crystal compound. One type of polymerizable liquid crystal compound may be contained, or two or more types may be contained.
The polymerizable liquid crystal compound may be a rod-like liquid crystal compound or a disc-like liquid crystal compound, and is preferably a rod-like liquid crystal compound.
The addition amount of the polymerizable liquid crystal compound in the liquid crystal composition is preferably 80 to 99.9 mass% with respect to the solid content mass (mass excluding the solvent) of the liquid crystal composition, and is 85 to 99.5. More preferably, it is 90 mass%, and 90-99 mass% is especially preferable.

  The polymerizable liquid crystal compound can be obtained by introducing a polymerizable group into the liquid crystal compound. Examples of the polymerizable group include a radical polymerizable group and a cationic polymerizable group. Among these, a radically polymerizable group is preferable. Examples of the radical polymerizable group include an unsaturated polymerizable group, and an ethylenically unsaturated polymerizable group is particularly preferable. Examples of the ethylenically unsaturated polymerizable group include (meth) acryloyl group and vinyl group, and (meth) acryloyl group is particularly preferable. Examples of the cationic polymerizable group include an oxetanyl group and a vinyl ether group.

  The polymerizable group can be introduced into the molecule of the liquid crystal compound by various methods. The number of polymerizable groups possessed by the polymerizable liquid crystal compound is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 2. Examples of polymerizable liquid crystal compounds are described in Makromol. Chem. 190, 2255 (1989), Advanced Materials 5, 107 (1993), US Pat. No. 4,683,327, US Pat. No. 95/24455, No. 97/00600, No. 98/23580, No. 98/52905, JP-A-1-272551, No. 6-16616, and No. 7-110469. 11-80081 and JP-A 2001-328773, and the like. Two or more kinds of polymerizable liquid crystal compounds may be used in combination. When two or more kinds of polymerizable liquid crystal compounds are used in combination, the alignment temperature can be lowered.

(Bar-shaped liquid crystal compound)
Examples of the rod-like liquid crystal compound include azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, alkoxy-substituted phenylpyrimidines, Phenyldioxanes, tolanes and alkenylcyclohexylbenzonitriles are preferably used.

Further, as rod-like liquid crystal compounds, Makromol. Chem., 190, 2255 (1989), Advanced Materials, 5, 107 (1993), US Pat. Nos. 4,683,327, 5,622,648 and 5,770,107, WO95 / No. 22586, No. 95/24455, No. 97/00600, No. 98/23580, No. 98/52905, JP-A-1-272551, No. 6-16616, No. 7-110469, No. 11-80081 And compounds described in JP 2001-329873 A can be used.
The rod-like liquid crystal compound is preferably a compound represented by the following general formula (X).

In the formula, Q ^X1 and Q ^X2 each independently represent a polymerizable group, L ^X1 and L ^X4 each independently represent a divalent linking group, and L ^X2 and L ^X3 each independently represent a single bond or a divalent group. Represents a linking group, Cy ^X1 , Cy ^X2 and Cy ^X3 represent a divalent cyclic group, and nx represents an integer of 0 to 3.

Hereinafter, the rod-like liquid crystal compound represented by the general formula (X) will be described.
In the formula, Q ^X1 and Q ^X2 are each independently a polymerizable group. The polymerization reaction of the polymerizable group is preferably addition polymerization. In other words, the polymerizable group is preferably a functional group capable of an addition polymerization reaction. Examples of the polymerizable group include the following formulas (M-1) to (M-5).

Among the above formulas (M-1) to (M-5), (M-1) or (M-2) is preferable, and (M-1) is more preferable.
L ^X1 and L ^X4 are each independently a divalent linking group. L ^X1 and L ^X4 are each independently —O—, —S—, —CO—, —NR ^x1 —, ^—C═N— , a divalent chain group, a divalent cyclic group, and combinations thereof. A divalent linking group selected from the group consisting of R ^x1 is a hydrogen atom or an alkyl group having 1 to 7 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group.
The example of the bivalent coupling group which consists of a combination is shown below. Here, the left side is bonded to Q (Q ^X1 or Q ^X2 ), and the right side is bonded to Cy (Cy ^X1 or Cy ^X3 ).

Lx-1: —O—divalent chain group —O—
Lx-2: —O—divalent chain group —OC (═O) —
Lx-3: —O—divalent chain group —OC (═O) O—
Lx-4: -O-divalent chain group -O-divalent cyclic group-
Lx-5: -O-divalent chain group -O-divalent cyclic group -C (= O) O-
Lx-6: -O-divalent chain group -O-divalent cyclic group -OC (= O)-
Lx-7: -O-divalent chain group-O-divalent cyclic group-divalent chain group-
Lx-8: -O-divalent chain group -O-divalent cyclic group -divalent chain group -C (= O) O-
Lx-9: -O-divalent chain group -O-divalent cyclic group -divalent chain group -OC (= O)-
Lx-10: —O—divalent chain group—OC (═O) —divalent cyclic group—
Lx-11: -O-divalent chain group -OC (= O) -divalent cyclic group -C (= O) O-
Lx-12: —O—divalent chain group —OC (═O) —divalent cyclic group —OC (═O) —
Lx-13: —O—divalent chain group—OC (═O) —divalent cyclic group—divalent chain group—
Lx-14: -O-divalent chain group-OC (= O) -divalent cyclic group-divalent chain group-C (= O) O-
Lx-15: -O-divalent chain group-OC (= O) -divalent cyclic group-divalent chain group-OC (= O)-
Lx-16: —O—divalent chain group—OC (═O) O—divalent cyclic group—
Lx-17: —O—divalent chain group —OC (═O) O—divalent cyclic group —C (═O) O—
Lx-18: —O—divalent chain group —OC (═O) O—divalent cyclic group —OC (═O) —
Lx-19: —O—divalent chain group—OC (═O) O—divalent cyclic group—divalent chain group—
Lx-20: -O-divalent chain group-OC (= O) O-divalent cyclic group-divalent chain group-C (= O) O-Lx-21: -C (= O ) O-Divalent chain group-OC (= O) O-Divalent cyclic group-Divalent chain group-OC (= O)-

Lx-21: -NR ^x1 -divalent chain group -O-
Lx-22: —NR ^x1 —Divalent chain group —OC (═O) —
Lx-23: ^{-NR x1} - divalent chain group -OC (= O) O-
Lx-24: —NR ^x1 —Divalent chain group—O—Divalent cyclic group—
Lx-25: —NR ^x1 —divalent chain group—O—divalent cyclic group —C (═O) O—
Lx-26: —NR ^x1 —divalent chain group—O—divalent cyclic group—OC (═O) —
Lx-27: —NR ^x1 —Divalent chain group—O—Divalent cyclic group—Divalent chain group—
Lx-28: ^{-NR x1} - divalent chain group -O- bivalent cyclic groups - divalent chain group -C (= O) O-
Lx-29: ^{-NR x1} - divalent chain group -O- bivalent cyclic groups - divalent chain group -OC (= O) -
Lx-30: —NR ^x1 —Divalent chain group—OC (═O) —Divalent cyclic group—
Lx-31: ^{-NR x1} - divalent chain group -OC (= O) - bivalent cyclic group -C (= O) O-
Lx-32: —NR ^x1 —Divalent chain group —OC (═O) —Divalent cyclic group —OC (═O) —
Lx-33: —NR ^x1 —Divalent chain group—OC (═O) —Divalent cyclic group—Divalent chain group—
Lx-34: —NR ^x1 —Divalent chain group—OC (═O) —Divalent cyclic group—Divalent chain group —C (═O) O—
Lx-35: —NR ^x1 —Divalent chain group—OC (═O) —Divalent cyclic group—Divalent chain group—OC (═O) —
Lx-36: —NR ^x1 —Divalent chain group—OC (═O) O—Divalent cyclic group—
Lx-37: ^{-NR x1} - divalent chain group -OC (= O) O- divalent cyclic group -C (= O) O-
Lx-38: —NR ^x1 —Divalent chain group —OC (═O) O—Divalent cyclic group —OC (═O) —
Lx-39: —NR ^x1 —Divalent chain group—OC (═O) O—Divalent cyclic group—Divalent chain group—
Lx-40: —NR ^x1 —Divalent chain group—OC (═O) O—Divalent cyclic group—Divalent chain group—C (═O) O—Lx-21: —C (= O) O-Divalent chain group-OC (= O) O-Divalent cyclic group-Divalent chain group-OC (= O)-

The divalent chain group means an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, or a substituted alkynylene group. An alkylene group, a substituted alkylene group, an alkenylene group and a substituted alkenylene group are preferred, and an alkylene group and an alkenylene group are more preferred.
The alkylene group may have a branch. The alkylene group preferably has 1 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, and most preferably 2 to 8 carbon atoms.
The alkylene part of the substituted alkylene group is the same as the above alkylene group. Examples of the substituent include a halogen atom.
The alkenylene group may have a branch. The alkenylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, and most preferably 2 to 8 carbon atoms.
The alkenylene part of the substituted alkenylene group is the same as the above alkenylene group. Examples of the substituent include a halogen atom.
The alkynylene group may have a branch. The alkynylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, and most preferably 2 to 8 carbon atoms.
The alkynylene part of the substituted alkynylene group is the same as the above alkynylene group. Examples of the substituent include a halogen atom.
Specific examples of the divalent chain group include ethylene, trimethylene, propylene, tetramethylene, 2-methyl-tetramethylene, pentamethylene, hexamethylene, octamethylene, 2-butenylene, 2-butynylene and the like.

The definition and examples of the divalent cyclic group are the same as the definitions and examples of Cy ^X1 , Cy ^X2 and Cy ^X3 described later.

L ^{X2 and} L ^X3 are each independently a single bond or a divalent linking group. L ^X2 and L ^X3 are each independently —O—, —S—, —CO—, —NR ^x2 —, ^—C═N— , a divalent chain group, a divalent cyclic group, and combinations thereof. It is preferably a divalent linking group or a single bond selected from the group consisting of R ^x2 is a hydrogen atom or an alkyl group having 1 to 7 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and preferably a hydrogen atom, a methyl group, or an ethyl group. More preferably, it is a hydrogen atom. The divalent chain group and the divalent cyclic group have the same definitions as in L ^X1 and L ^X4 .
As the divalent linking group preferable as L ^X2 or L ^X3 , —C (═O) O—, —OC (═O) —, —OC (═O) O—, —OC (═O) NR ^x2 — , —COS—, —SCO—, —CONR ^x2 —, —NR ^x2 CO—, — (CR ^xa R ^xb ) jx—, —C═C—C (═O) O—, —C═N—, — C = N-N = C- etc. are mentioned.
Here, R ^xa and R ^xb each independently represent a hydrogen atom or an alkyl group (for example, an alkyl group having 1 to 3 carbon atoms, preferably a methyl group), jx represents an integer of 1 or more, and 1 to 3 It is preferably an integer in the range.

In the compound represented by the general formula (X), nx represents 0, 1, 2, or 3. When nx is 2 or 3, a plurality of L ^X3 may be the same or different, and a plurality of Cy ^X2 may be the same or different. nx is preferably 1 or 2, and more preferably 1.

In the compound represented by the general formula (X), Cy ^X1 , Cy ^X2 and Cy ^X3 are each independently a divalent cyclic group. The ring contained in the divalent cyclic group is preferably a 5-membered ring, 6-membered ring, or 7-membered ring, more preferably a 5-membered ring or 6-membered ring, and a 6-membered ring. Most preferred. The ring contained in the cyclic group may be a condensed ring. However, it is more preferably a monocycle than a condensed ring.

The ring contained in the cyclic group may be any of an aromatic ring, an aliphatic ring, and a heterocyclic ring. Examples of the aromatic ring include a benzene ring and a naphthalene ring. Examples of the aliphatic ring include a cyclohexane ring. Examples of the heterocyclic ring include a pyridine ring and a pyrimidine ring.
As the cyclic group having a benzene ring, 1,4-phenylene is preferable. As the cyclic group having a naphthalene ring, naphthalene-1,5-diyl and naphthalene-2,6-diyl are preferable. The cyclic group having a cyclohexane ring is preferably 1,4-cyclohexylene, particularly trans-1,4-cyclohexylene. As the cyclic group having a pyridine ring, pyridine-2,5-diyl is preferable. The cyclic group having a pyrimidine ring is preferably pyrimidine-2,5-diyl.

  The cyclic group may have a substituent. Examples of the substituent include a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 5 carbon atoms, a halogen-substituted alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a carbon number Is an alkylthio group having 1 to 5 carbon atoms, an acyloxy group having 2 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, a carbamoyl group, an alkyl-substituted carbamoyl group having 2 to 6 carbon atoms, and 2 to 6 carbon atoms Or a combination of any two or more thereof.

  Preferred examples of the compound represented by the general formula (X) include a compound represented by the following general formula (XI), a compound represented by the following general formula (X-II), and the formula (X-III). ), A compound represented by formula (I-IV), a compound represented by formula (IV), and the like.

In general formula (XI) and general formula (X-II), R ^{101 to} R ¹⁰⁴ each independently represents a substituent, and X ¹⁰¹ and Y ¹⁰¹ each independently represent a hydrogen atom, a methyl group, or an ethyl group. Represents a halogen group, a fluorinated alkyl group, or an aldehyde group. Examples of the halogen group include a chlorine atom and a bromine atom.
R ^{101 to} R ¹⁰⁴ are preferably a group represented by — (CH ₂ ) _ny —O ( ^O═ ) C—CR ^{xc ═CH} ₂ . Here, R ^xc each independently represents a hydrogen atom or a methyl group, and ny is preferably an integer of 2 to 8.
From the viewpoint of suppressing crystal precipitation, in the general formula (XI) or (X-II), X ¹⁰¹ and Y ¹⁰¹ preferably represent a methyl group. From the viewpoint of exhibiting properties as a liquid crystal, ny is preferably an integer of 4 to 8.

In the formula, R ^X11 represents a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, or —Z ¹² —Sp ¹² —Q ^X12 ;
L ¹¹ represents a single bond, —C (═O) O—, or —O (C═O) —,
L ¹² represents —C (═O) O—, —OC (═O) — or —CONR ^X12 —,
Z ¹¹ and Z ¹² are each independently a single bond, —O—, —NH—, —N (CH ₃ ) —, —S—, —C (═O) O—, —OC (═O) —, -OC (= O) O- or -C (= O) NR ^X12-
R ^X12 represents a hydrogen atom or -Sp ¹² -Q ^X12 ;
Sp ¹¹ and ^{Sp 12} are each independently a single ^{bond, Q X11} at the carbon atoms 1 be substituted for 12 linear or branched alkylene group ^{or, Q X11} carbon atoms which may be substituted with, 1 Any one or more of —CH ₂ —, —O—, —S—, —NH—, —N (Q ^X11 ) —, or —C (= O)-represents a linking group obtained by substitution,
Q ^X11 represents a hydrogen atom, a cycloalkyl group, or a cycloalkyl group in which one or more of —CH ₂ — is —O—, —S—, —NH—, —N (CH ₃ ) —, —C (= O) —, —OC (═O) —, or a group substituted with —C (═O) O—, or a polymerizable group;
Q ^X12 represents a hydrogen atom or a polymerizable group,
l ¹¹ represents an integer of 0 to 2,
m ¹¹ represents an integer of 1 or 2,
When m ¹¹ is 2, the sum of the two ¹¹ is 2,
n ¹¹ represents an integer of 1 to 3,
The plurality of R ^X11 , the plurality of L ¹¹ , the plurality of L ¹² , the plurality of l ¹¹ , the plurality of Z ¹¹ , the plurality of Sp ¹¹ , and the plurality of Q ^{X 11} may be the same as or different from each other. In addition, the polymerizable compound represented by the formula (I-11) includes at least one —Z ¹² —Sp ¹² —Q ^{X12 in} which Q ^X12 is a polymerizable group as R ^X11 . Z ¹¹ is —C (═O) O— or —C (═O) NR ^X12 —, and Q ^X11 is a group consisting of groups represented by formula (Q-1) to formula (Q-5). ^-Z 11 ^-Sp 11 ^{-Q X11,} and ^{Z 12} is a polymerizable group selected is -C (= O) O- or -C (= ^{O) NR X12} from - a a, and ^{Q X12} is polymerized It is also preferable to include at least one group selected from the group consisting of —Z ¹² —Sp ¹² —Q ^X12 which is a functional group.

Any 1,4-cyclohexylene group contained in the compound represented by the formula (X-III) is a trans-1,4-cyclohexylene group.
As the polymerizable group contained in the compound represented by the formula (X-III), a polymerizable group represented by the above formulas (M-1) to (M-5) is preferable, and the above formula (M-1) or The polymerizable group represented by the polymerizable group represented by (M-2) is preferred.
As the compound represented by the formula (X-III), particularly preferable compounds include compounds in which L ¹¹ is a single bond, l ¹¹ is 1 (dicyclohexyl group), and Q ^{X 11} is a polymerizable group.
Another particularly preferred compound as the polymerizable compound represented by the formula (X-III) is as follows: m ¹¹ is 2, l ¹¹ is 0, and both R ^X11 are -Z ¹² -Sp ¹² -Q. Examples include compounds in which ^{X 12} is represented and Q ^{X 12} is a polymerizable group.

In the formula, Z ²¹ and Z ²² each independently represent a trans-1,4-cyclohexylene group which may have a substituent, or a phenylene group which may have a substituent,
Each of the above substituents is independently 1 to 4 substituents selected from the group consisting of —CO—X ²¹ —Sp ²³ —Q ^X23 , an alkyl group, and an alkoxy group,
m21 represents an integer of 1 or 2, n21 represents an integer of 0 or 1,
When m21 represents 2, n21 represents 0,
when m21 represents 2, two Z ²¹ may be the same or different;
At least one of Z ²¹ and Z ²² is an optionally substituted phenylene group,
L ²¹ , L ²² , L ²³ and L ²³ are each independently a single bond, —CH ₂ O—, —OCH ₂ —, — (CH ₂ ) ₂ OC (═O) —, —C (═O) O. (CH ₂ ) ₂ —, —C (═O) O—, —OC (═O) —, —OC (═O) O—, —CH═CH—C (═O) O—, and —OC ( ═O) —CH═CH—, which represents a linking group selected from the group consisting of:
X ²¹ is -O -, - S-, or ^-N (Sp ^{25 -Q X25)} - or show, or ^represents a nitrogen atom to form a ring structure with ^{Q X23} and ^{Sp 23,}
r ²¹ represents an integer of 1 to 4,
Sp ²¹ , Sp ²² , Sp ²³ , Sp ²⁴ , and Sp ²⁵ are each independently a single bond, a linear or branched alkylene group having 1 to 20 carbon atoms, and a linear or branched alkylene group having 1 to 20 carbon atoms. In which one or more —CH ₂ — is —O—, —S—, —NH—, —N (CH ₃ ) —, —C (═O) —, —OC (═O) —, or A linking group selected from the group consisting of groups substituted with -C (= O) O-;
Q ^X21 and Q ^X22 each independently represent a polymerizable group,
Q ^X23 represents a hydrogen atom, a cycloalkyl group, or a cycloalkyl group in which one or more —CH ₂ — is —O—, —S—, —NH—, —N (CH ₃ ) —, —C (= O)-, -OC (= O)-, a group substituted by -C (= O) O-, or a polymerizable group, or a nitrogen atom in which X ²¹ forms a ring structure with Q ^X23 and Sp ²³ Indicates a single bond in the case of
Q ^X25 is a hydrogen atom, a cycloalkyl group, or a cycloalkyl group in which one or more —CH ₂ — is —O—, —S—, —NH—, —N (CH ₃ ) —, —C ( ═O) —, —OC (═O) —, a group substituted with —C (═O) O—, or a polymerizable group, and when Sp ²⁵ is a single bond, Q ^X25 is not a hydrogen atom. .

The polymerizable compound represented by the formula (X-IV) preferably has a structure in which 1,4-phenylene groups and trans-1,4-cyclohexylene groups are alternately present, for example, m21 is 2. N21 is 0 and Z ²¹ is a trans-1,4-cyclohexylene group which may have a substituent from the side of Q ^X21 , an arylene group which may have a substituent, Alternatively, a structure in which m21 is 1, n21 is 1, Z ²¹ is an arylene group which may have a substituent, and Z ²² is an arylene group which may have a substituent is preferable. .
As the polymerizable group contained in the compound represented by the formula (X-IV), the polymerizable groups represented by the above formulas (M-1) to (M-5) are preferable, and the above formula (M-1) or The polymerizable group represented by the polymerizable group represented by (M-2) is preferred.

In the formula, R ³¹ and R ³² are each independently a group selected from the group consisting of an alkyl group, an alkoxy group, and —C (═O) —X ³¹ —Sp ³³ —Q ^X33 ;
n31 and n32 each independently represents an integer of 0 to 4,
X ³¹ represents a single bond, —O—, —S—, or —N (Sp ³⁴ -Q ^X34 ) —, or represents a nitrogen atom that forms a ring structure with Q ^X33 and Sp ³³ ,
Z ³¹ represents a phenylene group which may have a substituent,
Z ³² represents a trans-1,4-cyclohexylene group which may have a substituent, or a phenylene group which may have a substituent,
Each of the above substituents is independently an alkyl group, an alkoxy group, and 1 to 4 substituents selected from the group consisting of —C (═O) —X ³¹ —Sp ³³ —Q ^X33 ,
m31 represents an integer of 1 or 2, m32 represents an integer of 0 to 2,
m31 + m32 is 2,
When m31 and m32 represent 2, two Z ³¹ and Z ³² may be the same or different,
L ³¹ and L ³² are each independently a single bond, —CH ₂ O—, —OCH ₂ —, — (CH ₂ ) ₂ OC (═O) —, —C (═O) O (CH ₂ ) ₂ —. , -C (= O) O-, -OC (= O)-, -OC (= O) O-, -CH = CH-C (= O) O-, and -OC (= O) -CH = CH— represents a linking group selected from the group consisting of:
Sp ³¹ , Sp ³² , Sp ³³ and Sp ³⁴ are each independently 1 in a single bond, a linear or branched alkylene group having 1 to 20 carbon atoms, and a linear or branched alkylene group having 1 to 20 carbon atoms. Two or more —CH ₂ — may be —O—, —S—, —NH—, —N (CH ₃ ) —, —C (═O) —, —OC (═O) —, or —C. (= O) represents a linking group selected from the group consisting of groups substituted with O-,
Q ^X31 and Q ^X32 each independently represent a polymerizable group;
Q ^X33 and Q ^X34 each independently represent a hydrogen atom, a cycloalkyl group, or a cycloalkyl group in which one or more —CH ₂ — is —O—, —S—, ^—NH— , —N (CH ₃ ) -, - C (= O ) -, - OC (= O) -, or -C (= O) O- with a substituted radicals or polymerizable ^{group,, Q X33} together with ^{X 31} and ^{Sp 33} In the case of forming a ring structure, a single bond may be shown. When Sp ³⁴ is a single bond, Q ^X34 is not a hydrogen atom.
As the polymerizable group contained in the compound represented by the formula (X-V), a polymerizable group represented by the above formulas (M-1) to (M-5) is preferable, and the above formula (M-1) or The polymerizable group represented by the polymerizable group represented by (M-2) is preferred.
As the polymerizable compound represented by formula (X-V), a particularly preferred compound, Z ³² is include compounds compounds and m32 is a phenylene group is 0.

  Although the example of a compound represented by general formula (X) below is shown, it is not limited to these.

(Discotic liquid crystal compound)
The polymerizable liquid crystal compound may be a discotic liquid crystal compound. As an example of the discotic liquid crystal compound, a compound represented by the following general formula (I) is preferable.

In general formula (I), Y ¹¹ , Y ¹² and Y ¹³ each independently represent a methine or nitrogen atom which may have a substituent, and L ¹ , L ² and L ³ each independently represent a single bond Alternatively, it represents a divalent linking group, and H ¹ , H ² and H ³ each independently represent a group of the general formula (IA) or (IB).

In general formula (IA), YA ¹ and YA ² each independently represents a methine or nitrogen atom which may have a substituent, XA represents an oxygen atom, a sulfur atom, methylene or imino; Represents a position bonded to the L ^{1 to} L ³ side in the general formula (I), and ** represents a position bonded to the R ^{1 to} R ³ side in the general formula (I).

In the general formula (IB), YB ¹ and YB ² each independently represent a methine or nitrogen atom which may have a substituent, XB represents an oxygen atom, a sulfur atom, methylene or imino, * Represents a position bonded to the L ^{1 to} L ³ side in the general formula (I), and ** represents a position bonded to the R ^{1 to} R ³ side in the general formula (I).

R ¹ , R ² and R ³ each independently represents the following general formula (IR).

In General Formula (I-R), ** represents a position bonded to the H ^{1 to} H ³ side in General Formula (I), L ^r1 represents a single bond or a divalent linking group, and Q ² represents at least Represents a divalent group (cyclic group) having one kind of cyclic structure, n1 represents an integer of 0 to 4, L ^r2 and L ^r3 each independently represent a divalent linking group, and Q ¹ represents polymerization. Represents a polymerizable group or a hydrogen atom, and at least two of Q ¹ present in a plurality represent a polymerizable group.

In general formula (I), Y ¹¹ , Y ¹² and Y ¹³ each independently represent a methine which may have a substituent or a nitrogen atom, preferably a methine which may have a substituent, and no methine. More preferred is substitution.

  Examples of the substituent that methine may have include an alkyl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an acyloxy group, an acylamino group, an alkoxycarbonylamino group, an alkylthio group, an arylthio group, a halogen atom, and A cyano group can be mentioned as a preferred example. Among these substituents, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an acyloxy group, a halogen atom and a cyano group are more preferable, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and a carbon number A 2-12 alkoxycarbonyl group, a C2-C12 acyloxy group, a halogen atom, and a cyano group are more preferable.

L ¹ , L ² and L ³ each independently represents a single bond or a divalent linking group.
When L ¹ , L ² and L ³ are divalent linking groups, each independently represents —O—, —S—, —C (═O) —, —NR ⁷ —, —CH═CH—, —C. It is preferably a divalent linking group selected from the group consisting of ≡C—, a divalent cyclic group, and combinations thereof. R ⁷ is a hydrogen atom or an alkyl group having 1 to 7 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom, a methyl group, or an ethyl group. Preferably, it is a hydrogen atom.

The divalent cyclic group in L ¹ , L ² and L ³ is a divalent linking group having at least one cyclic structure (hereinafter sometimes referred to as a cyclic group). The cyclic group is preferably a 5-membered ring, a 6-membered ring, or a 7-membered ring, more preferably a 5-membered ring or a 6-membered ring, and most preferably a 6-membered ring. The ring contained in the cyclic group may be a condensed ring. However, it is more preferably a monocycle than a condensed ring. The ring contained in the cyclic group may be any of an aromatic ring, an aliphatic ring, and a heterocyclic ring. Preferred examples of the aromatic ring include a benzene ring and a naphthalene ring. A preferable example of the aliphatic ring is a cyclohexane ring. The heterocyclic ring is preferably a ring containing at least one sulfur atom, nitrogen atom or oxygen atom, and preferred examples include a pyridine ring, a pyrimidine ring and an oxadiazole ring. The cyclic group is more preferably an aromatic ring or a heterocyclic ring. In addition, the divalent cyclic group in the present invention is more preferably a divalent linking group consisting of only a cyclic structure (including a substituent) (hereinafter the same).

Of the divalent cyclic groups represented by L ¹ , L ² and L ³ , the cyclic group having a benzene ring is preferably a 1,4-phenylene group. As the cyclic group having a naphthalene ring, a naphthalene-1,5-diyl group and a naphthalene-2,6-diyl group are preferable. The cyclic group having a cyclohexane ring is preferably a 1,4-cyclohexylene group. The cyclic group having a pyridine ring is preferably a pyridine-2,5-diyl group. The cyclic group having a pyrimidine ring is preferably a pyrimidine-2,5-diyl group. As the cyclic group having an oxadiazole ring, a 1,2,4-oxadiazole-3,5-diyl group is preferable.

The divalent cyclic group represented by L ¹ , L ² and L ³ may have a substituent. Examples of the substituent include a halogen atom (preferably a fluorine atom and a chlorine atom), a cyano group, a nitro group, an alkyl group having 1 to 16 carbon atoms, an alkenyl group having 2 to 16 carbon atoms, an alkynyl group having 2 to 16 carbon atoms, C1-C16 halogen-substituted alkyl group, C1-C16 alkoxy group, C2-C16 acyl group, C1-C16 alkylthio group, C2-C16 acyloxy group, C2-C2 -16 alkoxycarbonyl groups, carbamoyl groups, carbamoyl groups substituted with 2-16 carbon atoms and acylamino groups with 2-16 carbon atoms are included.

L ¹ , L ² and L ³ include a single bond, * —O—C (═O) —, * —C (═O) —O—, * —CH═CH—, * —C≡C—, * -Divalent cyclic group-, * -OC (= O) -Divalent cyclic group-, * -C (= O) -O-Divalent cyclic group-, * -CH = CH-2 -Valent cyclic group-, * -C≡C-divalent cyclic group-, * -divalent cyclic group-OC (= O)-, * -divalent cyclic group-C (= O)- O-, * -divalent cyclic group -CH = CH- and * -divalent cyclic group -C≡C- are preferred. In particular, a single bond, * —CH═CH—, * —C≡C—, * —CH═CH—divalent cyclic group— and * —C≡C—divalent cyclic group— are preferable, and a single bond is Most preferred. Here, * represents the position bonded to the 6-membered ring side including Y ¹¹ , Y ¹² and Y ¹³ in the general formula (I).

In general formula (I), H ¹ , H ² and H ³ each independently represent a group of general formula (IA) or (IB).

In general formula (IA), YA ¹ and YA ² each independently represents a methine or nitrogen atom which may have a substituent, XA represents an oxygen atom, a sulfur atom, methylene or imino; Represents a position bonded to the L ^{1 to} L ³ side in the general formula (I), and ** represents a position bonded to the R ^{1 to} R ³ side in the general formula (I).

In the general formula (IB), YB ¹ and YB ² each independently represent a methine or nitrogen atom which may have a substituent, XB represents an oxygen atom, a sulfur atom, methylene or imino, * Represents a position bonded to the L ^{1 to} L ³ side in the general formula (I), and ** represents a position bonded to the R ^{1 to} R ³ side in the general formula (I).

R ¹ , R ² and R ³ each independently represents the following general formula (IR).

In the general formula (IR), ** represents a position bonded to the H ^{1 to} H ³ side in the general formula (I). L ^r1 represents a single bond or a divalent linking group. Q ² represents a divalent group (cyclic group) having at least one kind of cyclic structure.

L ^r1 represents a single bond or a divalent linking group. When L ^r1 is a divalent linking group, a group consisting of —O—, —S—, —C (═O) —, —NR ⁷ —, —CH═CH—, —C≡C—, and combinations thereof It is preferably a divalent linking group selected more. R ⁷ is a hydrogen atom or an alkyl group having 1 to 7 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group, or a methyl group. The hydrogen atom is most preferred.
L ^r1 is a single bond, ***-O-CO-, ***-CO-O-, ***-CH = CH- and ***-C≡C- (where *** is general Any one of the formulas (IR) is preferred, and a single bond is more preferred.

Q ² represents a divalent group (cyclic group) having at least one kind of cyclic structure. As such a cyclic group, a cyclic group having a 5-membered ring, a 6-membered ring, or a 7-membered ring is preferable, a cyclic group having a 5-membered ring or a 6-membered ring is more preferable, and a cyclic group having a 6-membered ring is preferable. Further preferred. The cyclic structure contained in the cyclic group may be a condensed ring. However, it is more preferably a monocycle than a condensed ring. The ring contained in the cyclic group may be any of an aromatic ring, an aliphatic ring, and a heterocyclic ring. Preferable examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring. A preferable example of the aliphatic ring is a cyclohexane ring. The heterocyclic ring preferably has at least one nitrogen atom or oxygen atom, and preferred examples include a pyridine ring, a pyrimidine ring, and an oxadiazole ring.

Of Q ^2, the cyclic group having a benzene ring is preferably a 1,4-phenylene group. As the cyclic group having a naphthalene ring, naphthalene-1,4-diyl group, naphthalene-1,5-diyl group, naphthalene-1,6-diyl group, naphthalene-2,5-diyl group, naphthalene-2,6 -A diylnaphthalene-2,7-diyl group is preferred. The cyclic group having a cyclohexane ring is preferably a 1,4-cyclohexylene group. The cyclic group having a pyridine ring is preferably a pyridine-2,5-diyl group. The cyclic group having a pyrimidine ring is preferably a pyrimidine-2,5-diyl group. As the oxadiazole ring, a 1,2,4-oxadiazole-3,5-diyl group is preferable. Among these, a 1,4-phenylene group, a naphthalene-2,6-diyl group, a 1,4-cyclohexylene group, and a 1,2,4-oxadiazole-3,5-diyl group are particularly preferable.

Q ² may have a substituent. Examples of the substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, nitro group, alkyl group having 1 to 16 carbon atoms, alkenyl group having 2 to 16 carbon atoms, and 2 carbon atoms. -16 alkynyl group, alkyl group substituted with halogen having 1 to 16 carbon atoms, alkoxy group having 1 to 16 carbon atoms, acyl group having 2 to 16 carbon atoms, alkylthio group having 1 to 16 carbon atoms, 2 carbon atoms -16 acyloxy groups, C2-C16 alkoxycarbonyl groups, carbamoyl groups, C2-C16 alkyl-substituted carbamoyl groups and C2-C16 acylamino groups are included. Among these, a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, and an alkyl group substituted with a halogen having 1 to 6 carbon atoms are preferable, a halogen atom, an alkyl group having 1 to 4 carbon atoms, and 1 carbon atom. An alkyl group substituted with 4 to 4 halogen atoms is more preferable, and a halogen atom, an alkyl group having 1 to 3 carbon atoms, and a trifluoromethyl group are more preferable.

  n1 represents the integer of 0-4. n1 is preferably an integer of 1 to 3, and more preferably 1 or 2.

L ^r2 is **-O-, **-O-C (= O)-, **-C (= O) -O-, **-O-C (= O) -O-, ** -S-, **-NH-, **-SO _2- , **-CH _2- , **-CH = CH- or **-C≡C-, where ** binds to Q ² Represents the position.
L ^r2 is preferably ** — O—, ** — O—C (═O) —, ** — C (═O) —O—, ** — O—C (═O) —O—. , ** — CH ₂ —, ** — CH═CH—, ** — C≡C—, and more preferably ** — O—, ** — O—C (═O) —, **. -O-C (= O) -O -, ** - CH 2 - is.
When L ^r2 is a group containing a hydrogen atom, this hydrogen atom may be substituted with a substituent. Examples of such a substituent include a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms, an alkyl group substituted with a halogen having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a carbon number A carbamoyl substituted with an alkyl group having 2 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, an acyloxy group having 2 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, a carbamoyl group, and an alkyl having 2 to 6 carbon atoms Group and a C2-C6 acylamino group are mentioned as a preferable example, A halogen atom and a C1-C6 alkyl group are more preferable.

L ^r3 is —O—, —S—, —C (═O) —, —SO ₂ —, —NH—, —CH ₂ —, —CH═CH— and —C≡C— and combinations thereof. Represents a divalent linking group selected from the group consisting of Here, the hydrogen atoms of —NH—, —CH ₂ —, and —CH═CH— may be substituted with a substituent. Examples of such a substituent include a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms, an alkyl group substituted with a halogen having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a carbon number A carbamoyl substituted with an alkyl group having 2 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, an acyloxy group having 2 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, a carbamoyl group, and an alkyl having 2 to 6 carbon atoms Group and a C2-C6 acylamino group are mentioned as a preferable example, A halogen atom and a C1-C6 alkyl group are more preferable. By substituting with these substituents, when preparing a liquid crystal composition from a liquid crystal compound, solubility in a solvent to be used can be improved.

L ^r3 is preferably selected from the group consisting of —O—, —C (═O) —, —CH ₂ —, —CH═CH—, —C≡C—, and combinations thereof. L ^r3 preferably contains 1 to 20 carbon atoms, more preferably 2 to 14 carbon atoms. Further, L ^r3 preferably contains 1 to 16 —CH ₂ —, and more preferably ₂ to 12 —CH ₂ —.

Q ¹ represents a polymerizable group or a hydrogen atom, and at least two of the plurality of Q ¹ represent a polymerizable group. Moreover, it is preferable that a plurality of Q ¹ are all polymerizable groups. Definition for Q ¹ has the same meaning as defined for ^{Q X1} and ^{Q x4,} the preferable range is also the same.

  Among the compounds of the general formula (I), compounds represented by the following general formula (Iz) are more preferable.

In the general formula ^(Iz), Y ^{11, Y 12} and ^{Y 13} are the general formula synonymous with ^{Y 11, Y 12} and ^{Y 13} in (I), the following ^{R 111, R 112} and ^{R 113} are each independently The general formula (Iz-A), the following general formula (Iz-B), or the following general formula (Iz-C) is represented.

In the general formula (Iz-A), A ¹¹ , A ¹² , A ¹³ , A ¹⁴ , A ¹⁵ and A ¹⁶ each independently represents a methine group or nitrogen atom which may have a substituent, and X ¹ represents Represents an oxygen atom, a sulfur atom, methylene or imino, L ¹¹ and L ¹² each independently represent a divalent linking group, and Q ¹¹ represents a polymerizable group or a hydrogen atom.

In the general formula (Iz-B), A ²¹ , A ²² , A ²³ , A ²⁴ , A ²⁵ and A ²⁶ each independently represents a methine or nitrogen atom which may have a substituent, and X ² represents Represents an oxygen atom, a sulfur atom, methylene or imino, L ²¹ and L ²² each independently represent a divalent linking group, and Q ²¹ represents a polymerizable group or a hydrogen atom.

In the general formula (Iz-C), A ³¹ , A ³² , A ³³ , A ³⁴ , A ³⁵ and A ³⁶ each independently represents a methine group or nitrogen atom which may have a substituent, and X ³ represents Represents an oxygen atom, a sulfur atom, methylene or imino, L ³¹ and L ³² each independently represent a divalent linking group, and Q ³¹ represents a polymerizable group or a hydrogen atom.

However, at least two of Q ¹¹ , Q ²¹ and Q ³¹ represent a polymerizable group.

In the general formula ^(Iz), Y ^{11, Y 12} and ^{Y 13} are the general formula synonymous with ^{Y 11, Y 12} and ^{Y 13} in (I), preferable ranges are also the same.

R ^{111, R 112} and ^{R 113} are each independently the above general formula (Iz-A), representing the general formula (Iz-B) or the general formula (Iz-C). In order to reduce the wavelength dispersion of intrinsic birefringence, general formula (IZ-A) or general formula (Iz-C) is preferable, and general formula (Iz-A) is more preferable. R ^{111, R 112} and ^{R 113} is preferably a ^{R 111 = R 112 = R 113} .

In the general formula (Iz-A), A ¹¹ , A ¹² , A ¹³ , A ¹⁴ , A ¹⁵ and A ¹⁶ each independently represents a methine group or nitrogen atom which may have a substituent.
At least one of A ¹¹ and A ¹² is preferably a nitrogen atom, and more preferably both are nitrogen atoms.
A ¹³ , A ¹⁴ , A ¹⁵ and A ¹⁶ are preferably methine which may have a substituent among them, more preferably methine which may have a substituent. preferable. Furthermore, this methine is preferably unsubstituted.
Examples of the substituent in the case of methine in which A ¹¹ , A ¹² , A ¹³ , A ¹⁴ , A ¹⁵ or A ¹⁶ may have a substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine Atom), a cyano group, a nitro group, an alkyl group having 1 to 16 carbon atoms, an alkenyl group having 2 to 16 carbon atoms, an alkynyl group having 2 to 16 carbon atoms, an alkyl group substituted with a halogen having 1 to 16 carbon atoms, C1-C16 alkoxy group, C2-C16 acyl group, C1-C16 alkylthio group, C2-C16 acyloxy group, C2-C16 alkoxycarbonyl group, carbamoyl group, carbon An alkyl-substituted carbamoyl group having 2 to 16 carbon atoms and an acylamino group having 2 to 16 carbon atoms are included. Among these, a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, and an alkyl group substituted with a halogen having 1 to 6 carbon atoms are preferable, a halogen atom, an alkyl group having 1 to 4 carbon atoms, and 1 carbon atom. An alkyl group substituted with -4 halogen is more preferred, and a halogen atom, an alkyl group having 1 to 3 carbon atoms, and a trifluoromethyl group are more preferred.
X ¹ represents an oxygen atom, a sulfur atom, methylene or imino, and preferably an oxygen atom.

In the general formula (Iz-B), A ²¹ , A ²² , A ²³ , A ²⁴ , A ²⁵ and A ²⁶ each independently represent a methine or nitrogen atom which may have a substituent.
At least one of A ²¹ and A ²² is preferably a nitrogen atom, and more preferably both are nitrogen atoms.
A ²³ , A ²⁴ , A ²⁵ and A ²⁶ are preferably methine which may have a substituent among them, more preferably methine which may have a substituent. preferable. Furthermore, this methine is preferably unsubstituted.
Examples of the substituent in the case of methine in which A ²¹ , A ²² , A ²³ , A ²⁴ , A ²⁵ or A ²⁶ may have a substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine Atom), a cyano group, a nitro group, an alkyl group having 1 to 16 carbon atoms, an alkenyl group having 2 to 16 carbon atoms, an alkynyl group having 2 to 16 carbon atoms, an alkyl group substituted with a halogen having 1 to 16 carbon atoms, C1-C16 alkoxy group, C2-C16 acyl group, C1-C16 alkylthio group, C2-C16 acyloxy group, C2-C16 alkoxycarbonyl group, carbamoyl group, carbon An alkyl-substituted carbamoyl group having 2 to 16 carbon atoms and an acylamino group having 2 to 16 carbon atoms are included. Among these, a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, and an alkyl group substituted with a halogen having 1 to 6 carbon atoms are preferable, a halogen atom, an alkyl group having 1 to 4 carbon atoms, and 1 carbon atom. An alkyl group substituted with -4 halogen is more preferred, and a halogen atom, an alkyl group having 1 to 3 carbon atoms, and a trifluoromethyl group are more preferred.
X ² represents an oxygen atom, a sulfur atom, methylene or imino, preferably an oxygen atom.

In the general formula (Iz-C), A ³¹ , A ³² , A ³³ , A ³⁴ , A ³⁵ and A ³⁶ each independently represents a methine group or a nitrogen atom which may have a substituent.
At least one of A ³¹ and A ³² is preferably a nitrogen atom, and more preferably both are nitrogen atoms.
A ³³ , A ³⁴ , A ³⁵ and A ³⁶ are each preferably methine which may have a substituent, and more preferably all methine which may have a substituent. Furthermore, this methine is preferably unsubstituted.
In the case where A ³¹ , A ³² , A ³³ , A ³⁴ , A ³⁵ or A ³⁶ is a methine which may have a substituent, the methine may have a substituent. Examples of the substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, nitro group, alkyl group having 1 to 16 carbon atoms, alkenyl group having 2 to 16 carbon atoms, and 2 carbon atoms. -16 alkynyl group, alkyl group substituted with halogen having 1 to 16 carbon atoms, alkoxy group having 1 to 16 carbon atoms, acyl group having 2 to 16 carbon atoms, alkylthio group having 1 to 16 carbon atoms, 2 carbon atoms -16 acyloxy groups, C2-C16 alkoxycarbonyl groups, carbamoyl groups, C2-C16 alkyl-substituted carbamoyl groups and C2-C16 acylamino groups are included. Among these, a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, and an alkyl group substituted with a halogen having 1 to 6 carbon atoms are preferable, a halogen atom, an alkyl group having 1 to 4 carbon atoms, and 1 carbon atom. An alkyl group substituted with -4 halogen is more preferred, and a halogen atom, an alkyl group having 1 to 3 carbon atoms, and a trifluoromethyl group are more preferred.
X ³ represents an oxygen atom, a sulfur atom, methylene or imino, preferably an oxygen atom.

L ^{11 in} the general formula (Iz-A), L ^{21 in} the general formula (Iz-B), and L ³¹ in the general formula (Iz-C) are each independently —O—, —C (═O ) —, —O—C (═O) —, —C (═O) —O—, —O—C (═O) —O—, —S—, —NH—, —SO ₂ —, —CH _2- , -CH = CH- or C≡C-. Preferably, —O—, —C (═O) —, —O—C (═O) —, —C (═O) —O—, —O—C (═O) —O—, —CH ₂ are preferred. —, —CH═CH—, —C≡C—, and more preferably —O—, —O—C (═O) —, —C (═O) —O—, —O—C (= O) —O—, —C≡C—. In particular, L ¹¹ in the general formula (Iz-A) that can be expected to have small intrinsic birefringence wavelength dispersibility is particularly preferably —O—, —C (═O) —O—, —C≡C—, Among these, -C (= O) -O- is preferable because it can exhibit a discotic nematic phase at a higher temperature. When the above group is a group containing a hydrogen atom, the hydrogen atom may be replaced with a substituent. Examples of such a substituent include a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms, an alkyl group substituted with a halogen having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a carbon number A carbamoyl substituted with an alkyl group having 2 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, an acyloxy group having 2 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, a carbamoyl group, and an alkyl having 2 to 6 carbon atoms Group and a C2-C6 acylamino group are mentioned as a preferable example, A halogen atom and a C1-C6 alkyl group are more preferable.

L ^{12 in} the general formula (Iz-A), L ^{22 in} the general formula (Iz-B), and L ³² in the general formula (Iz-C) are each independently -O-, -S-,- It represents a divalent linking group selected from the group consisting of C (═O) —, —SO ₂ —, —NH—, —CH ₂ —, —CH═CH—, C≡C—, and combinations thereof. Here, the hydrogen atoms of —NH—, —CH ₂ —, and —CH═CH— may be substituted with a substituent. Examples of such a substituent include a halogen atom, a cyano group, a nitro group, a hydroxyl group, a carboxyl group, an alkyl group having 1 to 6 carbon atoms, an alkyl group substituted with a halogen having 1 to 6 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. Alkoxy group, C2-C6 acyl group, C1-C6 alkylthio group, C2-C6 acyloxy group, C2-C6 alkoxycarbonyl group, carbamoyl group, C2-C6 alkyl Preferred examples include a carbamoyl group and an acylamino group having 2 to 6 carbon atoms substituted with a halogen atom, a hydroxyl group, and an alkyl group having 1 to 6 carbon atoms, and particularly preferred are a halogen atom, a methyl group, and an ethyl group. .

L ¹² , L ²² and L ³² are each independently selected from the group consisting of —O—, —C (═O) —, —CH ₂ —, —CH═CH— and C≡C—, and combinations thereof. It is preferable that

L ¹² , L ²² and L ³² each independently preferably have 1 to 20 carbon atoms, and more preferably 2 to 14 carbon atoms. The number of carbon atoms is preferably 2 to 14, more preferably 1 to 16 —CH ₂ —, and still more preferably ₂ to 12 —CH ₂ —.

The number of carbon atoms constituting L ¹² , L ²² , and L ³² affects the phase transition temperature of the liquid crystal and the solubility of the compound in the solvent. Generally the more increased the number of carbon atoms, transition temperature of the discotic nematic phase from (N _D phase) to the isotropic liquid tends to decrease. Further, the solubility in a solvent generally tends to improve as the number of carbon atoms increases.

Q ^{11 in} the general formula (Iz-A), Q ^{21 in} the general formula (Iz-B), and Q ³¹ in the general formula (Iz-C) each independently represent a polymerizable group or a hydrogen atom, Two represent polymerizable groups. Q ¹¹ , Q ²¹ , and Q ³¹ are preferably all polymerizable groups. About the example of a polymeric group, it is synonymous with the polymeric group represented by ^QX1 or ^QX2 in general formula (X), and its preferable example is also the same.

  Specific examples of the compound represented by the general formula (I) include the exemplified compounds described in paragraphs [0068] to [0077] of JP2010-244038, and paragraph [0040] of JP2007-2220A. ] To [0063] are included. However, it is not limited to these compounds.

  The above compound can be synthesized by various methods, for example, by the method described in JP-A 2007-2220, [0064] to [0070].

Discotic liquid crystal compound as a liquid crystal phase, it is preferred to exhibit a columnar phase and a discotic nematic phase (N _D phase), among these liquid crystal phases, a discotic nematic phase having a good monodomain property (N _D Phase) is preferred.

  As the discotic liquid crystal compound, a compound represented by the following general formula (1) is also preferable.

In the formula, D ⁴¹ represents a discotic core, L ⁴¹ represents a divalent linking group, Q ⁴¹ represents a polymerizable group, and n41 represents an integer of 2 to 12.

An example of the disk-shaped core (D ⁴¹ ) of the above formula is shown below. L represents a divalent linking group, and Q represents a polymerizable group.

In the general formula (1), the divalent linking group (L ⁴¹ ) is a group consisting of an alkylene group, an alkenylene group, an arylene group, —CO—, —NH—, —O—, —S—, and combinations thereof. It is preferably a divalent linking group selected more. The divalent linking group (L ⁴¹ ) is a combination of at least two divalent groups selected from the group consisting of an alkylene group, an alkenylene group, an arylene group, —CO—, —NH—, —O—, and —S—. More preferably, The divalent linking group (L ⁴¹ ) is most preferably a group obtained by combining at least two divalent groups selected from the group consisting of an alkylene group, an alkenylene group, an arylene group, —CO— and —O—. . The alkylene group preferably has 1 to 12 carbon atoms. The alkenylene group preferably has 2 to 12 carbon atoms. The arylene group preferably has 6 to 10 carbon atoms. The alkylene group, alkenylene group and arylene group may have a substituent (eg, alkyl group, halogen atom, cyano, alkoxy group, acyloxy group). Examples of the divalent linking group (L ⁴¹ ) are shown below. * Is bonded to the discotic core (D ⁴¹ ), and ** is bonded to the polymerizable group (Q ⁴¹ ). AL represents an alkylene group or an alkenylene group, and AR represents an arylene group.

L ₄₁ -1: * -AL-CO-O-AL-**
L ₄₁ -2: * -AL-CO-O-AL-O-**
L ₄₁ -3: * -AL-CO-O-AL-O-AL-**
L ₄₁ -4: * -AL-CO-O-AL-O-CO-**
L ₄₁ -5: * -CO-AR-O-AL-**
L ₄₁ -6: * -CO-AR-O-AL-O-**
L ₄₁ -7: * -CO-AR-O-AL-O-CO-**
L ₄₁ -8: * -CO-NH-AL-**
L ₄₁ -9: * -NH-AL-O-**
L ₄₁ -10: * -NH-AL-O-CO-**
L ₄₁ -11: * -O-AL-**
L ₄₁ -12: * -O-AL-O-**
L ₄₁ -13: * -O-AL-O-CO-**

L ₄₁ -14: * -O-AL-O-CO-NH-AL-**
L ₄₁ -15: * -O-AL-S-AL-**
L ₄₁ -16: * -O-CO-AL-AR-O-AL-O-CO-**
L ₄₁ -17: * -O-CO-AR-O-AL-CO-**
_{L 41 -18: * - O-} CO-AR-O-AL-O-CO - **
_{L 41 -19: * - O-} CO-AR-O-AL-O-AL-O-CO - **
L ₄₁ -20: * -O-CO-AR-O-AL-O-AL-O-AL-O-CO-**
L ₄₁ -21: * -S-AL-**
L ₄₁ -22: * -S-AL-O-**
_{L 41 -23: * - S-} AL-O-CO - **
L ₄₁ -24: * -S-AL-S-AL-**
L ₄₁ -25: * -S-AR-AL-**

Q ⁴¹ represents a polymerizable group and has the same meaning as the polymerizable group represented by Q ^X1 or Q ^{X2 in} formula (X). In addition, when n41 is 2 or more, a plurality of combinations of L ⁴¹ and Q ⁴¹ may be different, but are preferably the same.

  Examples of the structure derived from the compound represented by the general formula (1) include triphenylene derivatives represented by the general formulas (1) to (3) described in JP-A-7-306317, and JP-A-7-309813. The triphenylene derivative represented by the general formula (I) described in JP-A No. 2001-101, and the triphenylene derivative represented by the general formula (I) described in JP-A-2001-100028 are preferred. Among the triphenylene derivatives, the following compounds having a linking group between the triphenylene structure and the polymerizable group are most preferable.

[First alignment agent: mesogen-containing polymer]
The liquid crystal composition of the present invention contains a mesogenic group polymer as the first alignment agent.
In the present specification, the mesogen group polymer is a radical of a mesogen group monomer having a mesogen group derived from at least one liquid crystal compound selected from a rod-like liquid crystal compound and a discotic liquid crystal compound and two or more polymerizable groups. It means a polymer that includes a partial structure obtained by polymerization and is branched. The mesogen-containing polymer is a polymer containing a mesogenic group derived from a rod-like liquid crystal compound or a disk-like liquid crystal compound as a branched structure, and therefore has a number of branched structures in the molecule as compared with conventional polymer liquid crystal polymers. It has little entanglement between the molecular chains of the polymer, and is highly soluble in various solvents and compatible with matrix resins. Therefore, the liquid crystal composition of the present invention containing a mesogen-containing polymer can form a coating film having excellent surface properties. In addition, the liquid crystal composition containing the first alignment agent is excellent in alignment, and a coating film in which liquid crystals are uniformly aligned can be obtained.

In the present specification, the “branched” polymer means that the polymer has a three-dimensional cross-linked structure and at least one polymerization initiator fragment is incorporated at the end. The polymerization initiator fragment varies depending on the polymerization initiator structure used when polymerizing the polymer, but it can be determined by methods such as NMR (nuclear magnetic resonance) spectrum measurement, IR (infrared) spectrum measurement, mass spectrometry measurement, or elemental analysis measurement. It can be confirmed that polymer fragments are incorporated in the polymer.
The addition amount of the mesogen-containing polymer in the liquid crystal composition may be 0.0001% by mass to 10% by mass, and 0.001% by mass to 5% by mass with respect to the amount of the liquid crystal compound in the liquid crystal composition. It is preferable that it is 0.005 mass%-3 mass%.

(Mesogen-containing monomer)
The mesogenic group monomer may be a rod-like liquid crystal compound having a radical polymerizable group or a discotic liquid crystal compound having a radical polymerizable group. Examples of the mesogen-containing monomer include, for example, a rod-like liquid crystal compound having a radical polymerizable group or a discotic liquid crystal compound having a radical polymerizable group mentioned as examples of the polymerizable liquid crystal compound. That is, examples of the mesogen group-containing polymer are derived from a mesogenic group derived from the rod-like liquid crystal compound represented by the general formula (X) or a discotic liquid crystal compound represented by the general formula (I). The thing containing a mesogenic group is mentioned.
The mesogen-containing monomer is particularly preferably a rod-like liquid crystal compound represented by the general formula (X) or a discotic liquid crystal compound represented by the general formula (I). At this time, the rod-like liquid crystal compound represented by the general formula (X) is preferably a rod-like liquid crystal compound represented by the general formula (XI) or (X-II), represented by the formula (XI). The rod-shaped liquid crystal compound is particularly preferable.

  In the liquid crystal composition of the present invention, the polymerizable liquid crystal compound and the mesogen group monomer from which the partial structure of the mesogen group polymer is derived may be the same or different.

The mesogen-containing polymer may contain a mesogen group different from the mesogen group included in the above examples, for example, a mesogen group derived from a rod-like liquid crystal compound or a discotic liquid crystal compound having one polymerizable group. Good.
The mesogen-containing polymer may contain both a rod-like liquid crystal compound and a mesogenic group derived from a discotic liquid crystal compound in the same molecule.
From the viewpoint of compatibility, it preferably contains a mesogenic group derived from either a rod-like liquid crystal compound or a discotic liquid crystal compound. For example, when it contains a mesogenic group derived from a rod-like liquid crystal compound different from the compound represented by the general formula (X) or a discotic liquid crystal compound different from the compound represented by the general formula (I), The mesogenic group is preferably similar to the compound represented by the general formula (X) or the compound represented by the general formula (I).

(Structure derived from a compound having a fluorine atom or a compound having a siloxane bond)
The mesogen-containing polymer is a polymer containing a structure derived from a compound having a fluorine atom (hereinafter referred to as a fluorine-containing mesogen group polymer), or a polymer containing a structure derived from a compound having a siloxane bond. It is preferable that By making such a polymer containing a structure derived from a fluorine-containing mesogen group polymer or a compound having a siloxane bond, surface uneven distribution of the mesogen group polymer can be improved, for example, the surface of an optical film or the like. Modification is possible.

The partial structure derived from the compound having a fluorine atom is preferably the following structure.

In the formula, R ^a1 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R ^a2 represents an alkyl group having 1 to 20 carbon atoms or a carbon number of 1 to 1 in which at least one carbon atom has a fluorine atom as a substituent. 20 alkenyl groups are represented.
The partial structure may be obtained by polymerizing the compound represented by the general formula (a).

From the viewpoint of reducing the surface energy of the liquid crystal composition of the present invention and enhancing the effect of the present invention, in general formula (a), R ^a2 is a C 1 -C having at least one carbon atom as a substituent. An alkyl group having 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms is preferable, more preferably an alkyl group having 1 to 10 carbon atoms, and more than half of the carbon atoms contained in R ^a2 have a fluorine atom as a substituent. Is particularly preferred.
The compound represented by the general formula (a) is more preferably a compound represented by the general formula (b).

In general formula (b), R ^a1 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, ma and na represent an integer of 0 or more, and X represents a hydrogen atom or a fluorine atom. ma is preferably an integer of 1 to 10, and na is preferably 4 to 12. From the viewpoint of PFOA (perfluorooctanoic acid) regulation, na is more preferably 4 or more and 6 or less.

  For example, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, 2- (perfluorobutyl) ethyl (meth) acrylate, 2- (per Fluorohexyl) ethyl (meth) acrylate, 2- (perfluorooctyl) ethyl (meth) acrylate, 2- (perfluorodecyl) ethyl (meth) acrylate, 2- (perfluoro-3-methylbutyl) ethyl (meth) acrylate 2- (perfluoro-5-methylhexyl) ethyl (meth) acrylate, 2- (perfluoro-7-methyloctyl) ethyl (meth) acrylate, 1H, 1H, 3H-tetrafluoropropyl (meth) acrylate, 1H , 1H, 5H-Octafluoropentyl (meth) acrylate 1H, 1H, 7H-dodecafluoroheptyl (meth) acrylate, 1H, 1H, 9H-hexadecafluorononyl (meth) acrylate, 1H-1- (trifluoromethyl) trifluoroethyl (meth) acrylate, 1H, 1H, 3H-hexafluorobutyl (meth) acrylate, 3-perfluorobutyl-2-hydroxypropyl (meth) acrylate, 3-perfluorohexyl-2-hydroxypropyl (meth) acrylate, 3-perfluorooctyl-2-hydroxypropyl (Meth) acrylate, 3- (perfluoro-3-methylbutyl) -2-hydroxypropyl (meth) acrylate, 3- (perfluoro-5-methylhexyl) -2-hydroxypropyl (meth) acrylate, 3- (per Fluoro-7-methyl Rot) -2-hydroxypropyl (meth) acrylate.

  In the present invention, the ratio of copolymerizing the compound having a fluorine atom is preferably 0.01 to 100 mol, particularly preferably 0, per 1 mol of the mesogenic monomer, from the viewpoint of reactivity and surface modification effect. 0.1 to 50 mol, most preferably 1 to 30 mol.

The structure derived from the compound having a siloxane bond may be a structure having a repeating unit represented by —Si (R ^a3 ) (R ^a4 ) O— and may constitute at least a part of the molecule. It is preferable that the polysiloxane structure is a graft copolymer in which the side chain of the polymer is introduced. In the general formula (a), R ^a2 may include —Si (R ^a3 ) (R ^a4 ) O—. A structure obtained by polymerizing a compound represented by the following general formula (c) is more preferable.

R ^a3 and R ^a4 are each preferably an alkyl group (an alkyl group having 1 to 10 carbon atoms. For example, a methyl group, an ethyl group, a hexyl group, etc.) or a haloalkyl group (a fluorinated alkyl group having 1 to 10 carbon atoms is preferable). For example, a trifluoromethyl group, a pentafluoroethyl group, or the like) or an aryl group (preferably having 6 to 20 carbon atoms, such as a phenyl group, a naphthyl group, etc.), preferably a methyl group, a trifluoromethyl group, or a phenyl group. And particularly preferably a methyl group. R ^a1 has the same meaning as R ^a1 in formula (a), and the preferred range is also the same. R ^a5 is preferably an alkyl group having 1 to 12 carbon atoms, and more preferably 1 to 4 carbon atoms.
As for nn, 10-1000 are preferable, More preferably, it is 20-500, Most preferably, it is 30-200. The repeating unit may be a single unit or a plurality of repeating units. As for nm, 1-12 are preferred and 1-6 are more preferred.

  As the graft copolymer, one-terminal (meth) acryloyl group-containing polysiloxane macromer (for example, Silaplane 0721, 0725 (above, trade name, manufactured by JNC Corporation), AK-5, AK-30, AK-32) (Above, trade name, manufactured by Toagosei Co., Ltd.), KF-100T, X-22-169AS, KF-102, X-22-3701IE, X-22-164B, X-22-164C, X-22- 5002, X-22-173B, X-22-174D, X-22-167B, X-22-161AS (above, trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.

  In the present invention, the ratio of copolymerizing the compound having a siloxane bond is preferably from 0.1 to 50 mol, particularly preferably from 0 to 1 mol of the mesogenic group monomer from the viewpoint of reactivity and surface modification effect. .5 to 30 moles.

(Method for synthesizing mesogen-containing polymer)
The mesogen-containing polymer is used in the presence of a predetermined amount of a polymerization initiator with respect to the mesogen-containing monomer described above, or with respect to the mesogen-containing monomer described above and the compound having a fluorine atom or the compound having a siloxane bond. Examples of the polymerization method include known methods such as solution polymerization, dispersion polymerization, precipitation polymerization, and bulk polymerization. Among these, solution polymerization or precipitation polymerization is preferable. In particular, it is preferable to carry out the reaction by solution polymerization in an organic solvent from the viewpoint of molecular weight control. Examples of organic solvents used here include aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and tetralin; aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, mineral spirit, and cyclohexane Solvent: Halogen solvents such as methyl chloride, methyl bromide, methyl iodide, methylene dichloride, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene, orthodichlorobenzene; ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate , Ethyl cellosolve acetate, propylene glycol monomethyl ether acetate and other ester-based or ester ether-based solvents; diethyl ether, tetrahydrofuran, 1,4-dioxane, methyl cellosolve, ethyl Ether solvents such as rosolve, butyl cellosolve, propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, cyclohexanone; methanol, ethanol, n-propanol, isopropanol, n-butanol, iso Alcohol solvents such as butanol, tert-butanol, 2-ethylhexyl alcohol, benzyl alcohol; amide solvents such as N, N-dimethylformamide and N, N-dimethylacetamide; sulfoxide solvents such as dimethyl sulfoxide, N-methyl- Examples include heterocyclic compound solvents such as 2-pyrrolidone, and mixed solvents of two or more of these.
Of these, aromatic hydrocarbon solvents, halogen solvents, ester solvents, ether solvents, ketone solvents, alcohol solvents, amide solvents, sulfoxide solvents, and the like are preferred, with toluene being particularly preferred. Xylene, orthodichlorobenzene, butyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 1,4-dioxane, methyl cellosolve, methyl isobutyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, etc. .

  When the above polymerization reaction is carried out in the presence of an organic solvent, the content of the organic solvent in the entire polymerization reaction product is preferably 0.00 with respect to 1 part by mass of the rod-like liquid crystal compound or discotic liquid crystal compound forming the mesogenic group. 5-100 mass parts, More preferably, it is 1-50 mass parts.

The polymerization reaction is carried out under normal pressure, under pressure and under pressure, or under reduced pressure, and is preferably carried out under normal pressure in view of simplicity of the apparatus and operation. Further, preferably carried out in an atmosphere of inert gas such as N _2. The temperature of the polymerization reaction is preferably 50 to 200 ° C, more preferably 70 to 150 ° C. More preferably, the temperature of the polymerization reaction is carried out at a temperature that is 10 ° C. or more higher than the 10-hour half-life temperature of the polymerization initiator, more specifically, the rod-like liquid crystal compound or discotic liquid crystal compound that forms the mesogenic group described above, In an organic solvent in which the above-described compound having a fluorine atom or a compound having a siloxane bond, a solution containing a polymerization initiator described later and an organic solvent is maintained at a temperature higher by 10 ° C. than the 10-hour half-life temperature of this polymerization initiator. It is preferable to carry out the polymerization reaction by dripping the solution. After completion of the polymerization reaction, the obtained mesogen group polymer is recovered by an arbitrary method, and post-treatment such as washing is performed as necessary. Examples of a method for recovering the polymer from the reaction solution include a method such as reprecipitation.

The weight average molecular weight (hereinafter abbreviated as Mw) of the obtained mesogenic group polymer is preferably 1,000 to 300,000, more preferably 1,000 to 200, in terms of polystyrene based on gel permeation chromatography (GPC). 1,000, more preferably 1,000 to 100,000, and most preferably 2,000 to 6,000. By setting it as such a value, the viscosity of the composition containing a mesogenic group polymer or the composition for liquid crystal layer preparation can be adjusted to an appropriate value, and the effect of this invention can be heightened.
In this specification, examples of specific measurement conditions for GPC include the following measurement conditions.
GPC device: HLC-8320 (manufactured by Tosoh Corporation):
Column: TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 combined use (manufactured by Tosoh, 4.6 mm ID (inner diameter) x 15.0 cm)
Eluent: Tetrahydrofuran (THF)

As the polymerization initiator in the production of the mesogen-containing polymer, an azo polymerization initiator is preferably used. Examples of the azo polymerization initiator include compounds shown in the following (1) to (6).
(1) Azonitrile compound:
2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 1,1′-azobis ( 1-cyclohexanecarbonitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2- (carbamoylazo) isobutyronitrile and the like;
(2) Azoamide compound:
2,2′-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2′-azobis {2-methyl-N- [2-1 -Hydroxybutyl)] propionamide}, 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2′-azobis [N- (2-propenyl) -2-methyl Propionamide], 2,2′-azobis (N-butyl-2-methylpropionamide), 2,2′-azobis (N-cyclohexyl-2-methylpropionamide) and the like;
(3) Cyclic azoamidine compound:
2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] disulfate dihydrate, 2,2′-azobis [2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane] dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) Propane], 2,2′-azobis (1-imino-1-pyrrolidino-2-methylpropane) dihydrochloride and the like;
(4) Azoamidine compound:
2,2′-azobis (2-methylpropionamidine) dihydrochloride, 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] tetrahydrate, etc .;
(5) Other:
Dimethyl 2,2′-azobisisobutyrate, 4,4′-azobis-4-cyanovaleric acid, 2,2′-azobis (2,4,4-trimethylpentane), 1,1′-azobis (1-acetoxy-1 -Phenylethane), dimethyl 1,1'-azobis (1-cyclohexanecarboxylate), 4,4'-azobis (4-cyanopentanoic acid) and the like.
(6) Fluoroalkyl group-containing azo polymerization initiator:
4,4′-azobis (4-cyanopentanoic acid-2- (perfluoromethyl) ethyl), 4,4′-azobis (4-cyanopentanoic acid-2- (perfluorobutyl) ethyl), 4,4 ′ -Azobis (4-cyanopentanoic acid-2- (perfluorohexyl) ethyl) and the like.

  Among the azo polymerization initiators, those having a relatively low polarity substituent are desirable from the viewpoint of the surface energy of the obtained mesogenic group polymer, and in particular, dimethyl 2,2′-azobisisobutyrate or 2,2 ′ -Azobis (2,4,4-trimethylpentane) is preferred. Further, 4,4′-azobis (4-cyanopentanoic acid-2- (perfluoromethyl) ethyl), 4,4′-azobis (4-cyanopentanoic acid-2), which are fluoroalkyl group-containing azo polymerization initiators. -(Perfluorohexyl) ethyl) can be preferably used.

  The polymerization initiator is preferably 1 to 50 molar equivalents, more preferably 1 to 40 equivalents, and most preferably 2 to 30 molar equivalents with respect to the mesogenic group monomer.

  In the synthesis of the mesogen-containing polymer, the polymerization reaction is a radical polymerization reaction from the viewpoint of controlling the molecular weight.

  The double bond residual ratio in the mesogen-containing polymer obtained by the radical polymerization reaction is preferably 0.05 mol% or less, more preferably 0.01 mol% or less, most preferably 0, based on 1 mol of the polymer. 0.001 mol% or less. By setting the amount to 0.05 mol% or less, the monomer is not unevenly distributed at the air interface of the coating film by light irradiation, so that the coating property of the upper layer is good. The double bond residual ratio can be easily calculated from the peak intensity based on NMR (nuclear magnetic resonance) measurement.

  Although the preferable specific example of a mesogen group polymer is shown below, this invention is not limited to these. Numerical values in the following specific examples represent mass ratios of the partial structures.

[Second aligning agent: hydroxyl group-containing polymer]
The liquid crystal composition of the present invention contains a hydroxyl group-containing polymer as the second alignment agent. In the present specification, the hydroxyl group-containing polymer means a polymer including a partial structure obtained by polymerizing a hydroxyl group monomer having one or more hydroxyl groups and two or more radical polymerizable double bonds. The hydroxyl group-containing polymer may be any polymer obtained by polymerizing a monomer having two or more radical polymerizable double bonds and one or more hydroxyl groups. By having such a structure, when the hydroxyl group-containing polymer is used by adding it to the coating solution, it has good compatibility with other materials, and furthermore, the polymer has polarity due to having a hydroxyl group. It has high affinity with the surface to be coated, improves wettability, and hardly causes repellency. Further, since the hydroxyl group is present on the surface of the coating film, even when the upper layer is laminated and applied, the repellency of the coating solution hardly occurs. That is, the recoatability is excellent. Moreover, the optical film containing such a polymer has a surface with good surface shape and reduced orientation defects.
Although the mechanism is not clear, the present inventors presume as follows. That is, when the liquid crystal composition of the present invention containing a hydroxyl group-containing polymer is applied, repelling can be prevented since the polarity with the lower layer in application, particularly the liquid crystal layer, is close and easy to spread. Furthermore, when a copolymer with a fluorine-containing monomer is used as the hydroxyl-containing polymer, surface migration is improved, and the surface tension of the coating liquid is reduced, thereby providing a planar smoothing (leveling) function. It comes to express. In addition, it is considered that resistance to wind in the surrounding environment is improved, optical unevenness is less likely to occur, and repelling is further suppressed.

  The present inventors have found that by combining the second aligning agent with the first aligning agent, it has been difficult to achieve both recoatability and orientation at the time of lamination coating. . That is, the inventors have found that the excellent recoatability of the second alignment agent and the excellent alignment effect of the first alignment agent are both exhibited without canceling each other.

The addition amount of the hydroxyl group-containing polymer in the liquid crystal composition may be 0.0001% by mass to 10% by mass with respect to the amount of the liquid crystal compound in the liquid crystal composition, and is 0.001% by mass to 5% by mass. It is preferable that it is 0.005% by mass to 3% by mass.
Further, in the liquid crystal composition, the total amount of the first alignment agent and the second alignment agent combined with the mesogen-containing polymer and the hydroxyl-containing polymer is determined by the solid content mass (solvent of the liquid crystal composition). The mass is preferably 0.002 to 30% by mass, more preferably 0.004 to 20% by mass, and particularly preferably 0.004 to 2% by mass.
In the liquid crystal composition, the mass ratio of the mesogen-containing polymer to the hydroxyl-containing polymer is preferably 10: 1 to 1:10, more preferably 5: 1 to 1: 5, 30 : It is more preferable that it is 1-1: 3.

(Hydroxyl-containing monomer)
As the hydroxyl group-containing monomer, a monomer represented by the following general formula Y is preferable.

In the general formula Y, in the formula, Z ^Y1 and Z ^Y2 each independently represent a group having a radical polymerizable double bond, and L ^Y1 and L ^Y4 each independently represent a single bond or an alkylene group having a hydroxyl group. -O-, -S-, -CO-, -NR ^yy1- , -C = N-, and a divalent linking group composed of at least one selected from the group consisting of combinations thereof, R ^yy1 represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms, and L ^Y2 and L ^Y3 are each independently a single bond, —O—, — (C═O) O—, —O ( ^C═ O) — represents a divalent linking group composed of at least one selected from the group consisting of a divalent chain group, an alkylene group having a hydroxyl group, and a divalent cyclic group, and M is a single bond Or a divalent to tetravalent linking group which may have a hydroxyl group. n represents an integer of ^{1~3, L Y1, L Y2,} L Y3, L Y4, and one or more selected from the group consisting of M include a hydroxyl group.

Z ^Y1 and Z ^Y2 each independently represent a group having a radical polymerizable double bond. Examples of the group having a radical polymerizable double bond include the above formulas M-1 to M-5.

  Since the hydroxyl group-containing polymer has a large number of branched structures in the molecule, there are few entanglements between the molecular chains of the polymer, and the solubility in various solvents and the compatibility with the matrix resin are high. Therefore, the coating film excellent in surface property can be formed by using the composition containing a hydroxyl-containing polymer.

L ^Y1 and L ^Y4 are each independently a single bond or an alkylene group having a hydroxyl group, —O—, —S—, —CO—, —NR ^yy1 —, ^—C═N— , and combinations thereof. It represents a divalent linking group composed of at least one selected from the group. L ^Y1 _{is, -O-CH 2 CH (OH} ) CH 2 -, - O-CH 2 CH (CH 2 OH) - are _{preferred, -O-CH 2 CH (OH} ) CH 2 - is more preferable. And ^{L Y4} _{is, -CH 2 CH (OH) CH} 2 -O -, - CH 2 CH (CH 2 OH) -O- is _{preferable, -CH 2 CH (OH) CH} 2 -O- is more preferable. That is, it is preferable that —O— is bonded to the radical polymerizable double bond. L ^Y1 and L ^Y4 may be the same or different.

L ^Y2 and L ^Y3 each independently represent a single bond, —O—, — (C═O) O—, —O (C═O) —, a divalent chain group, an alkylene group having a hydroxyl group, or Represents a divalent cyclic group or a combination thereof. The divalent chain group may be linear or branched. The alkylene group having a hydroxyl _{group, -CH 2 CH (OH) CH} 2 -, - CH 2 CH (CH 2 OH) - are _{preferred, -CH 2 CH (OH) CH} 2 - is more preferable.
Examples of preferred combinations for L ^Y2 and L ^Y3 are shown below.

Preferred combinations of L ^Y2 are shown below. The left side is bonded to the ^ZY1 side, and the right side is bonded to M.
Ly21: -O-2 valent chain group-
Ly22: -O-2 valent cyclic group -bivalent chain group-
Ly23: —OC (═O) -2valent cyclic group—
Ly24: -valent cyclic group-(C = O) O-
Ly25:-(O-2 valent chain group) _n-
Ly26: -O-Hydroxyl alkylene group-

Preferred combinations of L ^Y3 are shown below. The left side is bonded to M, and the right side is bonded to the ^ZY2 side.
Ly31: -valent chain group -O-
Ly32: -bivalent chain group -bivalent cyclic group -O-
Ly33: -valent cyclic group -C (= O) O-
Ly34: -O (C = O) -2 valent cyclic group-
Ly35:-(divalent chain group -O-) _n-
Ly36: -alkylene group having a hydroxyl group -O-

The divalent chain group means an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, or a substituted alkynylene group. An alkylene group, a substituted alkylene group, an alkenylene group and a substituted alkenylene group are preferred, and an alkylene group and an alkenylene group are more preferred.
The alkylene group may have a branch. The alkylene group preferably has 1 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, and most preferably 2 to 8 carbon atoms.
The alkylene part of the substituted alkylene group is the same as the above alkylene group. Examples of the substituent include a halogen atom.
The alkenylene group may have a branch. The alkenylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, and most preferably 2 to 8 carbon atoms.
The alkenylene part of the substituted alkenylene group is the same as the above alkenylene group. Examples of the substituent include a halogen atom.
The alkynylene group may have a branch. The alkynylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, and most preferably 2 to 8 carbon atoms.
The alkynylene part of the substituted alkynylene group is the same as the above alkynylene group. Examples of the substituent include a halogen atom.
Specific examples of the divalent chain group include ethylene, trimethylene, propylene, tetramethylene, 2-methyl-tetramethylene, pentamethylene, hexamethylene, octamethylene, 2-butenylene, 2-butynylene and the like.

  The divalent cyclic group in the general formula Y is preferably a 5-membered ring, a 6-membered ring, or a 7-membered ring, more preferably a 5-membered ring or a 6-membered ring, and a 6-membered ring. Most preferred.

  The ring contained in the divalent cyclic group may be any of an aliphatic ring, an aromatic ring, and a heterocyclic ring. Examples of the aliphatic ring include a cyclohexane ring, a cyclopentane ring, and a norbornene ring. Examples of the aromatic ring include a benzene ring and a naphthalene ring. As the heterocyclic ring, a ring containing at least one sulfur atom, nitrogen atom or oxygen atom is preferable, and a pyridine ring, a pyrimidine ring and an oxadiazole ring are preferable.

  The divalent cyclic group may have a substituent. Examples of the substituent include a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 5 carbon atoms, a halogen-substituted alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a carbon number Is an alkylthio group having 1 to 5 carbon atoms, an acyloxy group having 2 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, a carbamoyl group, an alkyl-substituted carbamoyl group having 2 to 6 carbon atoms, and 2 to 6 carbon atoms Of the acylamino group. Of these, an alkyl group having 1 to 5 carbon atoms and a halogen-substituted alkyl group having 1 to 5 carbon atoms are preferable.

In General Formula Y, n represents an integer of 1 to 3. When n is 2 or 3, a plurality of L ^Y3 and L ^Y4 may be the same or different, and a plurality of Z ^Y2 may be the same or different. n is preferably 1 or 2, and more preferably 1.

In general formula Y, M is a single bond or a bivalent to tetravalent linking group. In general formula Y, when n is 1, it is a divalent linking group, when n is 2, it is a trivalent linking group, and when n is 3, it is a tetravalent linking group.
M is preferably a divalent to tetravalent chain group, a group having an aliphatic cyclic group, or a group having an aromatic ring. The divalent to tetravalent chain group represents a saturated hydrocarbon group having 2 to 4 bonds. 1-40 are preferable, as for carbon number of a saturated hydrocarbon group, 1-20 are more preferable, and it is more preferable that it is 1-10. The saturated hydrocarbon group may be linear or branched.
Examples of the group having an aliphatic cyclic group include a cyclohexane ring, a cyclopentane ring, and a norbornene ring.
Examples of the group having an aromatic cyclic group include a phenyl group and a naphthalene group.

  As the monomer represented by the general formula Y, a monomer represented by the following general formula Y1 is more preferable.

In general formula Y1, R ^Y1 , R ^Y2 , and R ^Y3 each independently represent a hydrogen atom or a methyl group, and L ^Y11 , L ^{Y12, and} L ^Y13 each independently represent a single bond, or —O—, — (C = O) O-, -O (C = O)-, a divalent group composed of at least one selected from the group consisting of a divalent chain group, an alkylene group having a hydroxyl group, and a divalent cyclic group. M ¹ represents a single bond or a divalent, trivalent or tetravalent linking group, and n1 represents an integer of 0 to 2.

R ^Y1 , R ^Y2 and R ^Y3 are preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and most preferably a hydrogen atom or a methyl group.
L ^Y11 , L ^Y12 , and L ^Y13 are synonymous with L ^Y2 and L ^Y3 in General Formula Y, and preferred combinations are also the same.

  When M is a divalent linking group, a monomer represented by the following general formula Y2 is preferred.

R ^Y1 and R ^Y2 are most preferably a hydrogen atom.
L ^Y11 and L ^Y12 are * -O-**, * -O-CH ₂ -**, * -OCH (CH ₃ )-**, * -O-C ₂ H ₄ -**, * -O. —C ₃ H ₆ — ** and * —OCH ₂ CH (OH) CH ₂ — ** are preferred, and * —O—CH ₂ — ** is more preferred. * Is attached to an alkyl group side having a hydroxyl group in the general formula Y2, ** binds to M ^1.
M ¹ is a single bond, —C ₆ H ₁₀ —, —O (C═O) C ₆ H ₄ (C═O) O—, —O (C═O) C ₆ H ₁₀ (C═O) O —, —O—C ₆ H ₄ —C (CH ₃ ) (CH ₃ ) —C ₆ H ₄ —O— are preferred.

The hydroxyl group-containing polymer also preferably has, for example, a partial structure represented by Y0 below.

In the formula Y0, R ^Y1 , R ^Y2 , R ^Y3 , L ¹¹ , L ^12, L ¹³ , M ¹ , and n1 have the same definitions as in the general formula Y1.
The hydroxyl group-containing polymer having the partial structure can be obtained using a monomer represented by the general formula Y1.

(Structure derived from a compound having a fluorine atom or a compound having a siloxane bond)
The hydroxyl group-containing polymer is a polymer including a structure derived from a compound having a fluorine atom (hereinafter referred to as a fluorine-containing hydroxyl group-containing polymer) or a polymer including a structure derived from a compound having a siloxane bond. Preferably there is. By making such a fluorine-containing hydroxyl group-containing polymer or a polymer containing a structure derived from a compound having a siloxane bond, the surface unevenness of the hydroxyl group-containing polymer can be improved. Quality is possible.

  The hydroxyl group-containing polymer may have a partial structure obtained by polymerizing a compound having a fluorine atom. The partial structure formed by polymerizing a compound having a fluorine atom includes the structure represented by a1 described above as the partial structure that the mesogen-containing polymer may contain. This partial structure may be obtained by polymerizing the compound represented by the general formula (a) in the same manner as described in the partial structure that the mesogen-containing polymer may contain, and is preferably in a preferred range. And so on.

  The hydroxyl group-containing polymer may be a copolymer of the above-described compound having a fluorine atom. In the hydroxyl group-containing polymer, the proportion of copolymerizing the compound having a fluorine atom is preferably 0.01 to 100 mol with respect to 1 mol of the hydroxyl group monomer, from the viewpoint of reactivity and surface modification effect. .1 to 50 mol is more preferable, and 0.5 to 30 mol is most preferable.

  The hydroxyl group-containing polymer may have a partial structure derived from a compound having a siloxane bond. As the structure derived from the compound having a siloxane bond, the same structure as the partial structure derived from the compound having a siloxane bond described above can be used as the partial structure that the mesogen-containing polymer may contain.

  In the hydroxyl group-containing polymer, the proportion of copolymerizing the compound having a siloxane bond is preferably 0.1 to 50 mol with respect to 1 mol of the hydroxyl group-containing monomer from the viewpoint of reactivity and surface modification effect. ˜30 mol is particularly preferred.

(Method for synthesizing hydroxyl-containing polymer)
The hydroxyl group-containing polymer is polymerized in the presence of a predetermined amount of a polymerization initiator with respect to the hydroxyl group-containing monomer described above or to the hydroxyl group-containing monomer and the compound having a fluorine atom or the compound having a siloxane bond. As this polymerization method, a method similar to the method for synthesizing the mesogen-containing polymer described above can be used.

However, the polymerization initiator used in the synthesis of the hydroxyl group-containing polymer is preferably 1 to 15 mole equivalents, more preferably 1 to 10 mole equivalents, most preferably 2.0 to 10 moles per mole of the hydroxyl group monomer. .
Moreover, the weight average molecular weight (hereinafter abbreviated as Mw) of the obtained hydroxyl-containing polymer is preferably 1,000 to 300,000, more preferably 1,000 to 300,000 in terms of polystyrene based on gel permeation chromatography (GPC). It may be 10,000.

  Examples of the hydroxyl group-containing polymer are shown below. The present invention is not limited to these. Numerical values in the following specific examples represent mass ratios of the partial structures.

[solvent]
The liquid crystal composition of the present invention preferably contains a solvent. The solvent may be a low surface tension solvent or a standard surface tension solvent. The composition for forming the liquid crystal layer preferably contains a low surface tension solvent.

The surface tension of the low surface tension solvent is 10 to 22 mN / m (10 to 22 dyn / cm), preferably 15 to 21 mN / m, and more preferably 18 to 20 mN / m. The surface tension of the standard surface tension solvent is larger than 22 mN / m, preferably 23 to 50 mN / m, and more preferably 23 to 40 mN / m.
The difference between the surface tension of the low surface tension solvent and the surface tension of the standard surface tension solvent is preferably 2 mN / m or more, more preferably 3 mN / m or more, and 4 to 20 mN / m or more. More preferably, it is 5-15 mN / m.

  In addition, in this specification, the surface tension of a solvent is a value as described in a solvent handbook (Kodansha, 1976 issuance). The surface tension of the solvent is a physical property value that can be measured by, for example, an automatic surface tension meter CBVP-A3 manufactured by Kyowa Interface Science Co., Ltd. The measurement may be performed at 25 ° C.

  As the solvent, an organic solvent is preferably used, and a low surface tension solvent and a standard surface tension solvent can be selected from these. Examples of organic solvents include alcohols (eg, ethanol, tert-butyl alcohol), amides (eg, N, N-dimethylformamide), sulfoxides (eg, dimethyl sulfoxide), heterocyclic compounds (eg, pyridine), hydrocarbons (Eg, heptane, cyclopentane, benzene, hexane, tetrafluoroethylene), alkyl halides (eg, chloroform, dichloromethane), esters (eg, methyl acetate, butyl acetate, isopropyl acetate), ketones (eg, acetone, methyl ethyl ketone, cyclohexanone) ), Ether (eg, tetrahydrofuran, 1,2-dimethoxyethane), and amine (eg, triethylamine). Two or more organic solvents may be used in combination.

  Examples of low surface tension solvents include tert-butyl alcohol (19.5 mN / m), tetrafluoroethylene (TFE, 20.6 mN / m), triethylamine (20.7 mN / m), cyclopentane (21.8 mN / m). m), heptane (19.6 mN / m), and a mixed solvent composed of a combination of any two or more of these solvents. The numerical value indicates the surface tension. Among these, tert-butyl alcohol, tetrafluoroethylene, triethylamine, and cyclopentane are preferable from the viewpoint of safety, tert-butyl alcohol or tetrafluoroethylene is more preferable, and tert-butyl alcohol is more preferable.

Examples of standard surface tension solvents include methyl ethyl ketone (MEK, 23.9 mN / m), methyl acetate (24.8 mN / m), methyl isobutyl ketone (MIBK, 25.4 mN / m), cyclohexanone (34.5 mN / m). ), Acetone (23.7 mN / m), isopropyl acetate (0.022.1 mN / m), and a mixed solvent composed of a combination of any two or more of these solvents. The numerical value indicates the surface tension. Of these, methyl ethyl ketone, a mixed solvent of cyclohexanone and another solvent, a mixed solvent of methyl acetate and methyl isobutyl ketone, and the like are preferable.
The concentration of the solvent in the liquid crystal composition of the present invention is preferably 95 to 50% by mass, more preferably 93 to 60% by mass, and still more preferably 90 to 75% by mass.

[Polymerization initiator]
The liquid crystal composition of the present invention preferably contains a polymerization initiator. For example, in an embodiment in which a curing reaction is caused to proceed by ultraviolet irradiation to form a cured film, the polymerization initiator to be used is preferably a photopolymerization initiator that can initiate a polymerization reaction by ultraviolet irradiation. Examples of the polymerization initiator include α-carbonyl compounds (described in US Pat. Nos. 2,367,661 and 2,367,670), acyloin ether (described in US Pat. No. 2,448,828), α-hydrocarbon substituted aromatics. An acyloin compound (described in US Pat. No. 2,722,512), a polynuclear quinone compound (described in US Pat. Nos. 3,046,127 and 2,951,758), a combination of a triarylimidazole dimer and p-aminophenyl ketone (US Pat. 3549367), acridine and phenazine compounds (JP-A-60-105667, US Pat. No. 4,239,850) and oxadiazole compounds (US Pat. No. 4,221,970), acylphosphine oxides Compound (Japanese Examined Patent Publication Sho 63-407) No. 99, JP-B-5-29234, JP-A-10-95788, JP-A-10-29997, and oxime compounds (JP-B 63-40799, JP-B-5-29234, JP-A-5-29234). JP-A-10-95788, JP-A-10-29997, JP-A-2001-233842, JP-A-2000-80068, JP-A-2006-342166, JP-A-2013-114249, JP-A-2014-137466, JP-A-4223071 JP, 2010-262028, JP, 2014-500852, A each gazette)) etc. are mentioned.

As the polymerization initiator, an acyl phosphine oxide compound or an oxime compound is preferably used.
As the acylphosphine oxide compound, for example, IRGACURE819 (compound name: bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide) manufactured by BASF Japan Ltd. can be used. Examples of the oxime compounds include IRGACURE OXE01 (manufactured by BASF), IRGACURE OXE02 (manufactured by BASF), TR-PBG-304 (manufactured by Changzhou Power Electronics New Materials Co., Ltd.), Adeka Arcles NCI-831, Adeka Arcles NCI-930 Commercial products such as (ADEKA) and Adeka Arcles NCI-831 (ADEKA) can be used.
Only one type of polymerization initiator may be used, or two or more types may be used in combination.
The photopolymerization initiator is preferably contained in the liquid crystal composition in an amount of 0.1 to 20% by mass, more preferably 1 to 8% by mass, based on the solid content of the liquid crystal composition. .

[Chiral compound]
The liquid crystal composition of the present invention may contain a chiral compound. By using a chiral compound, it can be prepared as a composition showing a cholesteric liquid crystal phase. The chiral compound may be liquid crystalline or non-liquid crystalline. Examples of chiral agents include liquid crystal device handbook (Chapter 3-4, TN, chiral agent for STN, 199 pages, edited by Japan Society for the Promotion of Science, 142nd Committee, 1989), JP-A 2003-287623, Examples thereof include compounds described in JP-A No. 2002-302487, JP-A No. 2002-80478, JP-A No. 2002-80851, JP-A No. 2010-181852 or JP-A No. 2014-034581. A chiral compound generally contains an asymmetric carbon atom, but an axial asymmetric compound or a planar asymmetric compound containing no asymmetric carbon atom can also be used. Examples of the axial asymmetric compound or the planar asymmetric compound include binaphthyl, helicene, paracyclophane, and derivatives thereof. The chiral compound (chiral agent) may have a polymerizable group. When the chiral compound has a polymerizable group and the rod-shaped liquid crystal compound used in combination also has a polymerizable group, a repeating unit derived from the rod-shaped liquid crystal compound by a polymerization reaction between the polymerizable chiral compound and the polymerizable rod-shaped liquid crystal compound And polymers having repeating units derived from chiral compounds. Accordingly, the polymerizable group possessed by the polymerizable chiral compound is preferably the same type as the polymerizable group possessed by the polymerizable rod-like liquid crystal compound, particularly the polymerizable compound represented by formula (I). Therefore, the polymerizable group of the chiral compound is also preferably an unsaturated polymerizable group, an epoxy group or an aziridinyl group, more preferably an unsaturated polymerizable group, and an ethylenically unsaturated polymerizable group. Particularly preferred.

  In the liquid crystal composition, the chiral compound is preferably 0.5 to 30% by mass with respect to the polymerizable liquid crystal compound. A smaller amount of chiral compound is preferred because it tends not to affect liquid crystallinity. Therefore, as the chiral compound, a compound having a strong twisting power is preferable so that a twisted orientation with a desired helical pitch can be achieved even with a small amount. Examples of such a chiral agent exhibiting a strong twisting force include the chiral agents described in JP-A-2003-287623. Moreover, the chiral agent as described in Unexamined-Japanese-Patent No. 2002-302487, Unexamined-Japanese-Patent No. 2002-80478, Unexamined-Japanese-Patent No. 2002-80851, and Unexamined-Japanese-Patent No. 2014-034581 is mentioned. As the chiral agent, an isosorbide derivative, an isomannide derivative, or a binaphthyl derivative can be preferably used. As the isosorbide derivative, commercially available products such as LC-756 manufactured by BASF may be used.

  A film formed by fixing a liquid crystal composition containing a chiral compound into a cholesteric liquid crystal phase and then fixing it exhibits selective reflection characteristics for light of a predetermined wavelength according to the helical pitch. It is useful as a reflection film (for example, a visible light reflection film or an infrared reflection film).

[Fluorine-based surfactant and silicone-based surfactant]
The liquid crystal composition of the present invention may contain a fluorine-based surfactant and a silicone-based surfactant. It is preferable that content of the fluorine-type surfactant and silicone-type surfactant of the composition for liquid crystal layer preparation is 5 mass% or less with respect to the total mass of a composition.

The fluorine-based surfactant is a compound containing fluorine and is unevenly distributed on the surface in the solvent used in the composition for producing a liquid crystal layer. Examples of the fluorosurfactant having a hydrophobic portion include those containing fluorine among compounds described as alignment control agents described in paragraphs 0028 to 0034 of JP2011-191582A, Japanese Patent No. 2841611 And fluorine-based surfactants described in paragraphs 0017 to 0019 of JP-A-2005-272560.
Examples of commercially available fluorosurfactants include Surflon (registered trademark) manufactured by AGC Seimi Chemical Co., Ltd. and MegaFac (registered trademark) manufactured by DIC Corporation.

The silicone-based surfactant is a compound containing silicone, and is a compound unevenly distributed on the surface in the solvent used in the composition for producing a liquid crystal layer.
Examples of the silicone surfactant include polymethylphenylsiloxane, polyether-modified silicone oil, polyether-modified dimethylpolysiloxane, dimethylsilicone, diphenylsilicone, hydrogen-modified polysiloxane, vinyl-modified polysiloxane, hydroxy-modified polysiloxane, Amino modified polysiloxane, carboxyl modified polysiloxane, chloro modified polysiloxane, epoxy modified polysiloxane, methacryloxy modified polysiloxane, mercapto modified polysiloxane, fluorine modified polysiloxane, long chain alkyl modified polysiloxane, phenyl modified polysiloxane, silicone modified copolymer And low molecular weight compounds containing silicon atoms.

  Examples of commercially available silicone surfactants include KF-96, X-22-945 (manufactured by Shin-Etsu Chemical Co., Ltd.), Tore Silicone DC3PA, DC7PA, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, FS-1265-300 (manufactured by Toray Dow Corning Silicone Co., Ltd.), TSF-4300, -4440, -4445, -4446, -4442, -4460 (above, GE Toshiba Silicon Co., Ltd.), polysiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), BYK-301, BYK-302, BYK-307, BYK-325, BYK-331, BYK-333 BYK-341, BYK-345, BYK-346, BYK-348, BYK-375 ( Top, manufactured by Big Chemie Japan Co., Ltd.), Aron GS-30 (above, manufactured by Toagosei Co., Ltd.), Silicone L-75, Silicone L-76, Silicone L-77, Silicone L-78, Silicone L-79, Silicone Examples thereof include L-520 and silicone L-530 (manufactured by Nippon Unica Co., Ltd.).

[Crosslinking agent]
The liquid crystal composition of the present invention may optionally contain a crosslinking agent in order to improve the film strength after curing and the durability. As the cross-linking agent, one that can be cured by ultraviolet rays, heat, moisture, or the like can be suitably used.
There is no restriction | limiting in particular as a crosslinking agent, According to the objective, it can select suitably, For example, polyfunctional acrylate compounds, such as a trimethylol propane tri (meth) acrylate, a pentaerythritol tri (meth) acrylate, a pentaerythritol tetraacrylate; Epoxy compounds such as glycidyl (meth) acrylate and ethylene glycol diglycidyl ether; 2,2-bishydroxymethylbutanol-tris [3- (1-aziridinyl) propionate], 4,4-bis (ethyleneiminocarbonylamino) diphenylmethane, etc. Aziridine compounds; isocyanate compounds such as hexamethylene diisocyanate and biuret type isocyanate; polyoxazoline compounds having an oxazoline group in the side chain; vinyltrimethoxysilane, N- Such as 2-aminoethyl) 3-aminopropyl alkoxysilane compounds such as trimethoxysilane. Moreover, a well-known catalyst can be used according to the reactivity of a crosslinking agent, and productivity can be improved in addition to membrane strength and durability improvement. These may be used individually by 1 type and may use 2 or more types together.
3 mass%-20 mass% are preferable with respect to solid content mass of a liquid-crystal composition, and, as for content of a crosslinking agent, 5 mass%-15 mass% are more preferable. When the content of the crosslinking agent is 3% by mass or more, the effect of improving the crosslinking density is higher, and when it is 20% by mass or less, the stability of the cholesteric liquid crystal layer is higher.

[Other additives]
The liquid crystal composition of the present invention comprises one or more kinds of antioxidants, ultraviolet absorbers, sensitizers, stabilizers, plasticizers, chain transfer agents, polymerization inhibitors, antifoaming agents, and leveling agents. , And other additives such as thickeners, flame retardants, surfactants, dispersants, dyes, pigments and other colorants.

<Film>
As described above, when the liquid crystal composition of the present invention is used, not only repelling is unlikely to occur at the time of coating formation, but also when the upper layer is formed with the layer produced using the liquid crystal composition as the lower layer, It is hard to produce. Therefore, using the liquid crystal composition of the present invention, it is possible to produce a film having various functions, particularly a film including two or more liquid crystal layers.
The liquid crystal composition can be applied onto a support, an alignment layer, a previously prepared liquid crystal layer or the like, and dried to obtain a coating film, which can be cured to form a liquid crystal layer. A film including a plurality of liquid crystal layers can be formed by repeating the manufacturing process of the liquid crystal layer. The film of this invention should just contain the liquid crystal layer formed from the liquid-crystal composition of this invention.

[Coating, orientation, curing]
The method for applying the liquid crystal composition to the support, alignment film, lower liquid crystal layer, etc. is not particularly limited and can be appropriately selected according to the purpose. For example, wire bar coating, curtain coating, extrusion Examples thereof include a coating method, a direct gravure coating method, a reverse gravure coating method, a die coating method, a spin coating method, a dip coating method, a spray coating method, and a slide coating method. In addition, a coating film can be formed by discharging the composition from a nozzle using an ink jet apparatus. Furthermore, it can also be carried out by transferring a liquid crystal composition separately coated on a support.

  Next, the liquid crystal composition applied to the surface to become a coating film is brought into a liquid crystal phase state such as a nematic phase or a cholesteric liquid crystal phase. In the aspect in which the liquid crystal composition is prepared as a coating solution containing a solvent, the liquid crystal phase may be obtained by drying the coating film and removing the solvent. Moreover, in order to set it as the transition temperature to a liquid crystal phase, you may heat a coating film if desired. For example, the liquid crystal phase can be stably formed by heating to the temperature of the isotropic phase and then cooling to the liquid crystal phase transition temperature. The liquid crystal phase transition temperature of the liquid crystal composition is preferably in the range of 10 to 250 ° C., more preferably in the range of 10 to 150 ° C. from the viewpoint of production suitability and the like. By setting the temperature to 10 ° C. or higher, a cooling step or the like for reducing the temperature to a temperature range exhibiting a liquid crystal phase becomes unnecessary. Further, by setting the temperature to 250 ° C. or lower, it is possible to prevent waste of heat energy, deformation of the substrate, or alteration due to the isotropic liquid state having a temperature higher than the temperature range once exhibiting the liquid crystal phase. .

Curing of the coating film in the liquid crystal phase may proceed according to any polymerization method such as a radical polymerization method, an anionic polymerization method, a cationic polymerization method, a coordination polymerization method, etc., but a radical polymerization method is preferred. A suitable polymerization method may be selected according to the polymerizable liquid crystal compound used. By this polymerization, a polymer having a unit derived from the polymerizable compound used in the constituent unit is obtained.
In one example, ultraviolet light is irradiated to advance the curing reaction. For ultraviolet irradiation, a light source such as an ultraviolet lamp is used. In this step, the curing reaction of the composition proceeds by irradiating with ultraviolet rays, the liquid crystal phase (nematic phase or cholesteric liquid crystal phase or the like) is fixed, and a cured film is formed.
No particular limitation is imposed on the amount of irradiation energy of ultraviolet rays, in ^{general, 0.1J / cm 2 ~0.8J / cm} 2 is preferably about. Moreover, there is no restriction | limiting in particular about the time which irradiates a coating film with an ultraviolet-ray, However, What is necessary is just to determine from the viewpoint of sufficient intensity | strength and productivity of a cured film.

  In order to accelerate the curing reaction, ultraviolet irradiation may be performed under heating conditions. Moreover, it is preferable to maintain the temperature at the time of ultraviolet irradiation in the temperature range which exhibits a liquid crystal phase so that a liquid crystal phase may not be disturbed. Also, since the oxygen concentration in the atmosphere is related to the degree of polymerization, if the desired degree of polymerization is not reached in the air and the film strength is insufficient, the oxygen concentration in the atmosphere is reduced by a method such as nitrogen substitution. It is preferable.

  In the above step, the liquid crystal phase is fixed and a cured film is formed. Here, the state in which the liquid crystal phase is “fixed” is the most typical and preferred state in which the orientation of the compound that is the liquid crystal phase is maintained. However, it is not limited to this. Specifically, in the temperature range of 0 ° C. to 50 ° C., and −30 ° C. to 70 ° C. under more severe conditions, the layer has no fluidity, and the orientation form is caused by an external field or external force. This means a state in which the fixed orientation form can be kept stable without causing a change in the above. In the present invention, the alignment state of the liquid crystal phase is preferably fixed by a curing reaction that proceeds by ultraviolet irradiation.

  There is no restriction | limiting in particular about the thickness of the said cured film. What is necessary is just to determine a preferable film thickness according to an application or according to the optical characteristic made desired. In general, the thickness is preferably 0.05 to 50 μm, more preferably 1 to 35 μm.

[Manufacture of a film including a plurality of liquid crystal layers]
When laminating a plurality of liquid crystal layers, a separately prepared liquid crystal layer may be laminated using an adhesive or the like, and a liquid crystal composition containing a polymerizable liquid crystal compound or the like is directly applied to the surface of the liquid crystal layer and aligned. And the curing step may be repeated, the latter being preferred.
For example, by forming the next cholesteric liquid crystal layer directly on the surface of the previously formed cholesteric liquid crystal layer, the orientation direction of the liquid crystal molecules on the air interface side of the previously formed cholesteric liquid crystal layer and the cholesteric liquid crystal formed thereon The alignment orientations of the liquid crystal molecules below the liquid crystal layer coincide with each other, and the polarization property of the laminate of the cholesteric liquid crystal layer can be improved. Moreover, it is laminated without using an adhesive layer in order to prevent interference unevenness derived from thickness unevenness of the adhesive layer, which may be observed when an adhesive layer provided with a film thickness of 0.5 to 10 μm is used. It is preferable.

  As described above, a layer obtained by curing the liquid crystal composition of the present invention (a layer obtained by curing the liquid crystal composition) is less likely to cause repellency even when a coating liquid for forming an upper layer is applied as a lower layer. Therefore, any one of the liquid crystal layers adjacent to the cured layer of the liquid crystal composition of the present invention is preferably in direct contact with the cured layer of the liquid crystal composition. And it is preferable that the liquid crystal layer is formed from the liquid crystal composition directly applied to the lower layer surface, with the layer obtained by curing the liquid crystal composition of the present invention as the lower layer. The liquid crystal composition constituting the coating liquid for forming the upper layer only needs to contain the above-described polymerizable liquid crystal compound and, if necessary, the above-described polymerization initiator, chiral agent, crosslinking agent and the like. The liquid crystal composition constituting the coating liquid for forming the upper layer may or may not contain the first alignment agent and the second alignment agent. When the coating liquid is further applied to the surface of the upper layer to be formed to provide the third and fourth liquid crystal layers, the first aligning agent is used as the liquid crystal composition constituting the upper layer forming coating liquid. It is preferable to use the liquid crystal composition of the present invention containing a second alignment agent. Furthermore, the liquid crystal composition when forming a layer in which no upper layer is formed may not contain either the first aligning agent or the second aligning agent, but preferably contains either one, It is more preferable that at least a first alignment agent is included, and it is further preferable that both a first alignment agent and a second alignment agent are included. This is because the alignment of the liquid crystal compound is also good in the upper layer.

[substrate]
The film may have a substrate. As long as the substrate is self-supporting and supports the cured film, there is no limitation on the material and optical characteristics. It can be selected from a glass plate, a quartz plate, a polymer film, and the like. Depending on the application, those having high transparency to ultraviolet light may be used. Examples of the polymer film having high transparency to visible light include polymer films for various optical films used as members of display devices such as liquid crystal display devices. Examples of substrates include polyester films such as polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate (PEN); polycarbonate (PC) films and polymethyl methacrylate films; polyolefin films such as polyethylene and polypropylene; polyimide films and triacetyl A cellulose (TAC) film etc. are mentioned. A polyethylene terephthalate film and a triacetyl cellulose film are preferred.

[Alignment layer]
The film may have an alignment layer between the substrate and the cured film. The alignment layer has a function of more precisely defining the alignment direction of the liquid crystal compound. The alignment layer can be provided by means such as a rubbing treatment of an organic compound (preferably a polymer), oblique vapor deposition of an inorganic compound, or formation of a layer having a microgroove. Furthermore, an alignment layer in which an alignment function is generated by application of an electric field, application of a magnetic field, or light irradiation is also known. The alignment layer is preferably formed on the surface of the polymer film by rubbing treatment.

  As a material used for the alignment layer, a polymer of an organic compound is preferable, and a polymer that can be crosslinked by itself or a polymer that is crosslinked by a crosslinking agent is often used. Of course, polymers having both functions are also used. Examples of polymers include polymethyl methacrylate, acrylic acid / methacrylic acid copolymer, styrene / maleimide copolymer, polyvinyl alcohol and modified polyvinyl alcohol, poly (N-methylolacrylamide), styrene / vinyl. Toluene copolymer, chlorosulfonated polyethylene, nitrocellulose, polyvinyl chloride, chlorinated polyolefin, polyester, polyimide, vinyl acetate / vinyl chloride copolymer, ethylene / vinyl acetate copolymer, carboxymethyl cellulose, gelatin, Mention may be made of polymers such as polyethylene, polypropylene and polycarbonate and compounds such as silane coupling agents. Examples of preferred polymers include water-soluble polymers such as poly (N-methylolacrylamide), carboxymethylcellulose, gelatin, polyvir alcohol and modified polyvinyl alcohol, of which gelatin, polyvir alcohol and modified polyvinyl alcohol. Alcohol is preferred, and polyville alcohol and modified polyvinyl alcohol are particularly preferred.

[Adhesive layer]
The film may include an adhesive layer. The adhesive layer may be formed from an adhesive.
Adhesives include hot melt type, thermosetting type, photocuring type, reactive curing type, and pressure-sensitive adhesive type that does not require curing, from the viewpoint of curing method, and the materials are acrylate, urethane, urethane acrylate, epoxy , Epoxy acrylate, polyolefin, modified olefin, polypropylene, ethylene vinyl alcohol, vinyl chloride, chloroprene rubber, cyanoacrylate, polyamide, polyimide, polystyrene, polyvinyl butyral, etc. can do. From the viewpoint of workability and productivity, the photocuring type is preferable as the curing method, and from the viewpoint of optical transparency and heat resistance, it is preferable to use an acrylate, urethane acrylate, epoxy acrylate, or the like material.
The thickness of the adhesive layer may be 0.5 to 10 μm, preferably 1 to 5 μm. When used as a projected image display half mirror, it is preferably provided with a uniform film thickness to reduce color unevenness and the like.

[Use of film]
As an example of the film formed using a liquid crystal composition, the film which fixed the orientation (for example, horizontal orientation, vertical orientation, hybrid orientation, etc.) of the liquid crystal phase of a liquid crystal composition is mentioned. Such a film usually exhibits optical anisotropy and is used as an optical compensation film for a liquid crystal display device or the like.
As another example, a film including a layer in which a cholesteric liquid crystal phase of a liquid crystal composition is fixed, which exhibits selective reflection characteristics with respect to light in a predetermined wavelength range (hereinafter referred to as “selective reflection film”). There is).
In the cholesteric liquid crystal phase, the liquid crystal molecules are arranged in a spiral. A layer in which a cholesteric liquid crystal phase is fixed (hereinafter sometimes referred to as a “cholesteric liquid crystal layer”) selectively reflects either right circularly polarized light or left circularly polarized light in the selective reflection wavelength region, and the other sense circle. It functions as a circularly polarized light selective reflection layer that transmits polarized light. A film containing one or more cholesteric liquid crystal layers can be used for various applications. In a film including two or more cholesteric liquid crystal layers, the sense of circularly polarized light reflected by each cholesteric liquid crystal layer may be the same or opposite depending on the application. Further, the center wavelength of selective reflection described later of each cholesteric liquid crystal layer may be the same or different depending on the application.

  In this specification, “sense” for circularly polarized light means right circularly polarized light or left circularly polarized light. The sense of circularly polarized light is right-handed circularly polarized light when the electric field vector tip turns clockwise as time increases when viewed as the light travels toward you, and left when it turns counterclockwise. Defined as being circularly polarized. In this specification, the term “sense” may be used for the twist direction of the spiral of the cholesteric liquid crystal. When the twist direction (sense) of the spiral of the cholesteric liquid crystal is right, it reflects right circularly polarized light and transmits left circularly polarized light. When the sense is left, it reflects left circularly polarized light and transmits right circularly polarized light.

For example, a film including a cholesteric liquid crystal layer exhibiting selective reflection characteristics in the visible light wavelength region (wavelength 400 to 750 nm) can be used as a screen for projecting image display and a half mirror. Further, by controlling the reflection band, it can be used as a color filter or a filter for improving the color purity of display light of a display (see, for example, JP-A-2003-294948).
The optical film can be used for various applications such as a polarizing element, a reflection film, an antireflection film, a viewing angle compensation film, a holography, and an alignment film, which are constituent elements of the optical element.
Hereinafter, the use as a projection image display member, which is a particularly preferable use, will be described.

[Projection display material]
With the above function of the cholesteric liquid crystal layer, it is possible to form a projected image by reflecting the circularly polarized light of one of the senses at a wavelength showing selective reflection in the projection light. The projected image may be displayed on the surface of the projected image display member and viewed as such, or may be a virtual image that appears above the projected image display member when viewed from the observer.

  The center wavelength λ of the selective reflection depends on the pitch P (= spiral period) of the helical structure in the cholesteric liquid crystal phase, and follows the relationship between the average refractive index n of the cholesteric liquid crystal layer and λ = n × P. Here, the selective reflection center wavelength λ of the cholesteric liquid crystal layer means the wavelength at the center of gravity of the reflection peak of the circularly polarized reflection spectrum measured from the normal direction of the cholesteric liquid crystal layer. As can be seen from the above equation, the center wavelength of selective reflection can be adjusted by adjusting the pitch of the helical structure. That is, by adjusting the n value and the P value, for example, to selectively reflect either the right circularly polarized light or the left circularly polarized light with respect to the blue light, the center wavelength λ is adjusted, and an apparent selection is made. The central wavelength of reflection can be in the wavelength range of 450 nm to 495 nm. The apparent selective reflection center wavelength is the wavelength at the center of gravity of the reflection peak of the circularly polarized reflection spectrum of the cholesteric liquid crystal layer measured from the observation direction in practical use (when used as a projection image display member). means. Since the pitch of the cholesteric liquid crystal phase depends on the type of chiral agent used together with the polymerizable liquid crystal compound or the concentration of the chiral agent, the desired pitch can be obtained by adjusting these. For the method of measuring spiral sense and pitch, use the methods described in “Introduction to Liquid Crystal Chemistry Experiments”, edited by the Japanese Liquid Crystal Society, Sigma Publishing 2007, page 46, and “Liquid Crystal Handbook”, Liquid Crystal Handbook Editing Committee, page 196. be able to.

  The half-value width Δλ (nm) of the selective reflection wavelength region showing the circularly polarized light selective reflection follows the relationship of Δλ = Δn × P, where Δλ depends on the birefringence Δn of the liquid crystal compound and the pitch P. Therefore, the width of the selective reflection wavelength region can be controlled by adjusting Δn. That is, in the cholesteric liquid crystal layer formed from the composition containing the polymerizable liquid crystal compound of the present invention having low birefringence, the wavelength selectivity of selective reflection can be increased.

  As an index indicating the wavelength selectivity of selective reflection, for example, Δλ / λ which is a ratio of the half-value width Δλ of the selective reflection wavelength region and the center wavelength λ of selective reflection can be used. In the film of the present invention, particularly a film used as a projection image display member, Δλ / λ is preferably 0.09 or less, and more preferably 0.07 or less. More specifically, in the cholesteric liquid crystal layer in the film, Δλ / λ preferably satisfies the above, and in a film including two or more cholesteric liquid crystal layers, Δλ / λ in each of the two or more cholesteric liquid crystal layers is It is preferable to satisfy the above. Each layer may have the same or different Δλ and λ.

  Using the liquid crystal composition, a cured film having an apparent selective reflection center wavelength in each of the red light wavelength region, the green light wavelength region, and the blue light wavelength region is prepared, and a full color is obtained by laminating them. A projection image display member capable of displaying a projection image can be produced. Specifically, the half mirror includes liquid crystal layers (cured films) each having a central wavelength of selective reflection that is different from each other (for example, 50 nm or more different) in the respective ranges of 750 nm to 620 nm, 630 nm to 500 nm, and 530 nm to 420 nm. It is preferable to laminate.

  By adjusting the central wavelength of selective reflection of each liquid crystal layer according to the emission wavelength range of the light source used for projection and the usage mode of the projection image display member, it is possible to display a clear projection image with high light utilization efficiency. it can. In particular, by adjusting the central wavelength of selective reflection of the liquid crystal layer according to the emission wavelength range of the light source used for projection, a clear color projection image can be displayed with high light utilization efficiency. Examples of usage of the projection image display member include an incident angle of projection light on the surface of the projection image display half mirror, a projection image observation direction on the surface of the projection image display member, and the like.

  For example, a half mirror that can be used as a combiner of a head-up display can be obtained by configuring the projection image display member to be transparent to light in the visible light region. The projected image display half mirror can display an image projected from a projector or the like so that the projected image can be viewed. When the projected image displayed half mirror is observed from the same side where the image is displayed, It is possible to observe information or scenery on the surface side at the same time.

When used as a projected image display half mirror, a liquid crystal layer produced as described above, particularly a laminate of three or more liquid crystal layers, is preferably provided on the surface of the substrate. The substrate is preferably transparent in the visible light region and low birefringence. For example, the retardation of the substrate at a wavelength of 550 nm is preferably 50 nm or less, and more preferably 20 nm or less.
Examples of base materials include inorganic glass and polymer resins (acrylic resins (acrylic esters such as polymethyl (meth) acrylate)), polycarbonate, cyclic polyolefins such as cyclopentadiene polyolefin and norbornene polyolefin, and polyolefins such as polypropylene. And aromatic vinyl polymers such as polystyrene, polyarylate, cellulose acylate, etc.).

  The half mirror for projecting image display may include an antireflection layer. The antireflection layer is preferably contained on the outermost surface. It may be provided on the outermost surface on the observation side when using the half mirror for projected image display, or may be provided on the outermost surface on the opposite side, but provided on the outermost surface on the observation side Is preferred. When providing a cured film on the substrate surface, an antireflection layer may be provided on both the substrate side surface and the cured film side on the observation side. This is because such a configuration makes it difficult to generate a double image that may occur particularly when the base material has high birefringence.

As the antireflection layer, for example, in addition to a film having fine surface irregularities, a two-layer film structure in which a high refractive index layer and a low refractive index layer are combined, a middle refractive index layer, a high refractive index layer, and a low refractive index layer are used. Examples thereof include a film having a three-layer film structure in which refractive index layers are sequentially stacked.
As a configuration example, two layers of a high refractive index layer / low refractive index layer or three layers having different refractive indexes are arranged in order from the bottom, and a medium refractive index layer (having a higher refractive index than the lower layer and a high refractive index). In some cases, a layer having a lower refractive index than a layer) / a layer having a higher refractive index / a layer having a lower refractive index are stacked in this order. Among them, from the viewpoint of durability, optical characteristics, cost, productivity, etc., it is preferable to have a medium refractive index layer / high refractive index layer / low refractive index layer in this order on the hard coat layer, for example, JP-A-8-122504. Examples include the configurations described in JP-A-8-110401, JP-A-10-300902, JP-A 2002-243906, JP-A 2000-11706, and the like. Further, an antireflection film having a three-layer structure excellent in robustness against film thickness fluctuation is described in JP-A-2008-262187. When the antireflection film having the above three-layer structure is installed on the surface of an image display device, the average value of reflectance can be reduced to 0.5% or less, reflection can be remarkably reduced, and a three-dimensional effect can be achieved. An excellent image can be obtained. Further, each layer may be provided with other functions, for example, an antifouling low refractive index layer, an antistatic high refractive index layer, an antistatic hard coat layer, an antiglare hard coat layer, and the like. (For example, JP-A-10-206603, JP-A-2002-243906, JP-A-2007-264113, etc.) and the like.

As the inorganic material constituting the anti-reflection _{layer, SiO 2, SiO, ZrO 2} , TiO 2, TiO, Ti 2 O 3, Ti 2 O 5, Al 2 O 3, Ta 2 O 5, CeO 2, MgO, Y ₂ O ₃ , SnO ₂ , MgF ₂ , WO _{3 and the} like can be mentioned, and these can be used alone or in combination of two or more. Among these, SiO ₂ , ZrO ₂ , TiO ₂ and Ta ₂ O ₅ are preferable because they can be vacuum-deposited at a low temperature and can form a film on the surface of a plastic substrate.
As a multilayer film formed of an inorganic material, the total optical film thickness of the ZrO ₂ layer and the SiO ₂ layer from the substrate side is λ / 4, the optical film thickness of the ZrO ₂ layer is λ / 4, and the outermost SiO ₂ layer is SiO _2. A laminated structure in which a high refractive index material layer and a low refractive index material layer having an optical film thickness of λ / 4 are alternately formed is exemplified. Here, λ is a design wavelength, and usually 520 nm is used. The outermost layer is preferably made of SiO ₂ because it has a low refractive index and can impart mechanical strength to the antireflection layer.
When the antireflection layer is formed of an inorganic material, for example, a vacuum deposition method, an ion plating method, a sputtering method, a CVD method, a method of depositing by a chemical reaction in a saturated solution, or the like can be employed.

Examples of the organic material used for the low refractive index layer include FFP (tetrafluoroethylene-hexafluoropropylene copolymer), PTFE (polytetrafluoroethylene), ETFE (ethylene-tetrafluoroethylene copolymer), and the like. And a composition containing a fluorine-containing curable resin and inorganic fine particles described in JP-A-2007-298974, JP-A-2002-317152, JP-A-2003-202406, and JP-A-2003-292831. The low-refractive-index coating composition containing hollow silica fine particles described in the Japanese Patent Publication No. 1 can be suitably used. Examples of the film forming method include a vacuum deposition method and a coating method excellent in mass productivity such as a spin coating method, a dip coating method, and a gravure coating method.
The low refractive index layer preferably has a refractive index of 1.30 to 1.51. It is preferably 1.30 to 1.46, more preferably 1.32 to 1.38.

Examples of organic materials used for the medium refractive index layer and the high refractive index layer include ionizing radiation curable compounds containing aromatic rings, ionizing radiation curable compounds containing halogenated elements other than fluorine (eg, Br, I, Cl, etc.), Examples thereof include binders obtained by crosslinking or polymerization reaction such as ionizing radiation curable compounds containing atoms such as S, N, and P, and inorganic particles mainly composed of TiO ₂ added thereto. Specifically, those described in JP-A-2008-262187, paragraph numbers [0074] to [0094] can be exemplified.
The refractive index of the high refractive index layer is preferably 1.65 to 2.20, and more preferably 1.70 to 1.80. The refractive index of the middle refractive index layer is adjusted to be a value between the refractive index of the low refractive index layer and the refractive index of the high refractive index layer. The refractive index of the medium refractive index layer is preferably 1.55 to 1.65, and more preferably 1.58 to 1.63.
The thickness of the antireflection layer is not particularly limited, but may be about 0.1 μm to 10 μm, 1 μm to 5 μm, or 2 μm to 4 μm.

  The features of the present invention will be described more specifically with reference to examples and comparative examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Accordingly, the scope of the present invention should not be construed as being limited by the specific examples shown below.

<Synthesis Example 1>
(Synthesis example of polymer 101)
A 300 ml three-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube was charged with 250 g of toluene and heated to 120 ° C. Next, 42 g of 2- (perfluorohexyl) ethyl acrylate, 13 g of a bifunctional rod-like liquid crystal compound represented by the following formula (A), 250 g of toluene, and 58 g of a polymerization initiator “V-601” (manufactured by Wako Pure Chemical Industries, Ltd.) The mixed solution consisting of was dropped at a constant speed so that the dropping was completed in 30 minutes. After completion of the dropwise addition, stirring was further continued for 2 hours, and then the solvent was distilled off under reduced pressure and dried under reduced pressure at 130 ° C. to obtain 52 g of a polymer (101). The weight average molecular weight (Mw) of this polymer is 4,900 (calculated by gel permeation chromatography (GPC) in terms of polystyrene, and the columns used are TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ200 (manufactured by Tosoh Corporation)). there were. It was confirmed by proton NMR (nuclear magnetic resonance) spectrum measurement and elemental analysis measurement that the polymer (101) had a branched structure. Moreover, it was confirmed by proton NMR spectrum measurement and mass spectrometry measurement that the polymerization initiator fragment when V-601 was used had a structure represented by the following.

<Synthesis Example 2>
(Synthesis example of polymer 102)
A 300 ml three-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube was charged with 250 g of toluene and heated to 120 ° C. Next, from 33 g of 2- (perfluorohexyl) ethyl acrylate, 12 g of a trifunctional liquid crystal compound represented by the following formula (B), 250 g of toluene, and 58 g of a polymerization initiator “V-601” (manufactured by Wako Pure Chemical Industries, Ltd.) The resulting mixed solution was added dropwise at a constant speed so that the addition was completed in 30 minutes. After completion of the dropwise addition, the mixture was further stirred for 2 hours, and then the solvent was distilled off under reduced pressure and dried under reduced pressure at 130 ° C. to obtain 52 g of a polymer (102). The weight average molecular weight (Mw) of this polymer is 10,700 (calculated in terms of polystyrene by gel permeation chromatography (GPC), and the columns used are TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ200 (manufactured by Tosoh Corporation)). there were. It was confirmed by proton NMR (nuclear magnetic resonance) spectrum measurement and elemental analysis measurement that the polymer (101) had a branched structure. Moreover, it was confirmed by proton NMR spectrum measurement and mass spectrometry measurement that the polymerization initiator fragment when V-601 was used had a structure represented by the following.

<Synthesis Example 3>
(Synthesis example of polymer B-101)
A 200 ml three-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube was charged with 25.0 g of t-amyl alcohol and heated to 120 ° C. Next, 3.25 g (7.8 mmol) of 2- (perfluorohexyl) ethyl acrylate, 2.26 g of a trifunctional hydroxyl group-containing compound which is monomer C shown below, 25.0 g of t-amyl alcohol, and a polymerization initiator “ A mixed solution consisting of 6.0 g of “V-601” (manufactured by Wako Pure Chemical Industries, Ltd.) was dropped at a constant speed so that the dropping was completed in 30 minutes. After completion of the dropwise addition, the mixture was further stirred for 3.5 hours, and then the solvent was distilled off under reduced pressure, followed by drying under reduced pressure at 130 ° C. to obtain 7.7 g of polymer B-101. The weight average molecular weight (Mw) of this polymer was 1,800. The weight average molecular weight (Mw) was calculated in terms of polystyrene by gel permeation chromatography (GPC). The columns used were TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ200 (manufactured by Tosoh Corporation).

<Synthesis Example 2>
(Synthesis example of polymer B-102)
A 200 ml three-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube was charged with 25.0 g of t-amyl alcohol and heated to 120 ° C. Subsequently, 3.25 g of 2- (perfluorohexyl) ethyl acrylate, 2.26 g of a bifunctional hydroxyl group-containing compound D shown below, 25.0 g of t-amyl alcohol, and a polymerization initiator “V-601” (sum) A mixed solution consisting of 6.0 g (manufactured by Kojun Pharmaceutical Co., Ltd.) was added dropwise at a constant speed so that the addition was completed in 30 minutes. After completion of the dropwise addition, the mixture was further stirred for 3.5 hours, and then the solvent was distilled off under reduced pressure, followed by drying under reduced pressure at 130 ° C. to obtain 7.7 g of polymer B-101. The weight average molecular weight (Mw) of this polymer was 1,500. The weight average molecular weight (Mw) was calculated in terms of polystyrene by gel permeation chromatography (GPC). The columns used were TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ200 (manufactured by Tosoh Corporation).

<Production of film>
A polymerizable composition coating liquid (A-1) having the following composition was prepared.

Coating liquid (A-1)
Liquid crystal composition (1) 100 parts by weight Polymerization initiator IRGACURE819 (manufactured by BASF) 4 parts by weight Chiral agent LC756 (manufactured by BASF) 4 parts by weight First alignment agent (polymer 101) 0.03 parts by weight Second Orienting agent (Polymer B-101) 0.03 parts by mass Methyl acetate 260 parts by mass Cyclohexanone 65 parts by mass

Liquid crystal composition (1)
Rod-like liquid crystal compound 101 55 parts by mass Rod-like liquid crystal compound 102 30 parts by mass Rod-like liquid crystal compound 201 13 parts by mass Rod-like liquid crystal compound 202 2 parts by mass

Similarly to the polymerizable composition coating liquid (A-1), a polymerizable composition coating liquid (B-1) having the following composition was prepared.

Coating liquid (B-1)
Liquid crystal composition (1) 100 parts by weight Polymerization initiator IRGACURE819 (manufactured by BASF) 4 parts by weight Chiral agent LC756 (manufactured by BASF) 5 parts by weight First alignment agent (polymer 101) 0.01 parts by weight Methyl acetate 260 Part by weight cyclohexanone 65 parts by weight

  In the polymerizable composition coating liquid (B-1), the polymerizable composition coating liquid (B-2) was prepared in the same manner except that the kind of the first alignment agent was changed from the polymer 101 to the polymer 102. Prepared.

A polymerizable composition coating liquid (C-1) having the following composition was prepared.

Coating liquid (C-1)
Liquid crystal composition (2) 100 parts by weight Polymerization initiator IRGACURE819 (manufactured by BASF) 4 parts by weight Chiral agent LC756 (manufactured by BASF) 4 parts by weight First alignment agent (polymer 101) 0.05 parts by weight Second Orienting agent (Polymer B-101) 0.03 parts by mass Methyl ethyl ketone 220 parts by mass

Liquid crystal composition (2)
Rod-like liquid crystal compound 201 83 parts by mass Rod-like liquid crystal compound 202 15 parts by mass Rod-like liquid crystal compound 203 2 parts by mass

Similar to the polymerizable composition coating liquid (C-1), a polymerizable composition coating liquid (D-1) having the following composition was prepared.

Coating liquid (D-1)
Liquid crystal composition (2) 100 parts by weight Polymerization initiator IRGACURE819 (manufactured by BASF) 4 parts by weight Chiral agent LC756 (manufactured by BASF) 5 parts by weight First alignment agent (polymer 101) 0.01 part by weight Methyl ethyl ketone 220 parts by weight Part

  In the polymerizable composition coating liquid (D-1), the polymerizable composition coating liquid (D-2) was prepared in the same manner except that the kind of the first alignment agent was changed from the polymer 101 to the polymer 102. Prepared.

[Example 1 (Production of single-layer and multi-layer selective reflection film using liquid crystal composition (1) coating solution)]
On the rubbing-treated surface of the Fujifilm Co., Ltd. PET subjected to rubbing treatment, a wire bar is placed at room temperature so that the dry film thickness after drying the polymerizable composition coating liquid (A-1) is 4.6 μm. Applied. The coating layer was dried at room temperature for 10 seconds, then heated in an atmosphere of 85 ° C. for 1 minute, and then UV irradiated at 60 ° C. with a fusion D bulb (lamp 90 mW / cm) at an output of 80% for 8 seconds. The selective reflection film was obtained. During the period after application and before heating, no precipitation of crystals was observed in the coating film.

  Subsequently, using the same process conditions as those for forming the single-layer liquid crystal layer made of the liquid crystal composition (1), the polymerizable composition coating liquid (B- The liquid crystal layer 1) was formed to obtain a laminated selective reflection film. During the period after application and before heating, no precipitation of crystals was observed in the coating film.

[Example 15 (Production of single-layer and multi-layer selective reflection film using liquid crystal composition (2) coating solution)]
On the rubbing-treated surface of the Fujifilm Co., Ltd. PET subjected to rubbing treatment, a wire bar is attached at room temperature so that the dry film thickness after drying the polymerizable composition coating liquid (C-1) becomes 3.8 μm. Applied. The coating layer is dried at room temperature for 10 seconds, heated in an atmosphere of 85 ° C. for 1 minute, and then selectively irradiated by UV irradiation at 40 ° C. with a fusion D bulb (lamp 90 mW / cm) at an output of 80% for 8 seconds. Film 2 was obtained. During the period after application and before heating, no precipitation of crystals was observed in the coating film.

  Subsequently, using the same process conditions as those for forming the single liquid crystal layer made of the liquid crystal composition (2), the polymerizable composition coating liquid (D- The liquid crystal layer 1) was formed to obtain a laminated selective reflection film. During the period after application and before heating, no precipitation of crystals was observed in the coating film.

[Examples 2 to 14 and Comparative Examples 1 and 2]
In Examples 2 to 14 and Comparative Examples 1 and 2, the coating liquid of the present invention was used in the same manner as in Example 1 except that the amount and type of the alignment agent were as shown in Table 1. Thus, single-layer and laminated selective reflection films were obtained.
[Examples 16 to 23 and Comparative Examples 3 and 4]
In Examples 16 to 23 and Comparative Examples 3 and 4, the coating liquid of the present invention was used in the same manner as in Example 15 except that the amount and type of the alignment agent were as shown in Table 1. Thus, single-layer and laminated selective reflection films were obtained.

<Evaluation of selective reflection film>
About the selective reflection film of the said Example and comparative example, orientation and repelling were evaluated by the method shown below.
[Orientation]
The superiority or inferiority of the liquid crystal alignment was determined according to the following criteria depending on the presence or absence of alignment defects when the film was observed with a deflection microscope. If it is evaluation standard A or B, it is excellent in production efficiency and can be used suitably, and it is more preferable that it is evaluation standard A.
A: No alignment failure B: Almost no alignment failure C: Some misalignment portions are scattered D: There is an alignment failure on the entire surface

[Repel]
The number of repellency of the layer formed using each composition in the film of 10 cm × 15 cm of each Example and Comparative Example was counted. Here, the area | region where the upper layer is not formed in the surface of the lower layer was made into a repellency. Based on the results, evaluation was made according to the following criteria. If it is evaluation standard A or B, it is excellent in production efficiency and can be used suitably, and it is more preferable that it is evaluation standard A.
A: 1 or less repellent B: 1-3 repellent C: 4-9 repellent D: More than 10 repellent

[Contact angle]
About the single-layer selective reflection film, the contact angle was evaluated by the method shown below.
Using a contact angle meter DropMaster 500 manufactured by Kyowa Interface Science Co., Ltd., the contact angle of the surface of the selective reflection film with respect to pure water was measured by a droplet method. The smaller the contact angle, the better the wettability at the time of lamination, and it is preferable that the evaluation is one of the following evaluation criteria A and B. If it is evaluation standard A, it is excellent in production efficiency, can be used suitably, and is more preferable.
A: Contact angle is less than 90 degrees B: Contact angle is 90 degrees or more and less than 95 degrees C: Contact angle is 95 degrees or more and less than 100 degrees D: Contact angle is 100 degrees or more

<Example 30 (Formation of selective reflection film of three-layer laminate)>
Polymeric composition coating liquids (E-1) to (E-3) having the following compositions were prepared.

Polymerizable composition coating liquid (E-1)
Liquid crystal composition (1) 100 parts by weight Polymerization initiator IRGACURE OXE01 (manufactured by BASF) 1 part by weight Chiral agent LC756 (manufactured by BASF) 3.7 parts by weight First alignment agent (polymer 101) 0.05 part by weight Second alignment agent (Polymer B-101) 0.03 parts by mass Methyl acetate 260 parts by mass Cyclohexanone 65 parts by mass

Polymerizable composition coating liquid (E-2)
Liquid crystal composition (1) 100 parts by weight Polymerization initiator IRGACURE OXE01 (manufactured by BASF) 1 part by weight Chiral agent LC756 (manufactured by BASF) 4.7 parts by weight First alignment agent (polymer 101) 0.02 parts by weight Second alignment agent (Polymer B-101) 0.03 parts by mass Methyl acetate 260 parts by mass Cyclohexanone 65 parts by mass

Polymerizable composition coating liquid (E-3)
Liquid crystal composition (1) 100 parts by mass Polymerization initiator IRGACURE OXE01 (manufactured by BASF) 1 part by mass Chiral agent LC756 (manufactured by BASF) 5.4 parts by mass First alignment agent (polymer 101) 0.02 parts by mass Second alignment agent (Polymer B-101) 0.03 parts by mass Methyl acetate 260 parts by mass Cyclohexanone 65 parts by mass

On the rubbing-treated surface of Toyobo Co., Ltd. PET (A-4100) subjected to rubbing treatment, the polymerizable composition coating liquid (E-1) was brought to room temperature so that the thickness of the dry film after drying was 5.0 μm. And applied using a wire bar. The coating layer was dried at room temperature for 30 seconds, then heated in an atmosphere of 85 ° C. for 1 minute, and irradiated with UV at 60 ° C. in a nitrogen gas atmosphere using a high-pressure mercury lamp so that the irradiation amount was 300 mJ / cm ² . A selective reflection film (30) was obtained. During the period after application and before heating, no precipitation of crystals was observed in the coating film.
When the transmission spectrum of this film was measured with a spectrophotometer UV-3100PC manufactured by Shimadzu Corporation, there was a selective reflection peak centered at 668 nm, and the half-value width was 40 nm.

Subsequently, the dry film thickness after drying the polymerizable composition coating liquid (E-2) on the surface of the liquid crystal layer of the selective reflection film (30) is 4.1 μm (the total film thickness with the lower layer is 9.2 μm). It apply | coated using the wire bar at room temperature so that it might become. The coating layer is dried at room temperature for 30 seconds, then heated in an atmosphere of 85 ° C. for 1 minute, and UV irradiation is performed using a high-pressure mercury lamp at 60 ° C. in a nitrogen gas atmosphere to select 300 mJ / cm ^2. A reflective film (31) was obtained.
Furthermore, the thickness of the dry film after drying the polymerizable composition coating liquid (E-3) on the surface of the liquid crystal layer of the selective reflection film (31) is 3.9 μm (the total film thickness with the lower layer is 13.1 μm). It applied so that it might become, using a wire bar at room temperature. The coating layer is dried at room temperature for 30 seconds, then heated in an atmosphere of 85 ° C. for 1 minute, and UV irradiation is performed using a high-pressure mercury lamp at 60 ° C. in a nitrogen gas atmosphere to select 300 mJ / cm ^2. A reflective film (32) was obtained.
When the transmission spectrum of this selective reflection film 10 was measured with a spectrophotometer UV-3100PC manufactured by Shimadzu Corporation, it was found that there were reflection peaks at 680 nm, 536 nm and 460 nm, and a high visible light transmittance of 75% or more. .

<Production of half mirror 1>
On the liquid crystal layer side of the selective reflection film (32), a UV curable adhesive Exp. U12034-6 was applied using a wire bar at room temperature so that the dry film thickness after drying was 5 μm. The surface of the transparent substrate made of (meth) acrylic resin (“Acrylite L” manufactured by Mitsubishi Rayon Co., Ltd., thickness 5 mm) and the adhesive-coated surface of the selective reflection film (32) were bonded together and irradiated with UV. The transparent base material is one in which color unevenness is not visually recognized in the plane when it is placed between two polarizing plates arranged with the transmission axes orthogonal to each other, and has a maximum phase difference of 5 nm in a 10 cm square plane. It was. By peeling the PET film of the selective reflection film (32), a visible light transmissive half mirror 1 for projecting image display was produced on a transparent substrate.

<Production of half mirror 2 with antireflection layer>
A hard coating layer having a refractive index of 1.52 and a thickness of 3.0 μm on a TAC film having a thickness of 40 μm, a medium refractive index layer having a refractive index of 1.594 and a thickness of 0.06 μm, and a refractive index of 1.708. With a high refractive index layer having a thickness of 0.13 μm and a low refractive index layer having a refractive index of 1.343 and a thickness of 0.094 μm formed thereon, with an antireflection layer having a surface reflectance at 550 nm of 0.4% A film was prepared. On the TAC film side, a UV curable adhesive Exp. U12034-6 was applied using a wire bar at room temperature so that the dry film thickness after drying was 5 μm. The coated surface and the liquid crystal layer side of the selective reflection film (32) produced above were bonded together so that no air bubbles would enter, and then 6 ° C. with a fusion D bulb (lamp 90 mW / cm) at 30 ° C. with an output of 60%. UV irradiation was performed for ˜12 seconds, and then the selective reflection film (33) with an antireflection layer was produced by peeling off the PET film of the selective reflection film (32).

  Next, with respect to the surface of the selective reflection film (33) on the liquid crystal layer side, a UV curable adhesive Exp. U12034-6 was applied using a wire bar at room temperature so that the dry film thickness after drying was 5 μm. A transparent substrate made of the same (meth) acrylic resin as described above ("Acrylite L" manufactured by Mitsubishi Rayon Co., Ltd.) and the adhesive-coated surface of the selective reflection film (33) are bonded to each other and irradiated with UV. A projection image display half mirror 2 having a base, a liquid crystal layer (three layers), and an antireflection layer in this order was produced.

Claims (21)

A polymerizable liquid crystal compound, a first alignment agent and a second alignment agent;
Obtained by polymerizing a mesogenic group monomer having a mesogenic group derived from at least one liquid crystal compound selected from a rod-like liquid crystal compound and a discotic liquid crystal compound and a mesogenic group monomer having two or more radical polymerizable double bonds. A mesogenic polymer containing a branched structure and being branched,
A liquid crystal composition comprising a hydroxyl group-containing polymer containing a partial structure obtained by polymerizing a hydroxyl group-containing monomer having one or more hydroxyl groups and two or more radical polymerizable double bonds. The liquid crystal composition according to claim 1, wherein the polymerizable liquid crystal compound is a rod-like liquid crystal compound. The liquid crystal composition according to claim 1 or 2, wherein the mesogenic group monomer is a compound represented by the general formula (X).

In the formula, Q ^X1 and Q ^X2 each independently represent a polymerizable group, L ^X1 and L ^X4 each independently represent a divalent linking group, and L ^X2 and L ^X3 each independently represent a single bond or divalent Cy ^X1 , Cy ^X2 and Cy ^X3 represent a divalent cyclic group, and nx represents an integer of 0 to 3. The liquid crystal composition according to claim 1, wherein the mesogen-containing monomer is a compound represented by the general formula (I).

In the general formula (I), Y ¹¹ , Y ¹² and Y ¹³ each independently represent a methine or nitrogen atom which may be substituted, and L ¹ , L ² and L ³ each independently represent a single bond or two H ¹ , H ² and H ³ each independently represent the following general formula (IA) or the following general formula (IB), and R ¹ , R ² and R ³ are: Each independently represents the following general formula (IR),

In general formula (IA), YA ¹ and YA ² each independently represents a methine or nitrogen atom which may have a substituent, XA represents an oxygen atom, a sulfur atom, methylene or imino; Represents a position bonded to the L ^{1 to} L ³ side in the general formula (I), ** represents a position bonded to the R ^{1 to} R ³ side in the general formula (I),

In the general formula (IB), YB ¹ and YB ² each independently represent a methine or nitrogen atom which may have a substituent, XB represents an oxygen atom, a sulfur atom, methylene or imino, * Represents a position bonded to the L ^{1 to} L ³ side in the general formula (I), ** represents a position bonded to the R ^{1 to} R ³ side in the general formula (I),

In General Formula (I-R), ** represents a position bonded to the H ^{1 to} H ³ side in General Formula (I), L ^r1 represents a single bond or a divalent linking group, and Q ² represents at least 1 represents a divalent group having a cyclic structure, n1 represents an integer of 0 to 4, L ^r2 and L ^r3 represents a divalent linking group independently, Q ¹ is a polymerizable group or a hydrogen atom Wherein at least two of Q ¹ present in a plurality represent a polymerizable group. The liquid crystal composition according to any one of claims 1 to 4, wherein the mesogen-containing polymer includes a partial structure obtained by a polymerization reaction of a fluorine-containing compound. The liquid crystal composition according to claim 5, wherein the partial structure obtained by polymerizing a fluorine-containing compound of the mesogen-containing polymer is represented by the general formula a1;

In general formula a1, R ^a1 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R ^a2 represents an alkyl group having 1 to 20 carbon atoms or a carbon number in which at least one carbon atom has a fluorine atom as a substituent. 1-20 alkenyl groups are represented. The liquid crystal composition according to any one of claims 1 to 6, wherein the hydroxyl group-containing monomer is a monomer represented by the general formula Y;

In the formula, Z ^Y1 and Z ^Y2 each independently represent a group having a radical polymerizable double bond, and L ^Y1 and L ^Y4 each independently represent a single bond or an alkylene group having a hydroxyl group, —O—, ^{-S -, - CO -, -} NR yy1 -, - C = N-, and from at least one selected from the group consisting of a divalent linking group ^{constituted, R yy1} is hydrogen Represents an atom or an alkyl group having 1 to 7 carbon atoms, L ^Y2 and L ^Y3 each independently represent a single bond, —O—, — (C═O) O—, —O (C═O) —, 2 Represents a divalent linking group composed of at least one selected from the group consisting of a valent chain group, an alkylene group having a hydroxyl group, and a divalent cyclic group, and M has a single bond or a hydroxyl group Represents a divalent to tetravalent linking group that may be present; Represents an ^{integer, L Y1, L Y2, L} Y3, L Y4, and one or more selected from the group consisting of M include a hydroxyl group. The liquid crystal composition according to claim 1, wherein the hydroxyl group-containing monomer is a monomer represented by the general formula Y1.

In the formula, R ^Y1 , R ^Y2 , and R ^Y3 each independently represent a hydrogen atom or a methyl group, and L ^Y11 , L ^{Y12, and} L ^Y13 each independently represent a single bond, or —O—, — (C═O ) O-, -O (C = O)-, a divalent linkage composed of at least one selected from the group consisting of a divalent chain group, an alkylene group having a hydroxyl group, and a divalent cyclic group. Represents a group, M ¹ represents a single bond or a divalent, trivalent or tetravalent linking group, and n1 represents an integer of 0 to 2. The liquid crystal composition according to any one of claims 1 to 8, wherein the hydroxyl group-containing polymer includes a partial structure obtained by polymerizing a compound containing fluorine. The liquid crystal composition according to claim 9, wherein the partial structure obtained by polymerizing a fluorine-containing compound of the hydroxyl group-containing polymer is represented by the following general formula a1;

In general formula a1, R ^a1 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R ^a2 represents an alkyl group having 1 to 20 carbon atoms or a carbon number in which at least one carbon atom has a fluorine atom as a substituent. 1-20 alkenyl groups are represented. The liquid crystal composition according to any one of claims 1 to 10, comprising a polymerization initiator. The liquid crystal composition according to claim 1, comprising a chiral compound. The film containing the layer which hardened | cured the liquid-crystal composition as described in any one of Claims 1-12. A film comprising a layer obtained by curing the liquid crystal composition according to claim 1, and a layer obtained by curing the liquid crystal composition as a layer in direct contact with the layer. Shows selective reflection,
The film according to claim 13 or 14, wherein Δλ / λ, which is a ratio of a half-value width Δλ of the selective reflection wavelength region to a central wavelength λ of the selective reflection, is 0.09 or less. The film according to any one of claims 13 to 15, which reflects visible light. A film comprising at least three layers obtained by curing the liquid crystal composition according to any one of claims 1 to 12,
The three layers are a layer in which a cholesteric liquid crystal phase having a central wavelength of selective reflection is fixed in a red light wavelength region, a layer in which a cholesteric liquid crystal phase having a central wavelength of selective reflection is fixed in a green light wavelength region, and a blue light wavelength region A film in which a cholesteric liquid crystal phase having a central wavelength of selective reflection is fixed. A half mirror for displaying projected images including the film according to claim 17. The half mirror for displaying projected images according to claim 18, comprising a base material made of inorganic glass or acrylic resin. The half mirror for displaying projected images according to claim 18 or 19, comprising an antireflection layer on the outermost surface. Applying a liquid crystal composition containing a polymerizable liquid crystal compound to the surface of a layer obtained by curing the liquid crystal composition according to any one of claims 1 to 12, and curing the applied liquid crystal composition. The manufacturing method of the film containing this.