JPWO2016208574A1 - Polymerizable liquid crystal composition and optical anisotropic body - Google Patents

Abstract

The present invention is a polymer obtained by polymerizing a polymerizable liquid crystal composition, and an optical anisotropic body including a polymethyl methacrylate resin substrate or a polycarbonate resin substrate, and the polymerizable liquid crystal composition is at least one or more. 85 masses of one or more liquid crystal compounds satisfying 0.22 <S <0.6 in the molecular structure parameter S represented by S = LR / (LR + LM). % Or more of the optically anisotropic substance is contained, and a polymerizable liquid crystal composition used for the optically anisotropic substance is also provided. The present invention provides an optically anisotropic body that exhibits excellent orientation when used on a polymethylmethacrylate resin substrate or a polycarbonate resin substrate, has low haze, is excellent in transparency, and retains adhesiveness. A liquid crystal composition is provided.

Description

  The present invention relates to a polymerizable liquid crystal composition containing a compound having a polymerizable group and an optical anisotropic body using the polymerizable liquid crystal composition.

The polymerizable liquid crystal composition is useful as a component of an optical anisotropic body, and the optical anisotropic body is applied to various liquid crystal displays as an optical compensation sheet (retardation film), a pattern retarder, a lenticular lens, and the like. . The retardation film is obtained by applying a polymerizable liquid crystal composition to a substrate and curing the polymerizable liquid crystal composition by irradiating active energy rays in a state where the polymerizable liquid crystal composition is aligned by an alignment film or the like. It is done. The retardation film has various forms such as an A plate, a negative C plate, a positive C plate, and a hybrid depending on the alignment state, and any of them can be produced with a polymerizable liquid crystal composition.
On the other hand, in the case of producing a retardation film, TAC or polycycloolefin has been used as a substrate, but from the viewpoint of cost, a change to other materials such as polymethyl methacrylate resin and polycarbonate resin is desired.

However, when a cured film of a polymerizable liquid crystal composition was formed on a substrate using a resin having relatively poor solvent resistance and mechanical properties such as polymethyl methacrylate resin and polycarbonate resin, the substrate was dissolved and dissolved by the solvent. Curing the polymerizable liquid crystal layer, for example, the transparency of the cured film decreases when the components enter the polymerizable liquid crystal layer, and the transparency of the substrate decreases when the polymerizable liquid crystal enters the substrate. In the case of a patterned retardation film (FPR) obtained by partially changing the alignment direction, alignment disorder occurs between pattern regions having different alignment states. There was a problem.
In order to solve this problem, improvements have been made on the polymerizable liquid crystal composition or the method for producing the polymerizable liquid crystal composition. For example, for a polymerizable liquid crystal composition, a method of forming a composition in which a non-liquid crystalline polymerizable compound is added to a polymerizable liquid crystal composition having a specific structure, and applying the composition on a substrate without adding a solvent (See Patent Document 1). However, even in this case, although the dissolution of the resin substrate by the solvent cannot surely occur, the polymerizable liquid crystal composition slightly dissolves the resin substrate, or the low molecular weight component in the resin substrate dissolves in the polymerizable liquid crystal layer. There is a concern that the orientation of the polymerizable liquid crystal layer may be reduced, and that the transparency of the polymerizable liquid crystal layer or the resin substrate may be reduced.

Also, when aligning a polymerizable liquid crystal using an alignment film, depending on the type of the polymerizable liquid crystal or the solvent in which the polymerizable liquid crystal is dissolved, the polymerizable liquid crystal enters the alignment film and reaches the resin substrate. There was concern to cause.
On the other hand, in order to obtain a practical retardation film, it is necessary to sufficiently increase the adhesion between the substrate and the polymerizable liquid crystal layer. As an example of such a method, a retardation film is formed by applying a polymerizable liquid crystal using an acrylate group as a polymerizable functional group on an acrylic substrate (Patent Document 2). In this example, although the adhesiveness is good, the compatibility between the polymerizable liquid crystal and the resin substrate becomes too high, and the phenomenon such as the dissolution and intrusion of both components described above is likely to occur, and the transparency and retardation accuracy are improved. The problem remained.
As described above, there has been a demand for a method of providing an optical anisotropic body made of a polymerizable liquid crystal composition on a polymethyl methacrylate resin substrate or a polycarbonate resin substrate without deteriorating the properties of the retardation film.

JP 2014-28916 A JP 2009-162870 A

  The problem to be solved by the present invention is that an optically anisotropic layer made of a polymerizable liquid crystal formed on a polymethyl methacrylate resin substrate or a polycarbonate resin substrate exhibits excellent orientation, has little haze, and is excellent in transparency. Further, it is to provide an optical anisotropic body that retains adhesiveness, and to provide an optical anisotropic body having excellent pattern resolution when the optical anisotropic body is FPR. Another object is to provide a polymerizable liquid crystal composition therefor.

  The inventors of the present invention have disclosed a polymethyl methacrylate resin, in which a component eluted from a polymethyl methacrylate resin substrate or a polycarbonate resin substrate does not easily enter the polymerizable liquid crystal layer, and the polymerizable liquid crystal does not easily enter the polycarbonate resin substrate or the polycarbonate resin substrate. The above-described problems have been solved by using a polymerizable liquid crystal composition having a low affinity with a methacrylate resin or a polycarbonate resin with a polymethyl methacrylate resin substrate or a polycarbonate resin substrate.

That is, the present invention is a polymer obtained by polymerizing a polymerizable liquid crystal composition, and an optical anisotropic body including a polymethyl methacrylate resin substrate or a polycarbonate resin substrate, and the polymerizable liquid crystal composition contains at least 1 Having at least two polymerizable functional groups and S = LR / (LR + LM)
(LM represents the number of atoms from the end of the ring structure at one end of the mesogenic group of the liquid crystal compound to the end of the ring structure at the other end, provided that a hydrogen atom and a substituent atom added in the lateral direction of the ring structure. LR represents the number of atoms from the molecular end of the liquid crystal compound to the atom bonded to the closest mesogen base end, and the portion from the molecular end to the atom bonded to the closest mesogenic base end If there is a plurality, the sum of all of them is included, and the substituents of the mesogenic group are also included, but the number of hydrogen atoms is not included.)
And an optical anisotropic body containing 85% by mass or more of one or more liquid crystal compounds satisfying 0.22 <S <0.6 in the molecular structure parameter S represented by A polymerizable liquid crystal composition used for a rectangular parallelepiped is provided.

  By using the polymerizable liquid crystal composition of the present invention, it is possible to obtain an optical anisotropic body that is excellent in adhesion to the substrate and excellent in orientation and transparency. In addition, an FPR with excellent pattern resolution can be obtained.

(Polymerizable liquid crystal compound)
The polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition used in the present invention is preferably a compound having a low affinity with a polymethyl methacrylate resin or a polycarbonate resin, and has the following characteristics in the structure of the polymerizable liquid crystal compound. The compound which has is preferable.
The polymerizable liquid crystal compound is divided into a mesogenic portion and another portion containing a polymerizable group. The mesogen in the present invention refers to a partial structure having high rigidity and the like that induces liquid crystallinity in the structure of molecules exhibiting liquid crystallinity. Examples thereof include a structure in which an aromatic or aliphatic ring structure is bonded directly or by a linking group, and forms a rod-like or disk-like liquid crystal molecule. Here, the term “showing liquid crystallinity” includes not only the liquid crystal phase alone but also the liquid crystal phase in a state where the molecule alone does not show liquid crystal property and is mixed with other liquid crystal molecules.

As a result of examining the affinity between the polymerizable liquid crystal compound and the polymethyl methacrylate resin or the polycarbonate resin constituting the substrate, the affinity of the compound having a specific size of the mesogen portion for the entire polymerizable liquid crystal molecule is low, It has been found that it meets the object of the present invention. In order to clarify this relationship, the structural parameter (S) of the polymerizable liquid crystal molecules is defined as follows.
S = LR / (LR + LM)
Here, the number of atoms from the end of the ring structure at one end of the mesogenic group of the liquid crystal compound to the end of the ring structure at the other end is defined as the mesogen length (LM). Note that LM does not include hydrogen atoms and the number of substituent atoms added to the ring structure. The length (LR) of the portion other than the mesogen is the number of atoms from the molecular end of the liquid crystal compound to the atom bonded to the closest mesogen base end, and when there are a plurality of portions other than the mesogen, Also includes mesogenic substituents. However, it is assumed that LR also does not contain a hydrogen atom.

When the parameter S is small, that is, when the length of the mesogen is relatively long, the affinity with the molecules constituting the substrate is considered to be reduced from the viewpoint of structural similarity and difficult to mix. The molecular structure of the unreacted monomer present is presumed to be a rigid structure, and it is considered that the affinity may rather increase.
The polymerizable liquid crystal compound in which the parameter S satisfies 0.22 <S <0.6 has low solubility in the unreacted monomer or oligomer of the polymethyl methacrylate resin or polycarbonate resin, and the polymerizable liquid crystal and monomer or oligomer after solvent evaporation Are difficult to mix and fluctuations in the phase difference are suppressed. Further, the above S is preferably 0.25 <S <0.57, and more preferably 0.28 <S <0.55.

Further, as a preferable condition other than the structural parameter (S), the affinity can be improved by making the polymerizable group of the polymerizable liquid crystal molecule a polymerizable group having a structure different from that of the terminal reaction site of the unreacted monomer or oligomer of the polymethyl methacrylate resin. Since it can reduce, it is still more preferable. For example, an acrylic group, an epoxy group, or an oxetane group is preferable. By including these components having a polymerizable group, it is difficult to mix the polymerizable liquid crystal compound after evaporation of the solvent and the monomer or oligomer of the resin, and the fluctuation in the retardation can be suppressed.
Similarly, impurities contained during polymerization of polycarbonate include 2,2-bis (4-hydroxyphenyl) propane (also known as bisphenol A), bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxy). Bis (4-hydroxyphenyl) alkane such as phenyl) ethane, 1,1-bis (4-hydroxyphenyl) butane, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxy) Phenyl) sulfoxide and the like, or unreacted dihydroxy monomers and oligomers such as halogen-substituted dihydroxy compounds having halogen atoms such as chlorine and bromine in the hydroxybenzene nucleus, and polymerization in addition to the limitation by the structural parameter (S) The number of polar groups in the liquid crystalline compound It is more preferable to reduce the polarity.

Moreover, since the miscibility with the monomer or oligomer of resin falls when the molecular weight of a polymeric liquid crystal compound is large, it is preferable. Among these, 270 or more is preferable, 300 or more is more preferable, and 400 or more is particularly preferable. By containing a component having a high molecular weight, it is difficult to mix the polymerizable liquid crystal after evaporation of the solvent and the monomer or oligomer, and it is possible to suppress fluctuations in the phase difference of the optical anisotropic body formed by polymerizing the polymerizable liquid crystal molecules. it can.
The content of the polymerizable liquid crystal compound satisfying the structural parameter (S) in the polymerizable liquid crystal composition of the present invention is 85% by mass or more, preferably 90% by mass or more, and more preferably 92% by mass or more. .

The polymerizable liquid crystal compound in the polymerizable liquid crystal composition of the present invention satisfies the above-mentioned structural parameter (S) of the polymerizable liquid crystal molecule, and if it satisfies this condition, a rod-like polymerizable liquid crystal compound, Various liquid crystal compounds such as a disk-like polymerizable liquid crystal compound or a banana-type polymerizable liquid crystal compound can be used, and a rod-like polymerizable liquid crystal compound is particularly preferable.
Among the rod-like polymerizable liquid crystal compounds, compounds represented by the following general formula (II) are preferable.

In the formula, P ² represents a polymerizable functional group, and S ¹ represents an alkylene group having 1 to 18 carbon atoms (the hydrogen atom in the alkylene group is one or more halogen atoms, a CN group, or a polymerizable group). may be substituted by an alkyl group having 1 to 8 carbon atoms having a functional group, each of the two or more CH ₂ groups not one CH ₂ group or adjacent existing independently of one another during this group Te, -O -, - COO -, -. the OCO- or --OCO-O-by may be substituted), ^{X 1} is _{-O -, - S -, -} OCH 2 -, - CH 2 O- , —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, —CO—NH—, —NH—CO—, —SCH ₂ —, _{-CH 2 S -, - CF 2} O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - CH = C -COO -, - CH = CH- OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH _{2 -COO -, - CH 2 CH} 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CH = CH -, - N ═N—, —CH═N—N═CH—, —CF═CF—, —C≡C— or a single bond (where P ² —S ¹ and S ¹ —X ¹ are —O— O—, —O—NH—, —S—S—, and —O—S— groups are not included.), Q 1 represents 0 or 1, MG represents a mesogenic group, R ² represents a hydrogen atom, halogen Represents an atom, a cyano group, or a linear or branched alkyl group having 1 to 12 carbon atoms, and the alkyl group may be linear May also be Toki, the alkyl group is one -CH ₂ - or nonadjacent two or more -CH ₂ - are each independently -O -, - S -, - CO -, - COO -, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-COO-, -CH = CH —OCO—, —COO—CH═CH—, —OCO—CH═CH—, —CH═CH—, —CF═CF— or —C≡C— may be substituted, or R ² may be Formula (II-a)

(Wherein P ³ represents a polymerizable functional group, S ² represents the same as defined in S ¹ , and X ² represents the same as defined in X ¹ ( Provided that P ³ —S ² and S ² —X ² do not include —O—O—, —O—NH—, —S—S— and —O—S— groups.), Q ² is 0 Or 1).
The mesogenic group represented by MG has the general formula (II-b)

(In the formula, B1, B2 and B3 are each independently 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group, 1, 3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene-2,6-diyl group, pyridine- 2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group-, 1,2,3,4-tetrahydronaphthalene

2,6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4,4a, 9 , 10a-octahydrophenanthrene-2,7-diyl group, 1,4-naphthylene group, benzo [1,2-b: 4,5-b ′] dithiophene-2,6-diyl group, benzo [1,2 -B: 4,5-b '] diselenophen-2,6-diyl group, [1] benzothieno [3,2-b] thiophene-2,7-diyl group, [1] benzoselenopheno [3,2- b] represents a selenophene-2,7-diyl group or a fluorene-2,7-diyl group, and has at least one F, Cl, CF ₃ , OCF ₃ , CN group or a C 1-8 carbon atom as a substituent. Alkyl group, alkoxy group having 1 to 8 carbon atoms, carbon atom number -8 alkanoyl group, alkanoyloxy group having 1 to 8 carbon atoms, alkoxycarbonyl group having 1 to 8 carbon atoms, alkenyl group having 2 to 8 carbon atoms, alkenyloxy group having 2 to 8 carbon atoms, carbon An alkenoyl group having 2 to 8 atoms, an alkenoyloxy group having 2 to 8 carbon atoms, and / or the general formula (II-c)

(Wherein P ⁴ represents a reactive functional group,
S ³ represents the same as defined in S ¹ , and X ³ represents —O—, —COO—, —OCO—, —OCH ₂ —, —CH ₂ O—, —CH ₂ CH _{2. OCO -, - COOCH 2 CH 2} -, - OCOCH 2 CH 2 -, or a single bond, ^{q 3} is 0 or 1, ^{q 4} represents 0 or 1. (However, P ⁴ —S ³ and S ³ —X ³ do not include —O—O—, —O—NH—, —S—S—, and —O—S— groups). Z1 and Z2 are each independently —COO—, —OCO—, —CH ₂ CH ₂ —, —OCH ₂ —, —CH ₂ O—, —CH═CH—, —C≡C. -, - CH = CHCOO -, - OCOCH = CH -, - CH 2 CH 2 COO -, - CH 2 CH 2 OCO -, - COOCH 2 CH 2 -, - OCOCH 2 CH 2 -, - C = N-, —N═C—, —CONH—, —NHCO—, —C (CF ₃ ) ₂ —, an alkyl group having 2 to 10 carbon atoms which may have a halogen atom, or a single bond; In the case where a plurality of B1 and Z1 are present, they may be the same or different. ).

P ² , P ³ and P ⁴ each independently represent a substituent selected from a polymerizable group represented by the following formula (P-2-1) to formula (P-2-20). preferable.

  Among these polymerizable functional groups, from the viewpoint of increasing the polymerizability, the formulas (P-2-1), (P-2-2), (P-2-7), (P-2-12), ( P-2-13) is preferable, and formulas (P-2-1) and (P-2-2) are more preferable.

(Monofunctional polymerizable liquid crystal compound)
Among the compounds represented by the general formula (II), as the monofunctional polymerizable liquid crystal compound having one polymerizable functional group in the molecule, a compound represented by the following general formula (II-2-1) preferable.

式中、Ｐ^２、Ｓ^１、Ｘ^１、ｑ１及び、ＭＧは、それぞれ、上記一般式（ＩＩ）の定義と同じものを表し、Ｒ^２１は、水素原子、ハロゲン原子、シアノ基、１個の−ＣＨ_２−又は隣接していない２個以上の−ＣＨ_２−が各々独立して−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−Ｓ−、−Ｓ−ＣＯ−、−Ｏ−ＣＯ−Ｏ−、−ＣＯ−ＮＨ−、−ＮＨ−ＣＯ−、−ＮＨ−、−Ｎ（ＣＨ_３）−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＣＨ＝ＣＨ−ＯＣＯ−、−ＣＯＯ−ＣＨ＝ＣＨ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−又は−Ｃ≡Ｃ−によって置換されても良い、炭素原子数１から１２の直鎖又は分岐アルキル基、炭素原子数１から１２の直鎖又は分岐アルケニル基を表し、該アルキル基、アルケニル基の有する１個又は２個以上の水素原子は、ハロゲン原子、シアノ基によって置換されても良く、複数置換されている場合それぞれ同一であっても、異なっていても良い。一般式（ＩＩ−２−１）の例として、下記一般式（ＩＩ−２−１−１）〜（ＩＩ−２−１−４）で表される化合物を挙げることができるが、下記の一般式に限定されるわけではない。

In the formula, P ² , S ¹ , X ¹ , q ¹ and MG each represent the same definition as in the general formula (II), and R ²¹ represents a hydrogen atom, a halogen atom, a cyano group, one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S. —CO—, —O—CO—O—, —CO—NH—, —NH—CO—, —NH—, —N (CH ₃ ) —, —CH═CH—COO—, —CH═CH—OCO. A straight chain of 1 to 12 carbon atoms which may be substituted by-, -COO-CH = CH-, -OCO-CH = CH-, -CH = CH-, -CF = CF- or -C≡C-. Represents a chain or branched alkyl group, a linear or branched alkenyl group having 1 to 12 carbon atoms, and the presence of the alkyl group or alkenyl group. One or two or more hydrogen atoms may be substituted with a halogen atom or a cyano group. When a plurality of hydrogen atoms are substituted, they may be the same or different. Examples of the general formula (II-2-1) include compounds represented by the following general formulas (II-2-1-1) to (II-2-1-4). The formula is not limited.

In the formula, P ² , S ¹ , X ¹ , and q ¹ each represent the same definition as in the general formula (II),
B11, B12, B13, B2, and B3 represent the same definitions as B1 to B3 in the general formula (II-b), and may be the same or different,
Z11, Z12, Z13 and Z2 represent the same definitions as Z1 to Z3 in the general formula (II-b), and may be the same or different,
R ²¹ represents a hydrogen atom, a halogen atom, a cyano group, one —CH ₂ —, or two or more non-adjacent —CH ₂ —, each independently —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, —CO—NH—, —NH—CO—, —NH—, —N (CH ₃ ). -, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -CH = CH-, -CF = CF- or -C≡C Represents a straight-chain or branched alkyl group having 1 to 12 carbon atoms or a straight-chain or branched alkenyl group having 1 to 12 carbon atoms, which may be substituted by-, one or two of the alkyl group or alkenyl group One or more hydrogen atoms may be substituted with a halogen atom or a cyano group. May be the same or different.

  Examples of the compounds represented by the general formulas (II-2-1-1) to (II-2-1-4) include the following formulas (II-2-1-1-1) to (II-2). The compound represented by (1-1-26) is exemplified, but not limited thereto.

In the formula, R ^c represents a hydrogen atom or a methyl group, m represents an integer of 0 to 18, n represents 0 or 1, and R ²¹ represents the above general formula (II-2-1-1) to ( II-2-1-4) represents the same definition, but R ²¹ represents a hydrogen atom, a halogen atom, a cyano group, one —CH ₂ — is —O—, —CO—, —COO—, It preferably represents a linear alkyl group having 1 to 6 carbon atoms or a linear alkenyl group having 1 to 6 carbon atoms, which may be substituted by -OCO-,
The cyclic group has one or more F, Cl, CF ₃ , OCF ₃ , CN groups, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and 1 to 1 carbon atoms as a substituent. An alkanoyl group having 8 carbon atoms, an alkanoyloxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkenyloxy group having 2 to 8 carbon atoms, and a carbon atom The alkenoyl group having 2 to 8 carbon atoms and the alkenoyloxy group having 2 to 8 carbon atoms may be contained.

The total content of the monofunctional polymerizable liquid crystal compound having one polymerizable functional group in the molecule is preferably 0 to 90% by mass in the total amount of the polymerizable liquid crystal compound to be used, and 0 to 85% by mass. % Is more preferable, and 0 to 80% by mass is particularly preferable. When placing importance on the orientation of the optical anisotropic body, the lower limit value is preferably 5% by mass or more, more preferably 10% by mass or more, and when emphasizing the hardness of the coating film, the upper limit value. Is preferably 80% by mass or less, and more preferably 70% by mass or less.

(Bifunctional polymerizable liquid crystal compound)
Among the compounds represented by the general formula (II), as a bifunctional polymerizable liquid crystal compound having two polymerizable functional groups in the molecule, a compound represented by the following general formula (II-2-2) preferable.

式中、Ｐ^２、Ｓ^１、Ｘ^１、ｑ１、ＭＧ、Ｘ^２、Ｓ^２、ｑ２、Ｐ^３は、それぞれ、上記一般式（ＩＩ）の定義と同じものを表す。一般式（ＩＩ−２−２）の例として、下記一般式（ＩＩ−２−２−１）〜（ＩＩ−２−２−４）で表される化合物を挙げることができるが、下記の一般式に限定されるわけではない。

In the formula, P ² , S ¹ , X ¹ , q ¹ , MG, X ² , S ² , q ² , and P ³ each represent the same definition as in the general formula (II). Examples of the general formula (II-2-2) include compounds represented by the following general formulas (II-2-2-1) to (II-2-2-4). The formula is not limited.

In the formula, P ² , S ¹ , X ¹ , q ¹ , MG, X ² , S ² , q ² , and P ³ each represent the same definition as in the general formula (II),
B11, B12, B13, B2, and B3 represent the same definitions as B1 to B3 in the general formula (II-b), and may be the same or different,
Z11, Z12, Z13, and Z2 represent the same definitions as Z1 to Z3 in the general formula (II-b), and may be the same or different.
Of the compounds represented by the general formulas (II-2-2-1) to (II-2-2-4), the general formulas (II-2-2-2) to (II-2-2-4) When a compound having three or more ring structures is used in the compound, it is preferable because the orientation of the obtained optical anisotropic body is good and the curability is good. It is particularly preferable to use a compound represented by the general formula (II-2-2-2) having a ring structure.
Examples of the compounds represented by the general formulas (II-2-2-1) to (II-2-2-4) include the following formulas (II-2-2-1-1) to (II-2). The compound represented by 2-1-22) is exemplified, but not limited thereto.

In the formula, R ^d and R ^e each independently represent a hydrogen atom or a methyl group,
The cyclic group has one or more F, Cl, CF ₃ , OCF ₃ , CN groups, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and 1 to 1 carbon atoms as a substituent. An alkanoyl group having 8 carbon atoms, an alkanoyloxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkenyloxy group having 2 to 8 carbon atoms, and a carbon atom The alkenoyl group having 2 to 8 carbon atoms and the alkenoyloxy group having 2 to 8 carbon atoms may be contained.
m1 and m2 each independently represent an integer of 0 to 18, and n1, n2, n3, and n4 each independently represent 0 or 1.

The liquid crystal compound having two polymerizable functional groups can be used singly or in combination of two or more, but preferably 1 to 6 types, more preferably 2 to 6 types.
The total content of the bifunctional polymerizable liquid crystal compound having two polymerizable functional groups in the molecule is preferably 10 to 100% by mass in the total amount of the polymerizable liquid crystal compound used, and is preferably 15 to 85% by mass. % Content is more preferable, and 20 to 80% by mass is particularly preferable. When importance is attached to the hardness of the coating film, the lower limit value is preferably 30% by mass or more, more preferably 50% by mass or more, and when importance is placed on the orientation of the optical anisotropic body, the upper limit value. Is preferably 85% by mass or less, and more preferably 80% by mass or less.

(Polyfunctional polymerizable liquid crystal compound)
As the polyfunctional polymerizable liquid crystal compound having three or more polymerizable functional groups, it is preferable to use a compound having three polymerizable functional groups. Among the compounds represented by the general formula (II), as a polyfunctional polymerizable liquid crystal compound having three polymerizable functional groups in the molecule, a compound represented by the following general formula (II-2-3) is used. preferable.

In the formula, P ² , S ¹ , X ¹ , q ¹ , MG, X ² , S ² , q ² , P ³ , X ³ , q 3, S ³ , q ⁴ , P ⁴ , q 5 are each represented by the above general formula (II ) Represents the same definition. Examples of the general formula (II-2-3) include compounds represented by the following general formulas (II-2-3-1) to (II-2-3-16). The formula is not limited.

In the formula, P ² , S ¹ , X ¹ , q ¹ , MG, X ² , S ² , q ² , P ³ , X ³ , q 3, S ³ , P ⁴ , X ⁴ , S ⁴ , q ⁴ , X ⁵ , S ⁵ and q5 each represent the same definition as in the general formula (II),
B11, B12, B13, B2, and B3 represent the same definitions as B1 to B3 in the general formula (II-b), and may be the same or different,
Z11, Z12, Z13, and Z2 represent the same definitions as Z1 to Z3 in the general formula (II-b), and may be the same or different.
Examples of the compounds represented by the general formulas (II-2-3-1) to (II-2-3-16) include the following formulas (II-2-3-1-1) to (II-2). Although the compound represented by -3-1-7) is illustrated, it is not necessarily limited to these.

In the formula, R ^f , R ^g, and R ^h each independently represent a hydrogen atom or a methyl group, and R ⁱ , R ^j, and R ^k are each independently a hydrogen atom, a halogen atom, or a carbon number of 1 to 6 An alkyl group, an alkoxy group having 1 to 6 carbon atoms, a cyano group, and when these groups are an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, all are unsubstituted, Alternatively, the cyclic group may be substituted with one or two or more halogen atoms, and the cyclic group has one or more F, Cl, CF ₃ , OCF ₃ , CN groups, 1 to 8 carbon atoms as a substituent. An alkyl group, an alkoxy group having 1 to 8 carbon atoms, an alkanoyl group having 1 to 8 carbon atoms, an alkanoyloxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, and 2 to 2 carbon atoms. 8 alkenyl groups, carbon atoms Number 2-8 alkenyloxy group, alkenoyl group having 2 to 8 carbon atoms, which may have a alkenoyloxy group having from 2 to 8 carbon atoms.
m4 to m9 each independently represents an integer of 0 to 18, and n4 to n9 each independently represents 0 or 1.

The polyfunctional polymerizable liquid crystal compound having three or more polymerizable functional groups can be used alone or in combination of two or more.
The total content of the polyfunctional polymerizable liquid crystal compound having three or more polymerizable functional groups in the molecule is preferably 0 to 80% by mass in the total amount of the polymerizable liquid crystal compound to be used. More preferably, it is contained in an amount of 0 to 40% by mass. When importance is attached to the rigidity of the optical anisotropic body, the lower limit value is preferably 10% by mass or more, more preferably 20% by mass or more, and particularly preferably 30% by mass or more. When emphasizing low curing shrinkage, the upper limit is preferably 50% by mass or less, more preferably 35% by mass or less, and particularly preferably 20% by mass or less.

(Polymerizable liquid crystal composition)
In the polymerizable liquid crystal composition of the present invention, it is preferable to use a mixture of a plurality of polymerizable liquid crystal compounds satisfying the condition of the structural parameter (S) of the polymerizable liquid crystal molecules. Curability of the optically anisotropic substance obtained when the above-mentioned at least one monofunctional polymerizable liquid crystal compound is used in combination with at least one bifunctional polymerizable liquid crystal compound and / or polyfunctional polymerizable liquid crystal compound is used. This is preferable because it improves the adhesion to the substrate and at least one monofunctional polymerizable liquid crystal compound and at least one bifunctional polymerizable liquid crystal compound are more preferably used in combination. Among them, when the polymerizable liquid crystal composition of the present invention is used as an optical anisotropic body, when the curability is to be further improved, the compound has three or more ring structures as a bifunctional polymerizable liquid crystal compound. A compound selected from (II-2-2-2) to (II-2-2-4) is preferably used as a mixture of polymerizable liquid crystal compounds, and the compound has three ring structures ( It is particularly preferable to use a mixture of the compound represented by II-2-1-2) and the compound represented by (II-2-2-2).
The total amount of the monofunctional polymerizable liquid crystal compound and the bifunctional polymerizable liquid crystal compound is preferably 70% by mass to 100% by mass of the total amount of the polymerizable liquid crystal compound to be used, and 80% by mass to 100% by mass. % Is particularly preferable.

(solvent)
The polymerizable liquid crystal composition used in the present invention may contain a solvent. As the solvent, cyclopentanone, methyl isobutyl ketone (MIBK), propylene glycol 1-monomethyl ether 2-acetate (PGMEA), and toluene are preferable because of their moderate affinity for polymethyl methacrylate resin or polycarbonate resin, and a mixed solvent thereof. And a mixed solvent with other solvents containing these is preferable.
These can be used alone or in combination of two or more. However, since the solubility of the base material differs depending on the solvent, the optimal solvent differs depending on the base material.
A solvent having high solubility in the polymethyl methacrylate resin is not preferable because it easily extracts components that are miscible with the polymerizable liquid crystal, such as a low molecular weight component in the polymethyl methacrylate resin. Examples of the unfavorable solvent include acetic acid, acetone, benzene, chlorobenzene, chloroform, cyclohexanone, cyclohexyl acetate, dioxane, ethyl acetate, MEK, methylene chloride and the like.

Similarly, a solvent having high solubility in the polycarbonate resin is not preferable because it easily extracts components that are miscible with the polymerizable liquid crystal, such as low molecular weight components in the resin. Examples of the unfavorable solvent include dioxane, acetone, benzene, methylene chloride, chloroform and the like.
However, even if it is a solvent with high solubility with respect to these board | substrate resin, if another solvent is mixed with this and it is set as the mixed solvent which suppressed the solubility with respect to polymethylmethacrylate resin or polycarbonate resin, it can be used.
The ratio of the solvent is not particularly limited as long as the polymerizable liquid crystal composition used in the present invention is usually applied by coating, so long as the applied state is not significantly impaired, but the solid content of the polymerizable liquid crystal composition and the solvent The ratio is preferably 0.1: 99.9 to 80:20, and more preferably 1:99 to 50:50 in view of applicability.

(Resin substrate)
The polymethylmethacrylate resin substrate or the polycarbonate resin substrate used in the present invention is a substrate usually used for an optical anisotropic body, and needs to be an organic material having heat resistance capable of withstanding heating at the time of manufacturing the optical anisotropic body. is there.
In the present invention, the polymethyl methacrylate resin may be a homopolymer of methyl methacrylate (PMMA), a copolymer of methyl methacrylate and a polymerizable compound other than methyl methacrylate, or the homopolymer described above. A mixed material of a polymer and another polymer may be used, or a mixed material of the copolymer and another polymer may be used. The methyl methacrylate structural unit is contained at least 50% by mass, preferably 65-100% by mass, more preferably 75-99.5% by mass, and more preferably 80-98.5% by mass. preferable. By using a resin material containing methyl methacrylate in these preferred ranges, chemical erosion by the solvent constituting the polymer solution of this embodiment can be prevented.
Examples of the polymethyl methacrylate resin in the present invention include polymethyl methyl methacrylate, polyethyl methyl methacrylate, polypropyl methyl methacrylate, polybutyl methyl methacrylate, polyisobutyl methyl methacrylate, polyhexyl methyl methacrylate, polyoctyl methyl methacrylate, poly-2-ethylhexyl. Polyalkylmethyl methacrylate such as methyl methacrylate, polydecylmethyl methacrylate, polylaurylmethyl methacrylate, polyhydroxyalkylmethyl methacrylate such as poly-2-hydroxyethylmethyl methacrylate, poly-2-hydroxybutylmethyl methacrylate, polydimethylaminoethylmethyl methacrylate , Polydiethylaminoethyl methyl methacrylate Includes polyaminomethyl methacrylate such as polyacrylic methyl methacrylate such as polycyclohexylmethyl methacrylate, polycyclohexylmethyl methacrylate, polybornylmethyl methacrylate, aromatic polymethyl methacrylate such as polyphenylmethyl methacrylate, polybenzylmethyl methacrylate, etc. It is.
The polymethyl methacrylate resin of the present invention may form a copolymer with another resin. Examples of polymerizable compounds other than methyl methacrylate in the polymethyl methacrylate resin include, for example, methyl acrylate, ethyl acrylate, acrylic acid-n-propyl, acrylic acid-n-butyl, acrylic acid isobutyl, acrylic acid-2-ethylhexyl. , Ethyl methacrylate, -n-propyl methacrylate, -n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, styrene, styrene derivatives and the like.
Generally, a polycarbonate resin is synthesized from a dihydroxy compound and a carbonyl halide compound such as phosgene. The dihydroxy component is not particularly limited as long as it is usually used as a dihydroxy component of an aromatic polycarbonate, and may be a bisphenol or an aliphatic diol. Examples of bisphenols include 4,4′-dihydroxybiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, and 1,1-bis (4-hydroxyphenyl) -1- Phenylethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) -3,3,5 -Trimethylcyclohexane, 2,2-bis (4-hydroxy-3,3'-biphenyl) propane, 2,2-bis (4-hydroxy-3-isopropylphenyl) propane, 2,2-bis (3-t- Butyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxypheny) ) Octane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3-cyclohexyl-4) -Hydroxyphenyl) propane, 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) diphenylmethane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dimethyldiphenyl ether, 4,4′-sulfoni Diphenol, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 2,2'-dimethyl-4,4'-sulfonyldiphenol, 4,4'-dihydroxy-3,3'-dimethyl Diphenyl sulfoxide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide, 2,2′-diphenyl-4,4′-sulfonyldiphenol, 4,4′-dihydroxy-3,3′-diphenyldiphenyl sulfoxide 4,4′-dihydroxy-3,3′-diphenyldiphenyl sulfide, 1,3-bis {2- (4-hydroxyphenyl) propyl} benzene, 1,4-bis {2- (4-hydroxyphenyl) propyl } Benzene, 1,4-bis (4-hydroxyphenyl) cyclohexane, 1,3-bis (4-hydro Cyphenyl) cyclohexane, 4,8-bis (4-hydroxyphenyl) tricyclo [5.2.1.02,6] decane, 4,4 ′-(1,3-adamantanediyl) diphenol, 1,3-bis (4-Hydroxyphenyl) -5,7-dimethyladamantane is mentioned, and examples of the aliphatic diols include 2,2-bis- (4-hydroxycyclohexyl) -propane, 1,14-tetradecanediol, octaethylene glycol. 1,16-hexadecanediol, 4,4′-bis (2-hydroxyethoxy) biphenyl, bis {(2-hydroxyethoxy) phenyl} methane, 1,1-bis {(2-hydroxyethoxy) phenyl} ethane, 1,1-bis {(2-hydroxyethoxy) phenyl} -1-phenylethane, 2,2-bis { (2-hydroxyethoxy) phenyl} propane, 2,2-bis {(2-hydroxyethoxy) -3-methylphenyl} propane, 1,1-bis {(2-hydroxyethoxy) phenyl} -3,3,5 -Trimethylcyclohexane, 2,2-bis {4- (2-hydroxyethoxy) -3,3'-biphenyl} propane, 2,2-bis {(2-hydroxyethoxy) -3-isopropylphenyl} propane, 2, 2-bis {3-tert-butyl-4- (2-hydroxyethoxy) phenyl} propane, 2,2-bis {(2-hydroxyethoxy) phenyl} butane, 2,2-bis {(2-hydroxyethoxy) Phenyl} -4-methylpentane, 2,2-bis {(2-hydroxyethoxy) phenyl} octane, 1,1-bis {(2-hydroxyeth Xyl) phenyl} decane, 2,2-bis {3-bromo-4- (2-hydroxyethoxy) phenyl} propane, 2,2-bis {3,5-dimethyl-4- (2-hydroxyethoxy) phenyl} Propane, 2,2-bis {3-cyclohexyl-4- (2-hydroxyethoxy) phenyl} propane, 1,1-bis {3-cyclohexyl-4- (2-hydroxyethoxy) phenyl} cyclohexane, bis {(2 -Hydroxyethoxy) phenyl} diphenylmethane, 9,9-bis {(2-hydroxyethoxy) phenyl} fluorene, 9,9-bis {4- (2-hydroxyethoxy) -3-methylphenyl} fluorene, 1,1- Bis {(2-hydroxyethoxy) phenyl} cyclohexane, 1,1-bis {(2-hydroxyethoxy) fe L} cyclopentane, 4,4′-bis (2-hydroxyethoxy) diphenyl ether, 4,4′-bis (2-hydroxyethoxy) -3,3′-dimethyldiphenyl ether, 1,3- Bis [2-{(2-hydroxyethoxy) phenyl} propyl] benzene, 1,4-bis [2-{(2-hydroxyethoxy) phenyl} propyl] benzene, 1,4-bis {(2-hydroxyethoxy) Phenyl} cyclohexane, 1,3-bis {(2-hydroxyethoxy) phenyl} cyclohexane, 4,8-bis {(2-hydroxyethoxy) phenyl} tricyclo [5.2.1.02,6] decane, 1, 3-bis {(2-hydroxyethoxy) phenyl} -5,7-dimethyladamantane, 3,9-bis (2-hydroxy-1,1-dimethylethyl) ) -2,4,8,10-tetraoxaspiro (5,5) undecane, 1,4: 3,6-dianhydro-D-sorbitol (isosorbide), 1,4: 3,6-dianhydro-D-mannitol (Isomannide), 1,4: 3,6-dianhydro-L-iditol (isoidid), and the like. You may use these individually or in combination of 2 or more types.
The polycarbonate resin of the present invention may be a branched polycarbonate resin by using a branching agent in combination with the above-mentioned dihydroxy compound. Examples of the trifunctional or higher polyfunctional aromatic compound used in the branched polycarbonate resin include phloroglucin, phloroglucid, or 4,6-dimethyl-2,4,6-tris (4-hydroxydiphenyl) heptene-2, 2 , 4,6-trimethyl-2,4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) Ethane, 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, 4- {4- [ Trisphenol such as 1,1-bis (4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol, tetra (4-hydride) Loxyphenyl) methane, bis (2,4-dihydroxyphenyl) ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and their acids Among them, 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are preferable. 1-Tris (4-hydroxyphenyl) ethane is preferred.
The resin substrate used in the present invention may have a retardation, and depending on the application purpose, the retardation of the resin substrate, the retardation of the alignment film on the substrate and the polymer of the polymerizable liquid crystal composition, Therefore, the optimum phase difference can be obtained. From the viewpoint of maintaining the stability of characteristics, the phase difference of the resin substrate is preferably 0 to 500 nm, and more preferably 0 to 250 nm.
The thickness of the resin substrate used in the present invention can be determined according to the application purpose. The thickness may be optimal from the viewpoint of phase difference or transparency, or may be optimal from the viewpoint of ease of handling in the process, heat resistance during use, and mechanical characteristics. The thickness of the resin substrate is preferably 10 to 400 μm, more preferably 10 to 200 μm.

(Polymerization initiator)
In general, the polymerizable liquid crystal composition of the present invention is polymerized by irradiation with light such as ultraviolet rays or heating. As the photopolymerization initiator used in the case of carrying out by light irradiation, known and conventional ones can be used. -Hydroxycyclohexyl phenyl ketone ("Irgacure 184" manufactured by Ciba Specialty Chemicals), 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one ("Darocur 1116" manufactured by Merck), 2-Methyl-1-[(methylthio) phenyl] -2-morpholinopropane-1 (“Irgacure 907” manufactured by Ciba Specialty Chemicals). Benzylmethylketal ("Irgacure 651" manufactured by Ciba Specialty Chemicals). A mixture of 2,4-diethylthioxanthone (“Kayacure DETX” manufactured by Nippon Kayaku Co., Ltd.) and ethyl p-dimethylaminobenzoate (“Kayacure EPA” manufactured by Nippon Kayaku Co., Ltd.) -ITX ") and a mixture of ethyl p-dimethylaminobenzoate, acylphosphine oxide (" Lucirin TPO "manufactured by BASF), and the like. The amount of the photopolymerization initiator used is preferably 10% by mass or less, particularly preferably 0.5 to 5% by mass with respect to the polymerizable liquid crystal compound.

  In addition, as the thermal polymerization initiator used in the thermal polymerization, known and conventional ones can be used, for example, methyl acetoacetate peroxide, cumene hydroperoxide, benzoyl peroxide, bis (4-t-butylcyclohexyl). Peroxydicarbonate, t-butylperoxybenzoate, methyl ethyl ketone peroxide, 1,1-bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane, p-pentahydroperoxide, t-butylhydro Organic peroxides such as peroxide, dicumyl peroxide, isobutyl peroxide, di (3-methyl-3-methoxybutyl) peroxydicarbonate, 1,1-bis (t-butylperoxy) cyclohexane, 2, 2'-azobisisobutyronitrile Azonitrile compounds such as 2,2′-azobis (2,4-dimethylvaleronitrile), azoamidin compounds such as 2,2′-azobis (2-methyl-N-phenylpropion-amidin) dihydrochloride, 2,2 ′ Azoamide compounds such as azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide} and alkylazo such as 2,2′azobis (2,4,4-trimethylpentane) Compounds and the like can be used. The amount of the thermal polymerization initiator used is preferably 10% by mass or less, particularly preferably 0.5 to 5% by mass with respect to the polymerizable liquid crystal compound.

(Other ingredients)
In the polymerizable liquid crystal composition of the present invention, a liquid crystal compound having no polymerizable group may be added as necessary. However, if the addition amount is too large, the liquid crystal compound may be eluted from the obtained optical anisotropic body to contaminate the laminated member, and in addition, the heat resistance of the optical anisotropic body may be reduced. In this case, the content is preferably 30% by mass or less, more preferably 15% by mass or less, and particularly preferably 5% by mass or less with respect to the total amount of the polymerizable liquid crystal compound.
The polymerizable liquid crystal composition used in the present invention may be added with a compound having a polymerizable group but not a polymerizable liquid crystal compound. Such a compound can be used without particular limitation as long as it is generally recognized as a polymerizable monomer or polymerizable oligomer in this technical field. When adding, it is preferable that it is 10 mass% or less with respect to the polymeric liquid crystal composition of this invention, and 3 mass% or less is still more preferable.

The polymerizable liquid crystal composition used in the present invention may be added with a compound having optical activity, that is, a chiral compound. The chiral compound itself does not need to exhibit a liquid crystal phase, and may or may not have a polymerizable group. Moreover, the direction of the spiral of the chiral compound can be appropriately selected depending on the intended use of the polymer.
Specifically, for example, “CB-15”, “C-15”, Merck manufactured by BDH Corporation having cholesterol as a chiral group having cholesterol as a chiral group, cholesterol stearate, and 2-methylbutyl as a chiral group. "S-1082" manufactured by the company, "CM-19", "CM-20", "CM" manufactured by Chisso, "S-811" manufactured by Merck having 1-methylheptyl group as a chiral group, Chisso “CM-21”, “CM-22” and the like manufactured by the company can be mentioned. A chiral compound having a polymerizable group can also be used.

When adding a chiral compound, depending on the use of the polymer of the polymerizable liquid crystal composition of the present invention, the value obtained by dividing the thickness (d) of the obtained polymer by the helical pitch (P) in the polymer (d / P) is preferably added in an amount in the range of 0.1 to 100, more preferably in the range of 0.1 to 20.
In order to uniformly apply the polymerizable liquid crystal composition used in the present invention and obtain a photo-alignment film having a uniform film thickness, a general-purpose additive can be used. For example, additives such as a leveling agent, a thixotropic agent, a surfactant, an ultraviolet absorber, an infrared absorber, an antioxidant, and a surface treatment agent can be added to such an extent that the liquid crystal alignment ability is not significantly reduced.

(Orientation layer)
(Orientation treatment)
In addition, the substrate is usually subjected to an alignment treatment or provided with an alignment film so that the polymerizable liquid crystal composition is aligned when the polymerizable liquid crystal composition of the present invention is applied and dried. Also good. Examples of the alignment treatment include stretching treatment, rubbing treatment, polarized ultraviolet visible light irradiation treatment, ion beam treatment, and the like. When the alignment film is used, a known and conventional alignment film is used. Such alignment films include polyimide, polysiloxane, polyamide, polyvinyl alcohol, polycarbonate, polystyrene, polyphenylene ether, polyarylate, polyethylene terephthalate, polyether sulfone, epoxy resin, epoxy acrylate resin, acrylic resin, coumarin compound, chalcone. Examples of the compound include compounds, cinnamate compounds, fulgide compounds, anthraquinone compounds, azo compounds, and arylethene compounds. The compound subjected to the alignment treatment by rubbing is preferably an alignment treatment or a compound in which crystallization of the material is promoted by inserting a heating step after the alignment treatment. Among the compounds that perform alignment treatment other than rubbing, it is preferable to use a photo-alignment material.
As the rubbing type alignment film, at least one kind of polyimide selected from polyamic acids and imidized polymers thereof as exemplified below is preferably used.

<Polyamic acid>
The polyamic acid constituting the liquid crystal aligning agent of the present invention is obtained by reacting a tetracarboxylic dianhydride and a diamine compound.
[Tetracarboxylic dianhydride]
Examples of the tetracarboxylic dianhydride include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene. -1,2-dicarboxylic acid anhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3 -Furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3 -Furanyl) -naphtho [1,2-c] furan-1,3-dione, pyromellitic dianhydride.

[Diamine compound]
Examples of the diamine compound used for the synthesis of the polyamic acid include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, 4,4′-diaminodiphenyl sulfide, 4,4′-diaminodiphenyl sulfone, 3,3′-dimethyl-4,4′-diaminobiphenyl, 4,4′-diaminobenzanilide, 4,4′-diaminodiphenyl ether, 1,5-diaminonaphthalene, 2, Aromatic diamines such as 2'-dimethyl-4,4'-diaminobiphenyl;
1,1-metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-diaminoheptamethylenediamine, 1 , 4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-methanoindanylene methylenediamine, tricyclo [6.2.1.0 ^2,7 ] -undecylenedimethyldiamine, 4 Aliphatic and cycloaliphatic diamines such as 4,4'-methylenebis (cyclohexylamine);
2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 5,6-diamino-2,3-dicyanopyrazine, 5,6-diamino-2,4 -Dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-triazine, 1,4-bis (3-aminopropyl) piperazine, 2,4-diamino-6-isopropoxy-1,3 , 5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-diamino-6-phenyl-1,3,5-triazine, 2,4-diamino-6-methyl A diamine having two primary amino groups and a nitrogen atom other than the primary amino group in the molecule, such as -s-triazine;
And so on. These diamine compounds can be used alone or in combination of two or more.

[Synthetic reaction of polyamic acid]
The ratio of the tetracarboxylic dianhydride and the diamine compound used in the polyamic acid synthesis reaction is such that the acid anhydride group of the tetracarboxylic dianhydride is 0.1 relative to 1 equivalent of the amino group contained in the diamine compound. A ratio of 2 to 2 equivalents is preferable, and a ratio of 0.3 to 1.2 equivalents is more preferable.

<Imidized polymer>
The imidized polymer used for the liquid crystal aligning agent of the present invention can be synthesized by dehydrating and ring-closing the polyamic acid. The imidized polymer referred to here includes a partially imidized polymer obtained by partially imidizing the polyamic acid and a polymer imidized by 100%. Hereinafter, these are collectively referred to as an “imidized polymer”. Describe. The polyamic acid is dehydrated and closed by (i) a method of heating the polyamic acid, or (ii) dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydrating ring-closing catalyst to this solution, and heating as necessary. By the method.
The reaction temperature in the method of heating the polyamic acid (i) is preferably 50 to 200 ° C, more preferably 60 to 170 ° C. When the reaction temperature is less than 50 ° C., the dehydration ring-closing reaction does not proceed sufficiently, and when the reaction temperature exceeds 200 ° C., the molecular weight of the imidized polymer obtained may decrease.

  On the other hand, in the method (ii) of adding a dehydrating agent and a dehydrating ring-closing catalyst to the polyamic acid solution, an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride is used as the dehydrating agent. Can do. The amount of the dehydrating agent used is preferably 0.01 to 20 mol relative to 1 mol of the polyamic acid repeating unit. Moreover, as a dehydration ring closure catalyst, tertiary amines, such as a pyridine, a collidine, a lutidine, a triethylamine, can be used, for example. However, it is not limited to these. The amount of the dehydration ring-closing catalyst used is preferably 0.01 to 10 mol with respect to 1 mol of the dehydrating agent used. In addition, as an organic solvent used for dehydration ring closure reaction, the organic solvent illustrated as what is used for the synthesis | combination of a polyamic acid can be mentioned. And the reaction temperature of dehydration ring closure reaction becomes like this. Preferably it is 0-180 degreeC, More preferably, it is 10-150 degreeC. In addition, the imidized polymer can be purified by performing the same operation as the polyamic acid purification method on the reaction solution thus obtained.

(Photo-alignment layer)
The alignment layer according to the present invention is preferably a photo-alignment layer. The photo-alignment layer is composed of a photo-alignment film, and the average thickness of the photo-alignment layer is preferably 10 to 1000 nm, more preferably 20 to 500 nm, and still more preferably 50 to 300 nm.

(Photoresponsive molecule)
The photo-alignment layer according to the present invention is preferably composed of a photo-alignment component, and more preferably contains an ultraviolet absorber. Moreover, the said photo-alignment component should just contain 1 or more types of photoresponsive molecules. The photoresponsive molecule is a photoresponsive isomerized molecule that isomerizes in response to light and is oriented substantially perpendicularly or parallel to the polarization axis, and a photoresponsive property that forms a cross-linked structure by dimerization in response to light At least one selected from the group consisting of a dimerization molecule and a photoresponsive decomposable polymer in which a polymer chain is cleaved in response to light is preferable, and a photoresponsive isomerized molecule is sensitive and has orientation regulating power. This is particularly preferable.

  The photoresponsive isomerized molecule according to the present invention is preferably a dichroic dye, and the specific structure is particularly preferably an azo compound represented by the general formula (a) or a polymer thereof.

In general formula (a), R ¹ and R ² are each independently a hydroxy group, or (meth) acryloyl group, (meth) acryloyloxy group, (meth) acryloylamino group, vinyl group, vinyloxy group and maleimide group. Represents a polymerizable functional group selected from the group consisting of A ¹ and A ² each independently represents a divalent hydrocarbon group which may be substituted with a single bond or an alkoxy group, and B ¹ and B 2 ² are each independently a single bond, —O—, —CO—O—, —O—CO—, —CO—NH—, —NH—CO—, —NH—CO—O— or —O—CO—. NH— represents that in the bond of R ¹ and R ² , an —O—O— bond is not formed, and m and n each independently represent an integer of 0 to 4 (provided that m or n is when 2 or more, a plurality of ^{a 1,} B 1, ^{a 2} and ^{B 2} the May be different even represent two B ¹ or A ¹ or A ² is sandwiched between B ² is which may be optionally divalent hydrocarbon group substituted by an alkoxy group.), R ^{3 to} R ⁶ are each independently a hydrogen atom, halogen atom, halogenated alkyl group, allyloxy group, cyano group, nitro group, alkyl group, hydroxyalkyl group, alkoxy group, carboxyl group or an alkali metal salt thereof, alkoxycarbonyl Group, halogenated methoxy group, hydroxy group, sulfo group or alkali metal salt thereof, amino group, carbamoyl group, sulfamoyl group, —OR ⁷ (where R ⁷ is a lower alkyl group having 1 to 6 carbon atoms, carbon atom number) A lower alkyl group having 1 to 6 carbon atoms substituted with a 3 to 6 cycloalkyl group or a lower alkoxy group having 1 to 6 carbon atoms; Be), a hydroxyalkyl group or -CONR 1 to 4 carbon atoms ⁸ R ^{9 (R 8} and ^{R 9} represents a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms each independently), or ( It represents a polymerizable functional group selected from the group consisting of (meth) acryloyl group, (meth) acryloyloxy group, (meth) acryloylamino group, vinyl group, vinyloxy group and maleimide group, and X is a single bond, —CH═CH. -, - ^{NR 10} - ^{(where, R 10} represents a hydrogen atom or a hydrocarbon group having 20 or less carbon atoms), - NH-CO-NH -, - S-, or -CH ₂ - represents, ^{G 1} and G ² are each independently 1,4-phenylene group such as phenylene group; represents a 2,6-diyl such as arylene group group, one or more present in the phenylene group or an arylene group Each hydrogen atom is independently substituted with a hydroxy group, a halogen group, a cyano group, a nitro group, an amino group, a sulfo group, an alkali metal salt of a sulfo group, an alkyl group having 1 to 7 carbon atoms, an alkoxy group, or an alkanoyl group. May be.

In the general formula (a), it is preferable that at least one of R ¹ or R ² is a polymerizable functional group because stability to light and heat is increased. Among the polymerizable functional groups, a (meth) acryloyloxy group is particularly preferable. A maleimide group is preferable because a polymerization initiator is unnecessary. When R ¹ is a hydroxy group, m is preferably 0, and when R ¹ is a polymerizable functional group, m preferably represents an integer of 1 to 3, and more preferably 1 or 2. When R ² is a hydroxy group, n is preferably 0, and when R ² is a polymerizable functional group, n preferably represents an integer of 1 to 3, and more preferably 1 or 2.

A ¹ and A ² each independently represent a single bond or a divalent hydrocarbon group which may be substituted by an alkoxy group. Examples of the divalent hydrocarbon group include a methylene group, an ethylene group and a trimethylene group. A linear alkylene group having 1 to 18 carbon atoms such as tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group; -Methylethylene group, 1-methyltriethylene group, 2-methyltriethylene group, 1-methyltetraethylene group, 2-methyltetraethylene group, 1-methylpentamethylene group, 2-methylpentamethylene group, 3-methyl A branched alkylene group having 1 to 18 carbon atoms such as a pentamethylene group; a phenylene group such as a p-phenylene group; An arylene group such as a phthalenediyl group is exemplified, and as the divalent hydrocarbon group substituted by an alkoxy group, one of the carbon atoms of the aforementioned linear alkylene group having 1 to 18 or branched alkylene group is Substituents substituted with oxygen atoms, 2-methoxy-1,4-phenylene group, 3-methoxy-1,4-phenylene group, 2-ethoxy-1,4-phenylene group, 3-ethoxy-1,4-phenylene A phenylene group having a linear or branched alkoxy group having 1 to 18 carbon atoms such as a group, 2,3,5-trimethoxy-1,4-phenylene group is preferred.

B ¹ and B ² are preferably each independently a single bond, —O—, —CO—O— or —O—CO—.
In R ^{3 to} R ⁶ , examples of the halogen atom include a fluorine atom and a chlorine atom. Examples of the halogenated alkyl group include a trichloromethyl group and a trifluoromethyl group. Examples of the halogenated methoxy group include a chloromethoxy group and a trifluoromethoxy group. As the alkoxy group, the alkyl group portion is substituted with a lower alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or a lower alkoxy group having 1 to 6 carbon atoms. -6 lower alkyl groups. Examples of the lower alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a 1-methylethyl group. Examples of the lower alkyl group having 1 to 6 carbon atoms substituted with a lower alkoxy group having 1 to 6 carbon atoms include a methoxymethyl group, 1-ethoxyethyl group, tetrahydropyranyl group and the like. Examples of the hydroxyalkyl group include a hydroxyalkyl group having 1 to 4 carbon atoms, specifically, a hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group. Group, 3-hydroxypropyl group, 1-hydroxybutyl group and the like. Examples of the carbamoyl group include those having an alkyl group portion of 1 to 6 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a 1-methylethyl group. Among these, a halogen atom, a carboxy group, a halogenated methyl group, a halogenated methoxy group, a methoxy group, an ethoxy group, a propoxy group, a hydroxymethyl group, a carbamoyl group, a dimethylcarbamoyl group or a cyano group are preferable, and a carboxy group, hydroxymethyl A group or a trifluoromethyl group is particularly preferred in that good orientation can be obtained.

Further, when R ³ and R ⁴ are substituted at the meta positions of the phenylene group at both ends of the 4,4′-bis (phenylazo) biphenyl skeleton, an excellent photo-alignment film is obtained, and R ⁵ and R ⁶ are , 4,4′-bis (phenylazo) biphenyl skeleton is preferably substituted at the 2,2′-position, and thus excellent photo-alignment properties can be obtained.

  The azo compound represented by the general formula (a) according to the present invention is preferably the following general formula (b).

In formula ^(b), R 3 ~R ⁶ represents the same meaning as ^R 3 to R ⁶ in formula (a).
Examples of the halogen atom include a fluorine atom and a chlorine atom. Examples of the halogenated methyl group include a trichloromethyl group and a trifluoromethyl group. Examples of the halogenated methoxy group include a chloromethoxy group and a trifluoromethoxy group.
Examples of the lower alkyl group having 1 to 6 carbon atoms of R ⁷ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a 1-methylethyl group. Examples of the lower alkyl group having 1 to 6 carbon atoms substituted by the lower alkoxy group having 1 to 6 carbon atoms represented by R ⁷ include a methoxymethyl group, a 1-ethoxyethyl group, and a tetrahydropyranyl group. It is done. Examples of the hydroxyalkyl group having 1 to 4 carbon atoms include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy A butyl group etc. are mentioned.
Examples of the alkyl group having 1 to 6 carbon atoms represented by R ⁸ and R ⁹ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a 1-methylethyl group.

Among these, a halogen atom, carboxyl group, halogenated methyl group, halogenated methoxy group, methoxy group, ethoxy group, propoxy group, hydroxymethyl group, carbamoyl group, dimethylcarbamoyl group, and cyano group are preferable, carboxyl group, hydroxymethyl A group or a trifluoromethyl group is particularly preferred in that good orientation can be obtained.
Further, when R ³ and R ⁴ are substituted at the meta position as viewed from the azo group of the phenylene group at both ends of the 4,4′-bis (phenylazo) biphenyl skeleton, excellent photoalignment is obtained, preferable.
R ⁵ and R ⁶ each independently represent a carboxyl group, a sulfo group, a nitro group, an amino group, an alkoxycarbonyl group or a hydroxy group. However, the carboxyl group and the sulfo group may form a salt with an alkali metal such as lithium, sodium or potassium.
When R ⁵ and R ⁶ are substituted at the 2,2′-position of the 4,4′-bis (phenylazo) biphenyl skeleton, excellent photoalignment can be obtained, which is particularly preferable.

R ⁵ and R ⁶ in the general formula (b) are presumed to be sites that most affect the photo-alignment performance and other characteristics, and may vary depending on the type and combination of substituents that can be introduced into R ⁵ and R ^6. Characteristics can be obtained. When R ⁵ and R ⁶ are a carboxyl group or a salt thereof, a sulfo group or a salt thereof, it has high affinity for a transparent electrode such as glass or ITO, and a photo-alignment film can be uniformly formed on the substrate surface. This is preferable because it is possible. The compound represented by the general formula (b) may be a single compound or a mixture of compounds having different R ^{3 to} R ⁶ within the range of the compound represented by the general formula (b).

  Examples of the compounds represented by the general formulas (a) and (b) include compounds having the following structures. Among these, the weight average molecular weight of the polymer is preferably 5,000 to 1,000,000, and preferably 10,000 to 500,000 from the viewpoint of setting the viscosity of a solution that is easy to apply, maintaining the heat resistance of the dried film after coating, and increasing the orientation regulating force. Particularly preferred.

  Among the azo compounds represented by the general formula (a) according to the present invention, the following general formula (c-1) is preferable.

In general formula (c-1), R ¹¹ and R ¹² are each independently hydroxy, or (meth) acryloyl group, (meth) acryloyloxy group, (meth) acrylamide group, vinyl group, vinyloxy group and maleimide group. Represents a polymerizable functional group selected from the group consisting of X ^11, when R ¹¹ is a hydroxy group, a single bond, when R ¹¹ is a polymerizable functional _{^{group, - (A 1 -B 1)}} m - represents a linking group represented by, X ¹² is When R ¹² is a hydroxy group, it represents a single bond, and when R ¹² is a polymerizable functional group, it represents a linking group represented by — (A ² —B ² ) _n —. Here, A ¹ is bonded to R ¹¹ , and A ² is bonded to R ¹² . A ¹ and A ² each independently represent a single bond or a divalent hydrocarbon group, and B ¹ and B ² each independently represent a single bond, —O—, —CO—O—, —O—CO—. , -CO-NH-, -NH-CO-, -NH-CO-O- or -O-CO-NH-. m and n each independently represents an integer of 0 to 4. However, when m or n is 2 or more, a plurality of A ¹ , B ¹ , A ² and B ² may be the same or different. However, A ¹ or A ² sandwiched between two B ¹ or B ² is not a single bond.

R ¹³ and R ¹⁴ are each independently a hydrogen atom, a halogen atom, a carboxyl group, a halogenated methyl group, a halogenated methoxy group, a cyano group, a nitro group, or —OR ¹⁷ (wherein R ¹⁷ is a group having 1 to 6 represents a lower alkyl group having 6 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or a lower alkyl group having 1 to 6 carbon atoms substituted with a lower alkoxy group having 1 to 6 carbon atoms). 4 hydroxyalkyl group or —CONR ¹⁸ R ¹⁹ (R ¹⁸ and R ¹⁹ each independently represents a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms) or a methoxycarbonyl group. However, the carboxyl group may form a salt with the alkali metal. R ¹⁵ and R ¹⁶ each independently represents a carbamoyl group or a sulfamoyl group.

Among the compounds of the general formula (c-1), compounds in which R ¹¹ and R ¹² are hydroxy groups, and R ¹³ and R ¹⁴ are hydroxyalkyl groups having 1 to 4 carbon atoms are preferred, and R ¹¹ and R ¹² Particularly preferred are compounds wherein is a hydroxy group and R ¹³ and R ¹⁴ are hydroxymethyl groups.

  Examples of the compound represented by the general formula (c-1) include compounds having the following structure.

  Among the azo compounds represented by the general formula (a) according to the present invention, the following general formula (c-2) is more preferable.

In formula (c-2), R ²¹ and R ²² each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and A ¹¹ and A ¹² Each independently represents a naphthalene ring having an amino group and a sulfo group as substituents, or a benzene ring having an amino group and a sulfo group as substituents. However, the sulfo group may form a salt with an alkali metal. As the compound represented by the general formula (c-2), those in which R ²¹ and R ²² are each independently a hydrogen atom, a methyl group, or a methoxy group are preferable.

  As an example of a compound represented by general formula (c-2), the compound of the following structure is mentioned, for example.

The compound represented by the general formula (a) exhibits high solubility in water or a polar organic solvent, and exhibits good affinity for glass and the like. After a solution obtained by dissolving the compound in water or a polar organic solvent is applied to a substrate, a uniform and stable coating film is formed on the substrate simply by removing the water or the polar organic solvent. be able to.
Moreover, the compound represented by general formula (a) can also be used independently, and 2 or more types of compounds can also be mixed and used for it.
At least one compound (c) selected from the group consisting of the compound represented by the general formula (b), the compound represented by the general formula (c-1), and the compound represented by the general formula (c-2) ), It is possible to obtain a photo-alignment film having excellent heat resistance while maintaining sensitivity.

  The specific structure of the photoresponsive dimerization molecule according to the present invention is represented by at least one selected from the group consisting of the following general formulas (1A) and (1B) and the following general formula (2). A photoresponsive dimerization type polymer is preferred. The photoresponsive dimerization type molecule is preferably a photoresponsive dimerization type polymer obtained by polymerizing a compound represented by the general formula (4) and / or the general formula (5).

  The photoresponsive dimerization type molecule according to the present invention has the following general formula (1A) or (1B):

(In the general formula (1), Sp is a single bond, — (CH ₂ ) _u — (wherein _u represents 1 to 20), —OCH ₂ —, —CH ₂ O—, —COO—. , —OCO—, —CH═CH—, —CF═CF—, —CF ₂ O—, —OCF ₂ —, —CF ₂ CF ₂ —, and —C≡C—. In these substituents, one or more of non-adjacent CH ₂ groups independently represent —O—, —CO—, —CO—O—, —O—CO—, — Si (CH ₃ ) ₂ —O—Si (CH ₃ ) ₂ —, —NR—, —NR—CO—, —CO—NR—, —NR—CO—O—, —O—CO—NR—, — NR—CO—NR—, —CH═CH—, —C≡C— or —O—CO—O— (wherein R is independently hydrogen or an alkyl group having 1 to 5 carbon atoms) Can be substituted with
A ¹ and A ² are each independently
(A) trans-1,4-cyclohexylene group (in this group, one methylene group or two or more methylene groups which are not adjacent to each other are replaced by —O—, —NH— or —S—) May be)
(B) a 1,4-phenylene group (one or more of —CH═ present in this group may be replaced by —N═), and (c) a 1,4-cyclohexenylene group 2,5-thiophenylene group, 2,5-furylene group, 1,4-bicyclo (2.2.2) octylene group, naphthalene-1,4-diyl group, naphthalene-2,6-diyl group, deca Represents a group selected from the group consisting of a hydronaphthalene-2,6-diyl group and a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, the group (a), group (b) or group (C) is each unsubstituted or one or more hydrogen atoms may be substituted with a fluorine atom, a chlorine atom, a cyano group, a methyl group or a methoxy group,
Z ¹ , Z ² and Z ³ are each independently a single bond, —O—, — (CH ₂ ) _u — (wherein _u represents 1 to 20), —OCH ₂ —, —CH. ₂ O—, —COO—, —OCO—, —CH═CH—, —CF═CF—, —CF ₂ O—, —OCF ₂ —, —CF ₂ CF ₂ — or —C≡C—. In these substituents, one or more of non-adjacent CH ₂ groups are independently —O—, —CO—, —CO—O—, —O—CO—, —Si (CH ₃ ) ₂ —O. —Si (CH ₃ ) ₂ —, —NR—, —NR—CO—, —CO—NR—, —NR—CO—O—, —O—CO—NR—, —NR—CO—NR—, — CH═CH—, —C≡C— or —O—CO—O— (wherein R independently represents hydrogen or an alkyl group having 1 to 5 carbon atoms) can be substituted.
X is —O—, a single bond, —NR— or a phenylene group,
R ^b is a polymerizable group, an alkoxy group, a cyano group, or a fluorinated alkyl group having 1 to 12 carbon atoms,
m is 0, 1, or 2;
M _b and M _d may be independently the same or different and each represents a monomer unit of the following general formulas (U-1) to (U-13);

(In the above general formulas (U-1) to (U-10), a broken line represents a bond to Sp, and R ^a is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a halogen atom. Any hydrogen atom in each structure may be substituted by a fluorine atom, a chlorine atom, a methyl group, a phenyl group, a methoxy group,
In the general formulas (U-11) to (U-13), a broken line represents a bond to Sp, R ¹ is a tetravalent ring structure, R ² is a trivalent organic group, R ³ is a hydrogen atom, a hydroxyl group Represents an alkyl group having 1 to 15 carbon atoms and an alkoxy group having 1 to 15 carbon atoms. )
y and w represent the molar fraction of the copolymer, 0 <y ≦ 1 and 0 ≦ w <1, n represents 4 to 100,000, and the monomer units of M _b and M _d are each independently One type or two or more types of different units may be used. )
It is preferable that it is a photoresponsive dimerization type | mold polymer | macromolecule represented by these, its hydrolyzate, or the condensate of a hydrolyzate.

Moreover, as a preferable form of the photoresponsive molecule represented by the general formula (1) according to the present invention, a photoresponsive dimerization polymer in which Z ² is a single bond is preferable. The trivalent organic group is preferably a skeleton selected from benzene, biphenyl, diphenyl ether, diphenylethane, diphenylmethane, and diphenylamine.

  Examples of the tetravalent ring structure include the following formulas (1.1) to (1.26).

  The photoresponsive dimerization molecule according to the present invention has the following general formula (2):

(In the general formula (2), M ¹ and M ² are each independently of each other, acrylate, polymethyl methacrylate, 2-chloroacrylate, 2-phenyl acrylate, acrylamide optionally substituted with a lower alkyl group. , Methacrylamide, 2-chloroacrylamide, 2-phenylacrylamide, vinyl ether, vinyl ester, styrene derivative, and at least one repeating unit selected from the group consisting of siloxanes,
M ³ is acrylate, polymethyl methacrylate, 2-chloroacrylate, 2-phenyl acrylate, acrylamide, methacrylamide, 2-chloroacrylamide, 2-phenylacrylamide, vinyl ether, vinyl ester which may be N-substituted with lower alkyl. Linear or branched alkyl esters of acrylic acid or methacrylic acid, allyl esters of acrylic acid or methacrylic acid, alkyl vinyl ethers or esters, phenoxynialkyl acrylate or phenoxyalkyl polymethyl methacrylate or hydroxyalkyl acrylate or hydroxyalkyl poly Methyl methacrylate, phenyl alkyl acrylate or phenyl alkyl polymethyl methacrylate, At least one repeating unit selected from the group consisting of acrylonitrile, methacrylonitrile, styrene, 4-methylstyrene and siloxanes;
A ¹ , B ¹ , C ¹ , A ² , B ² and C ² are each independently of each other,
(A) trans-1,4-cyclohexylene group (in this group, one methylene group or two or more methylene groups which are not adjacent to each other are replaced by —O—, —NH— or —S—) May be)
(B) a 1,4-phenylene group (one or more of —CH═ present in this group may be replaced by —N═), and (c) a 1,4-cyclohexenylene group 2,5-thiophenylene group, 2,5-furylene group, 1,4-bicyclo (2.2.2) octylene group, naphthalene-1,4-diyl group, naphthalene-2,6-diyl group, deca Represents a group selected from the group consisting of a hydronaphthalene-2,6-diyl group and a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, the group (a), group (b) or group (C) is each unsubstituted or one or more hydrogen atoms may be substituted with a fluorine atom, a chlorine atom, a cyano group, a methyl group or a methoxy group,
S ¹ and S ² are each independently a linear or branched alkylene group (— (CH ₂ ) _r —) or — (CH ₂ ) _r substituted with at least one fluorine atom, chlorine atom or cyano group. —L— (CH ₂ ) _s — (wherein L is a single bond or —O—, —COO—, —OOC—, —NR ¹ —, —NR ¹ —CO—, —CO—NR ¹ —, —NR ¹ —COO—, —OCO—NR ¹ —, —NR ¹ —CO—NR ¹ —, —CH═CH— or —C≡C—, wherein R ¹ is a hydrogen atom or lower alkyl And r and s are integers from 1 to 20 under the condition r + s ≦ 24,
D ¹ and D ² each independently represent —O—, —NR ² —, or the following formulas (d) to (f):
(D) trans-1,4-cyclohexylene group (in this group, one methylene group or two or more methylene groups which are not adjacent to each other are replaced by —O—, —NH— or —S—). May be)
(E) 1,4-phenylene group (one or more of —CH═ present in this group may be replaced by —N═), and (f) 1,4-cyclohexenylene group 2,5-thiophenylene group, 2,5-furylene group, 1,4-bicyclo (2.2.2) octylene group, naphthalene-1,4-diyl group, naphthalene-2,6-diyl group, deca A group selected from the group consisting of a hydronaphthalene-2,6-diyl group and a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, the group (d), group (e) or group (F) means that each is unsubstituted or one or more hydrogen atoms may be substituted by a fluorine atom, a chlorine atom, a cyano group, a methyl group or a methoxy group, wherein R ² is hydrogen An atom or a lower alkyl group,
X ¹ , X ² , Y ¹ and Y ² are each independently of one another substituted with a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, or optionally a fluorine atom, and a CH ₂ group or a plurality of non-adjacent CH ₂ groups Means an alkyl group having 1 to 12 carbon atoms which may be optionally replaced with -O-, -COO-, -OOC- and / or -CH = CH-,
Z ^1a , Z ^1b , Z ^2a and Z ^2b are each independently a single bond, — (CH ₂ ) t—, —O—, —CO—, —CO—O—, —O—OC—, — NR ⁴ −, —CO—NR ⁴ —, —NR ⁴ —CO—, — (CH ₂ ) _u —O—, —O— (CH ₂ ) _u —, — (CH ₂ ) _u —NR ⁴ — or — NR ⁴ — (CH ₂ ) _u —, wherein R ⁴ represents a hydrogen atom or a lower alkyl group; t represents an integer of 1 to 4; u is an integer of 1 to 3;
p ¹ , p ² , q ¹ and q ² are each independently 0 or 1,
R ^1a and R ^2a each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a nitro group, a linear or branched alkyl group having 1 to 20 carbon atoms, an alkoxy group, an alkyl group, COO—, alkyl-CO—NR ³ or alkyl-OCO group, wherein R ³ represents a hydrogen atom or a lower alkyl group, and one or more hydrogen atoms of the alkyl group or the alkoxy group are fluorine May be substituted with an atom, a chlorine atom, a cyano group or a nitro group, and the CH ₂ group or a plurality of non-adjacent CH ₂ groups of the alkyl group or the alkoxy group may be —O—, —CH═CH— or —C≡. C- may be substituted,
n ¹ , n ² and n ³ are mole fractions of comonomer where 0 <n ¹ ≦ 1, 0 ≦ n ² <1 and 0 ≦ n ³ ≦ 0.5)
It is preferable that it is a photoresponsive dimerization type | mold polymer represented by these.

  The photoresponsive dimerization type molecule represented by the general formula (1) according to the present invention has the following general formula (3):

(In the general formula (3), X is 6 to 12, Y is 0 to 2, and R ^{1 to} R ⁴ are each independently a hydrogen atom or an alkoxy group having 1 to 5 carbon atoms. And R ³⁰ is a group represented by the formula (2-a) or the formula (2-b):

R ³¹ in the formula (2-a) is a polymerizable group, an alkoxy group having 1 to 10 carbon atoms, a cyano group, or a fluorinated alkyl group having 1 to 12 carbon atoms, and j is 0 It is an integer of 6 or less. It is more preferable that the polymer is a photoresponsive dimerization polymer represented by
The alkyl group and alkoxy group according to the present invention are preferably linear, cyclic or branched, and more preferably linear or branched. Furthermore, examples of the “alkyl group” according to the present invention include methyl group, ethyl group, propyl group, butyl group, isopropyl group, isobutyl group, t-butyl group, 3-pentyl group, isopentyl group, neopentyl group, pentyl. Group, hexyl group, heptyl group, octyl group and the like. In the present specification, examples of alkyl groups are common and are appropriately selected from the above examples depending on the number of carbon atoms of each alkyl group.
Examples of the “alkoxy group” according to the present invention are preferably groups in which an oxygen atom is directly bonded to the alkyl group. For example, methoxy group, ethoxy group, propoxy group (n-propoxy group, i-propoxy group) , Butoxy group, pentyloxy group, and octyloxy group are more preferable. In addition, in this specification, the example of an alkoxy group is common and is suitably selected from the said illustration according to the number of carbon atoms of each alkoxy group.

  The photoresponsive dimerization type molecule according to the present invention is preferably a photoresponsive dimerization type polymer obtained by polymerizing a compound represented by the following general formula (4) and / or general formula (5). .

(Wherein R ²⁰¹ and R ²⁰² each independently represents a linear or branched alkyl group having 1 to 30 carbon atoms, a hydrogen atom or a polymerizable functional group containing a fluorine atom, Two or more —CH ₂ — groups may be —O—, —S—, —NH—, —N (CH ₃ ) —, —CO—, —, as oxygen or sulfur atoms are not directly bonded to each other. CO—O—, —O—CO—, —O—CO—O—, —S—CO—, —CO—S—, —O—SO ₂ —, —SO ₂ —O—, —CH═CH—. , —C≡C—, a cyclopropylene group, or —Si (CH ₃ ) ₂ —, and one or more hydrogen atoms of the alkyl group may be a fluorine atom, a chlorine atom, a bromine atom, or a CN group. Or may have a polymerizable group, and the alkyl group is The alkyl group may contain one or more aromatic or aliphatic rings, which may contain one or more heteroatoms, These rings may be optionally substituted with an alkyl group, an alkoxy group or a halogen,
Z ²⁰¹ and Z ²⁰² are each independently —O—, —S—, —CO—, —CO—O—, —O—CO—, —O—CO—O—, —CO—N (R ^a ) —. , —N (R ^a ) —CO—, —OCH ₂ —, —CH ₂ O—, —SCH ₂ —, —CH ₂ S—, —CF ₂ O—, —OCF ₂ —, —CF ₂ S—, _{-SCF 2 -, - CH 2 CH} 2 -, - CF 2 CH 2 -, - CH 2 CF 2 -, - CF 2 CF 2 -, - CH = CH -, - CF = CH -, - CH = CF- , —CF═CF—, —C≡C—, —CH═CH—CO—O—, —O—CO—CH═CH— or a single bond, —CO—N (R ^a ) — or —N R ^{a in} (R ^a ) —CO— represents ^a hydrogen atom or ^a linear or branched alkyl group having 1 to 4 carbon atoms,
A ²⁰¹ and A ²⁰² each independently represent a phenylene group, a cyclohexylene group, a dioxolanediyl group, a cyclohexenylene group, a bicyclo [2.2.2] octylene group, a piperidinediyl group, a naphthalenediyl group, a decahydronaphthalenediyl group, Represents a cyclic group selected from a tetrahydronaphthalenediyl group or an indanediyl group, wherein the phenylene group, naphthalenediyl group, tetrahydronaphthalenediyl group, or indanediyl group has one or more —CH═ groups in the ring. May be replaced by a nitrogen atom, the cyclohexylene group, dioxolanediyl group, cyclohexenylene group, bicyclo [2.2.2] octylene group, piperidinediyl group, decahydronaphthalenediyl group, tetrahydronaphthalenediyl group, or Indandiyl group -CH 2 that is not one or two adjacent inner _- group, may be replaced by -O- and / or -S-, one or more of the hydrogen atoms of the cyclic group, fluorine An atom, a chlorine atom, a bromine atom, a CN group, a NO ₂ group, or an alkyl group having 1 to 7 carbon atoms in which one or more hydrogen atoms may be replaced by a fluorine atom or a chlorine atom, May be substituted with an alkoxy group, an alkylcarbonyl group or an alkoxycarbonyl group,
n ₂₀₁ and n ₂₀₂ each independently represent an integer of 1 to 3,
P ²⁰¹ and P ²⁰² each independently represent a photoalignable group such as cinnamoyl, coumarin, benzylidenephthaldiimide, chalcone, azobenzene, stilbene, P ²⁰¹ is a monovalent group, and P ²⁰² is a divalent group.

In the present invention, in the compound represented by the general formula (4) or the general formula (5), it is preferable that at least one end has a polymerizable functional group, that is, R in the general formula (5). It is preferable that at least one of ²⁰¹ or R ²⁰² is a polymerizable functional group.
More preferable compounds include compounds of the general formula (6) having a cinnamoyl group, the general formula (7) having a coumarin group, and the general formula (8) having a benzylidenephthaldiimide group.

In general formulas (6), (7), and (8), R ²⁰¹ , R ²⁰² , A ²⁰¹ , A ²⁰² , Z ²⁰¹ , Z ²⁰² , n _201, and n ₂₀₂ are defined by formulas (4) and (5). The same as in
R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ , R ²⁰⁶ and R ²⁰⁷ are each independently a halogen atom (F, Cl, Br, I), methyl group, methoxy group, —CF ₃ , —OCF ₃ , carboxy group, sulfo group, Represents a nitro group, an amino group, or a hydroxy group,
n ²⁰³ represents an integer of 0 to 4, n ²⁰⁴ represents an integer of 0 to 3, n ²⁰⁵ represents an integer of 0 to 1, n ²⁰⁶ represents an integer of 0 to 4, and n ²⁰⁷ represents 0 to 5 Represents an integer.

In the present invention, the photoresponsive decomposition type polymer in which the polymer chain is cleaved in response to light is preferably produced by condensation of tetracarboxylic dianhydride and a diamine compound.
Examples of the tetracarboxylic dianhydride include the following formulas (A-1) to (A-43):

Is mentioned. Among these compounds, the formula (A-14), the formula (A-15), the formula (A-16), the formula (A-17), the formula (A-20), the formula (A-21), Formula (A-28), Formula (A-29), Formula (A-30), or Formula (A-31) is preferable, and Formula (A-14) and Formula (A-21) are particularly preferable.

  Examples of the diamine compound include the following formulas (III-1) to (VIII-17).

(In the above formula (VIII-12), two of R ^{1 to} R ¹⁰ are primary amino groups, and the rest are hydrogen atoms or monovalent organic groups other than primary amino groups, which may be the same or different. Is also good.)

で挙げられる化合物を用いることが好ましい。

It is preferable to use the compound mentioned by these.

The diamine compound having a cinnamic acid skeleton represented by the above formulas (VIII-14) to (VIII-17) can also be dimerized in response to light, so that a photoresponsive dimerized polymer is used. Can also be preferably used.
The weight-average molecular weight of the photoresponsive decomposition type polymer according to the present invention is preferably 3000 to 300,000, more preferably 5000 to 100,000, still more preferably 10,000 to 50,000, and 10,000 to 30,000. It is particularly preferred.
In the photoresponsive decomposition type polymer, the light used for cleaving the molecular chain is preferably 200 to 400 nm, more preferably 200 to 280 nm, and further preferably 240 to 280 nm. preferable.

The other photoresponsive isomerization type molecule is produced by synthesizing a tetracarboxylic dianhydride and a diamine compound, and at least one of the tetracarboxylic dianhydride compound and the diamine has a diazo bond. A polymer comprising
Examples of the tetracarboxylic dianhydride having a diazo bond include compounds represented by the following formula (1-8).

また、ジアゾ結合を備えているジアミン化合物としては、以下の式（Ｉ−１）〜（Ｉ−７）：

Examples of the diamine compound having a diazo bond include the following formulas (I-1) to (I-7):

で表される化合物が挙げられる。

The compound represented by these is mentioned.

Therefore, as a preferable form of the photoresponsive isomerization polymer according to the present invention, when formulas (I-1) to (I-7) are selected as diamine compounds having a diazo bond, tetracarboxylic acid is used. It is preferable that it is a compound represented by Formula (1-8) and Formula (A-1)-(A-43) as a dianhydride. On the other hand, as a preferable form of the photoresponsive isomerization polymer according to the present invention, when formula (1-8) is selected as a tetracarboxylic dianhydride having a diazo bond, a formula (1 Compounds represented by formulas (I-1) to (I-7) and formulas (III-1) to (VIII-11) are preferred.
In the photoresponsive isomerization type polymer, the light used when isomerizing in response to light and orienting substantially perpendicular to the polarization axis is preferably 200 to 500 nm, and preferably 300 to 500 nm. It is more preferable that the thickness is 300 to 400 nm.

The weight average molecular weight of the photoresponsive isomerization type polymer according to the present invention is preferably 10,000 to 800,000, more preferably 10,000 to 400,000, still more preferably 50,000 to 400,000, and 50,000 to 300,000. It is particularly preferred that
The said weight average molecular weight (Mw) is obtained as a result of the GPC (gel permeation chromatography, Gel Permeation Chromatography) measurement.

The photo-alignment layer according to the present invention is preferably formed from a photo-responsive liquid crystal aligning agent. The photoresponsive liquid crystal aligning agent includes a solvent component and a photoalignable component, and the yellowness (YIS) is preferably 0.001 <YIS <500, and more preferably 0.005 <YIS <300. Preferably, 0.008 <YIS <150. Therefore, the photoresponsive liquid crystal aligning agent according to the present invention is preferably a solution.
As a result, the alignment regulating force of the alignment film can be made large, the definition of the liquid crystal display element is increased, the disorder of the liquid crystal alignment near the boundary region is reduced, or the alignment state of the liquid crystal molecules is made highly uniform. This is because the display quality can be improved.

Here, the yellowness (YIS) of the photoresponsive liquid crystal aligning agent is set to 0.001 <YIS <500, or the yellowness (YI) of the photoalignment layer as a liquid crystal display element is in a specific range (for example, Setting the yellowness of the substrate on which the photo-alignment layer is formed to 0.001 <YI <100) is a photo-alignment property that induces an alignment regulating force on the liquid crystal in response to light contained in the photo-responsive liquid crystal aligning agent. This means that the π-electron conjugation length of the molecule is increased, and the structure is similar to the rigidity of the whole molecule or the mesogenic structure of the liquid crystal molecule. This can increase the affinity of the liquid crystal and increase the alignment regulating force on the liquid crystal molecules. Thereby, in a liquid crystal display element, the alignment defect of a liquid crystal can be reduced and the uniformity of the alignment of the thickness direction of a liquid crystalline compound can be improved. In any case, by increasing the alignment regulating force, the alignment disorder of the liquid crystal can be reduced and a high-definition liquid crystal display element can be obtained.
The yellowness (YIS) of the photoresponsive alignment material solution is calculated by the following measurement method. The photoresponsive alignment material is dissolved in a solvent so as to be a 0.2 or 3.5 wt% solution. As the solution, NMP / 2-butoxyethanol = 1/1 is used. If the photoresponsive alignment material has poor solubility and it is difficult to obtain a uniform solution, a minimum amount of a highly soluble solvent may be added. The solution was put in a transparent cell having an optical path length of 1 mm or 10 mm, and the yellowness was calculated according to JIS 7373 (former JIS K7105) using a spectrophotometer (V-560 manufactured by JASCO). When the measured value obtained is proportional to the concentration and the optical path length, the yellowness YIS is calculated in terms of measurement using a cell having a photoresponsive alignment material solution concentration of 0.2% by weight and an optical path length of 1 mm. .

  The solvent component according to the present invention is not particularly limited as long as it can dissolve the photoresponsive molecule, and can be appropriately selected depending on the properties of the photoresponsive molecule to be used. Solvents to be dissolved include water, lactones such as γ-butyrolactone; ketones such as cyclopentanone, cyclohexanone, MEK and MIBK; esters such as propylene glycol monomethyl ether acetate, NMP (N-methyl-2-pyrrolidone) ). In addition, as a solvent for improving the coating property to the substrate, alcohol ethers such as 2-methoxyethanol, 2-butoxyethanol (butyl cellosolve) and carbitol (diethylene glycol monoethyl ether); It may be added to the solvent.

The concentration of the photoresponsive molecule in the photoresponsive liquid crystal aligning agent according to the present invention is preferably 0.1 to 10% by mass, more preferably 0.2 to 10% by mass, and 0.5 to 10 mass% is further more preferable, and 0.5-7 mass% is still more preferable.
When the photoresponsive molecule is in the range of 0.1 to 10% by mass, it is preferable from the viewpoint of easiness of dissolution, easiness of filtration of the solution, stability of the solution, and surface uniformity of the coating film after drying. .

When the photoresponsive liquid crystal aligning agent according to the present invention is applied to the substrate by screen printing, the photoresponsive liquid crystal agent is preferably adjusted so that the viscosity of the photoresponsive liquid crystal agent is 20 to 50 mPa · s. In the case of forming a film on a substrate by an inkjet method, it is preferable to adjust the solution viscosity to be 3 to 15 mPa · s for the purpose of forming good droplets and preventing clogging of the nozzle head. The tension is preferably adjusted to 20 to 50 N / m, and the boiling point of the solvent is preferably in the range of 150 to 220 ° C.
In addition, the photoresponsive liquid crystal aligning agent according to the present invention preferably further includes an ultraviolet absorber that absorbs ultraviolet rays of 320 nm or less, preferably 280 nm or less, more preferably 250 nm or less if necessary.

When the photoresponsive alignment agent according to the present invention contains an ultraviolet absorber, the photoresponsive molecule which is a material having a high yellow index is used for the alignment treatment because the light absorption band for alignment is biased to the visible light region. The liquid crystal element can be protected from ultraviolet rays without affecting the ultraviolet treatment process.
The ultraviolet absorber according to the present invention is not particularly limited, whether it is an organic ultraviolet absorber or an inorganic ultraviolet absorber, but is organic from the viewpoint of the film thickness and transparency of the alignment film. A UV absorber is preferred. Examples of the ultraviolet absorber include benzoate series, benzotriazole series, benzophenone series, cyclic imino ester series, hindered amine series, and combinations thereof.

There is no particular limitation as long as it absorbs ultraviolet rays having a shorter wavelength than the absorbance specified in the present invention. Among these, benzoate type is more preferable.
Examples of the benzoate-based, benzophenone-based UV absorber, benzotriazole-based UV absorber, and acrylonitrile-based UV absorber include 3,5-di-tert-butyl-4-hydroxybenzoic acid 2,4-di-tert-butylphenyl. 2- [2′-hydroxy-5 ′-(methacryloyloxymethyl) phenyl] -2H-benzotriazole, 2- [2′-hydroxy-5 ′-(methacryloyloxyethyl) phenyl] -2H-benzotriazole, 2, -[2'-hydroxy-5 '-(methacryloyloxypropyl) phenyl] -2H-benzotriazole, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2', 4,4'-tetrahydroxy Benzophenone, 2,4-di-tert-butyl-6- (5-chlorobenzotriazole- 2-yl) phenol, 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (5-chloro (2H) -benzotriazol-2-yl ) -4-Methyl-6- (tert-butyl) phenol, 2,2'-methylenebis (4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) Examples of the cyclic iminoester-based ultraviolet absorber include 2,2 ′-(1,4-phenylene) bis (4H-3,1-benzoxazinon-4-one), 2-methyl-3. , 1-benzoxazin-4-one, 2-butyl-3,1-benzoxazin-4-one, 2-phenyl-3,1-benzoxazin-4-one, etc. The present invention is not limited to, et al.

These ultraviolet absorbers may be used alone or in combination of two or more ultraviolet absorbers. When a plurality of types are combined, ultraviolet rays having different wavelengths can be absorbed simultaneously, so that the ultraviolet absorption effect can be further improved.
The ultraviolet absorbent according to the present invention is preferably contained in the photoresponsive liquid crystal aligning agent in an amount of 0 to 5.0% by mass, more preferably 0.01 to 1.0% by mass, More preferably, it is contained in an amount of 0.1 to 1.0% by mass.
When the ultraviolet absorber is contained in the photoresponsive liquid crystal aligning agent in an amount of 0.01 to 5.0% by mass, the liquid crystal display element can be efficiently protected from ultraviolet rays when the photoalignment film is used.

The photoresponsive liquid crystal aligning agent according to the present invention is preferably a solution containing the above-described photoresponsive molecule. The photoresponsive molecule contains at least one polymer selected from the group consisting of an azo derivative as a photoisomerization type, a polyimide derivative as a photolysis type and a cinnamic acid derivative as a dimerization type, and the organic solvent. It is more preferable.
The photoresponsive liquid crystal aligning agent of the present invention is preferably applied by an offset printing method, a spin coating method, a roll coater method or an ink jet printing method, respectively. Here, as the substrate, for example, a glass such as float glass or soda glass; a transparent substrate made of a plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, or poly (alicyclic olefin) can be used. As the transparent conductive film provided on one surface of the (first) substrate, a NESA film made of tin oxide (SnO ₂ ), an ITO film made of indium oxide-tin oxide (In ₂ O ₃ —SnO ₂ ), or the like is used. Also good. Furthermore, in order to obtain a patterned transparent conductive film, for example, a method of forming a pattern by photo-etching after forming a transparent conductive film without a pattern, or a mask having a desired pattern when forming a transparent conductive film is used. It can be employed in methods. When applying the photoresponsive liquid crystal aligning agent, in order to further improve the adhesion between the substrate surface and the transparent conductive film and the coating film, the substrate surface is a known method such as a functional silane compound or a functional titanium compound. The surface treatment may be performed in advance.

After applying the photoresponsive liquid crystal aligning agent, pre-baking may be performed if necessary, and the pre-baking temperature in that case is preferably 30 to 200 ° C. The prebake time is preferably 0.25 to 10 minutes. Then, it is preferable to perform a baking process for the purpose of removing a solvent completely and removing an unreacted component etc. as needed. The firing temperature at this time is preferably 80 to 300 ° C. The firing time is preferably 5 to 200 minutes. The film thickness thus formed is preferably 0.001 to 1 μm.
In addition, when the polymer contained in the photoresponsive liquid crystal aligning agent of the present invention is an imidized polymer having a polyamic acid or an imide ring structure and an amic acid structure, it is further heated after the coating film is formed. It is good also as a more imidized coating film by making a dehydration ring-closing reaction proceed.

In the method for producing a liquid crystal display device according to the present invention, it is preferable to irradiate a coating film containing a photoresponsive molecule (if necessary, an ultraviolet absorber) formed on the substrate (step (2)). Moreover, you may perform the said process (2) after the below-mentioned process (3). As light with which the coating film is irradiated, ultraviolet light or visible light containing light having a wavelength of 150 to 800 nm can be used, and ultraviolet light containing light having a wavelength of 200 to 400 nm is preferable. Moreover, the said wavelength is suitably adjusted with the kind of photoresponsive molecule to be used. Specifically, in the case of the photoresponsive molecule for the decomposition type photo-alignment film, 254 nm, in the case of the photo-responsive molecule for the dimerization type photo-alignment film, 313 nm, in the case of the photo-responsive molecule for the isomerization type photo-alignment film Use 365 nm.
As a light source for the irradiation light, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, or the like can be used. The ultraviolet rays in the preferable wavelength region can be obtained by means of using a light source in combination with, for example, a filter or a diffraction grating. The irradiation dose of light is preferably 100 J / ^{m 2} or more 100,000J / ^{m 2} or less.

(Polymerization process of polymerizable liquid crystal composition)
The polymerization operation of the polymerizable liquid crystal composition of the present invention is generally performed by light irradiation such as ultraviolet rays or heating after removing the solvent in the polymerizable liquid crystal composition by heating or the like. When the polymerization is performed by light irradiation, specifically, it is preferable to irradiate ultraviolet light having a wavelength of 390 nm or less, and it is most preferable to irradiate light having a wavelength of 250 to 370 nm. However, when the photo-alignment film and the polymerizable liquid crystal composition cause decomposition or the like due to ultraviolet light having a wavelength of 390 nm or less, it may be preferable to perform a polymerization treatment with ultraviolet light having a wavelength of 390 nm or more.
This light is preferably diffused light and unpolarized light so as not to disturb the orientation of the photoalignable group already obtained.

On the other hand, the polymerization by heating is preferably performed at a temperature at which the polymerizable liquid crystal composition exhibits a liquid crystal phase or at a temperature lower than that. In particular, when a thermal polymerization initiator that releases radicals by heating is used, the cleavage temperature is the above. It is preferable to use the one in the temperature range. When the thermal polymerization initiator and the photopolymerization initiator are used in combination, the polymerization temperature and the polymerization temperature are set so that the polymerization speeds of both the photo-alignment film and the polymerizable liquid crystal film are not significantly different from the above temperature range limitation. It is preferred to select each initiator. Although the heating temperature depends on the transition temperature from the liquid crystal phase to the isotropic phase of the polymerizable liquid crystal composition, the heating temperature is preferably lower than the temperature at which inhomogeneous polymerization is induced by heat. However, if the glass transition point of the base material made of an organic material is exceeded, thermal deformation of the base material becomes remarkable, and therefore, the glass transition point of the room temperature to the base material is preferable. For example, when a polymeric group is a (meth) acryloyl group, it is preferable to carry out at a temperature lower than 90 degreeC.
In order to stabilize the solvent resistance and heat resistance of the obtained optical anisotropic body, the optical anisotropic body can be heat-treated. In this case, it is preferable to heat above the glass transition point of the prepolymerizable liquid crystal film. Usually, heating within a range not exceeding the glass transition point of a base material made of an organic material is preferable.

When the optical anisotropic body of the present invention is used, for example, as a raw material for a polarizing film or an alignment film, or for printing ink, paint, protective film, etc., the polymerizable liquid crystal composition used in the present invention has its Depending on the purpose, metals, metal complexes, dyes, pigments, fluorescent materials, phosphorescent materials, surfactants, leveling agents, thixotropic agents, gelling agents, polysaccharides, ultraviolet absorbers, infrared absorbers, antioxidants, ions An exchange resin, a metal oxide such as titanium oxide, or the like may be added.
The optical anisotropic body in the present invention refers to an optical compensation sheet, a retardation film, a pattern retarder, a lenticular lens, and the like. Among these, the optical compensation sheet or the retardation film has various forms such as an A plate, a negative C plate, a positive C plate, an O plate, and a hybrid depending on the orientation state.
Further, these optical anisotropic bodies can be realized by only one layer depending on the purpose, but can also be formed in multiple layers depending on the purpose. In order to widen the application range, it may be preferable to make a multilayer. For example, in a circularly polarizing plate comprising a quarter-wave plate, a half-wave plate and a polarizing plate, a quarter-wave plate and a half-wave are formed on the resin substrate of this patent by a polymer of a polymerizable liquid crystal composition. For example, a plate is prepared and laminated to form a circularly polarizing plate.

  The optical anisotropic body of the present invention can be peeled off from the substrate and used alone as an optical anisotropic body, or it can be used as it is without being peeled off from the substrate. In particular, since it is difficult to contaminate other members, it is useful when used as a laminated substrate or by being attached to another substrate. In some cases, optical anisotropic bodies can be laminated over several layers. In that case, the above process may be repeated a plurality of times, and an optically anisotropic laminate can be formed.

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

(Preparation Example 1 of Photoresponsive Liquid Crystal Alignment Material Solution)
3,3 ′-[(2,2′-disulfo-1,1′-biphenyl-4,4′-diyl) bis (azo)] bis [6-hydroxybenzoic acid] as a coating liquid for photoresponsive liquid crystal alignment material A mixture of 1 part by weight of tetrasodium (common name CI Mordant Yellow 26), 42 parts by weight of 2-butoxyethanol, 42 parts by weight of carbitol (diethylene glycol monoethyl ether), and 15 parts by weight of water at room temperature The mixture was stirred for 10 minutes and filtered through a 0.45 μm membrane filter to prepare a uniform solution (photoresponsive liquid crystal alignment material solution 1).

(Preparation example 2 of photoresponsive liquid crystal alignment material solution)
As a photoresponsive liquid crystal alignment material coating solution, a mixture of 3.5 parts by weight of a cinnamic acid-based photoalignable polymer having the following structure, 68 parts by weight of 2-methoxyethanol, and 28.5 parts by weight of isopropyl alcohol was stirred at room temperature for 10 minutes. The solution was filtered through a 0.45 μm membrane filter to prepare a uniform solution (photoresponsive liquid crystal alignment material solution 2).

(Adjustment of polymerizable liquid crystal composition)
For the compounds shown below, formula (A-1) to formula (A-8), formula (B-1) to formula (B-13), and formula (C-1), cyclopentanone as an organic solvent, Methyl isobutyl ketone (MIBK), propylene glycol monomethyl ether acetate (PGMEA), toluene, polymerization inhibitor methylhydroquinone (MEHQ), polymerization initiator Irgacure 907 (Irg.907, manufactured by BASF), Lucillin TPO (TPO, manufactured by BASF) ) To prepare a polymerizable liquid crystal composition.

(Preparation of polymerizable liquid crystal composition (1))
As shown in Table 1, 11.95 parts by mass of the compound represented by formula (A-3), 11.95 parts by mass of the compound represented by formula (A-4), and represented by formula (B-1) To a total of 31.05 parts by mass of 1.55 parts by mass of the compound, 3.88 parts by mass of the compound represented by the formula (B-6), and 3.88 parts by mass of the compound represented by the formula (B-7) In contrast, 1.75 parts by mass of a polymerization initiator (Irg.907), 0.04 parts by mass of a polymerization inhibitor (MEHQ), 49 parts by weight of MIBK as an organic solvent, and 16 parts by weight of PGMEA, and a stirring device having a stirring propeller. The resulting mixture was stirred for 1 hour under conditions of a stirring speed of 500 rpm and a solution temperature of 60 ° C., and then filtered through a 0.2 μm membrane filter to obtain a polymerizable liquid crystal composition (1).

(Preparation of polymerizable liquid crystal compositions (2) to (23))
Similarly to the preparation of the polymerizable liquid crystal composition (1) of the present invention, the formula (A-1) to the formula (A-8), the formula (B-1) to the formula (B-13), the formula (C-1) ), A polymerization initiator, and a polymerization inhibitor, respectively, except that each compound selected from the ratios shown in Tables 1 to 3 was changed to the ratios shown in Tables 1 to 3 under the same conditions as the preparation of the polymerizable liquid crystal composition (1). (2) to (16) and comparative polymerizable liquid crystal compositions (17) to (23) were obtained.

(Evaluation of optical anisotropic bodies)
About the optical anisotropic body obtained by the method described in the following Example, the characteristic was evaluated by the following method.

(Transparency test)
Three points were measured using a turbidimeter NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd., and the average value of haze was evaluated.
◎: Less than 0.1 ○: 0.1 or more and less than 0.2 Δ: 0.2 or more and less than 0.5 ×: 0.5 or more

(Orientation appearance test)
A: There are no defects visually, and there are no defects even when observed with a polarizing microscope.
B: Although there is no defect visually, there is a non-oriented part by observation with a polarizing microscope.
C: Although there is no defect visually, there is a non-oriented portion as a whole by observation with a polarizing microscope.
D: Some defects are visually observed, and non-oriented portions are present as a whole in the polarization microscope observation.
E: Unevenness occurs in the entire photo-alignment film by visual inspection.

(Adhesion test)
In order to evaluate the adhesive force of the substrate / photo-alignment layer / polymerizable liquid crystal layer of the obtained optical anisotropic body (retardation film and pattern retarder), the obtained optical anisotropic body has a grid pattern with a cutter on 1 cm square. A cut was made into 2 mm square grids. Next, cellophane tape was applied to the grid area and pulled up in the vertical direction to count the number of remaining grid lines. The above operation was repeated 5 times to obtain an average value.

(Pattern resolution test)
In order to evaluate the pattern resolution of the pattern retarder, the contrast of the pattern retarder was evaluated. A pattern retarder contains multiple regions with different orientation directions, and the contrast decreases when the alignment failure of the polymerizable liquid crystal is large or the alignment failure at the boundary region between adjacent regions is large. It is evaluated that the image quality is high.
Between a polarizer and an analyzer of an optical measuring device (OMS-DI4RD, manufactured by Chuo Seiki Co., Ltd.) equipped with a white light source, a polarizer (incident side polarizing plate), an analyzer (outgoing side polarizing plate), and a detector. A device to be measured (a retardation film, a pattern retarder, and a lenticular land described in the following examples) is arranged, and the amount of transmitted light is detected by a detector while rotating the polarizer and the analyzer, and the contrast The (contrast) = (parallel Nicol luminance) / (cross Nicol luminance) was measured by the following equation.

(Example 1)
The photoresponsive liquid crystal alignment material solution 1 was coated on a 125 μm-thick polymethyl methacrylate (PMMA) film (manufactured by Mitsubishi Rayon Co., Ltd., Acryprene HBA002P) with a spin coater after applying a corona treatment to the surface. For 10 minutes. The dry film thickness at this time was 90 nm. When the formed coating film was visually observed, it was confirmed that a smooth film was formed.
Next, using a polarized light irradiation device equipped with an ultra-high pressure mercury lamp, a wavelength cut filter, a band pass filter, and a polarizing filter, ultraviolet light (wavelength 365 nm) is linearly polarized (illuminance: 20 mW / cm ² ) to the substrate. The film was irradiated for 10 seconds from the vertical direction to obtain a photo-alignment film. The irradiation amount was 200 mJ / cm ² . At this time, ultraviolet light having a polarization direction different by 90 ° was irradiated using a photomask so as to be in stripes and adjacent to each other, and was irradiated twice in total.

The polymerizable liquid crystal composition (1) is applied by spin coating on the PMMA substrate having the photo-alignment layer formed as described above, dried at 70 ° C. for 2 minutes, and then a high-pressure mercury lamp is used. Then, ultraviolet light was irradiated at an intensity of 40 mW / cm ² for 25 seconds to obtain a pattern retarder having a phase difference that functions as a quarter-wave plate in a stripe shape with an orientation direction different by 90 °. The pattern retarder had no defects and good orientation. In particular, there was little alignment disorder in the boundary region between patterns with different alignment directions, and the pattern retarder became high definition. The characteristics of the obtained pattern retarder were evaluated by a transparency test, an orientation appearance test, an adhesion test, and a pattern resolution test. The results are shown in Table 4.

(Example 2)
The photoresponsive liquid crystal alignment material solution 1 was subjected to corona treatment on a 125 μm-thick PMMA film as a substrate, coated with a spin coater, and dried at 70 ° C. for 10 minutes. The dry film thickness at this time was 90 nm. When the formed coating film was visually observed, it was confirmed that a smooth film was formed.
Next, a linearly polarized light (illuminance: 20 mW / cm ² ) of ultraviolet light (wavelength 365 nm) is obtained using a polarized light irradiation device including an ultra-high pressure mercury lamp, a wavelength cut filter, a band pass filter, and a polarizing filter. The material was irradiated from the vertical direction for 10 seconds to obtain a photo-alignment film. The irradiation amount was 200 mJ / cm ² .
A polymerizable liquid crystal composition (2) is applied onto the obtained photo-alignment film with a spin coater, dried at 70 ° C. for 2 minutes, and then irradiated with 1 J / cm ² of ultraviolet light in a nitrogen atmosphere to form a uniform A plate. A functional retardation film (2) was obtained. The retardation was 270 nm. The properties of the obtained retardation film (2) were evaluated by a transparency test, an orientation appearance test, and an adhesion test. The results are shown in Table 4.

(Example 3)
The polymerizable liquid crystal composition (3) is used in place of the polymerizable liquid crystal composition (1), the photoresponsive liquid crystal alignment material solution 2 is used in place of the photoresponsive liquid crystal alignment material solution 1, and other conditions are used. In the same manner as in Example 1, a pattern retarder (3) was obtained. The characteristics were evaluated by a transparency test, an orientation appearance test, and an adhesion test. The results are shown in Table 4.

Example 4
The photoresponsive alignment material solution 1 was subjected to corona treatment on a 125 μm-thick PMMA film as a substrate, then applied with a spin coater, and dried at 70 ° C. for 10 minutes. The dry film thickness at this time was 90 nm. When the formed coating film was visually observed, it was confirmed that a smooth film was formed.
Next, a linearly polarized light (illuminance: 20 mW / cm ² ) of ultraviolet light (wavelength 365 nm) is obtained using a polarized light irradiation device including an ultra-high pressure mercury lamp, a wavelength cut filter, a band pass filter, and a polarizing filter. The material was irradiated from the vertical direction for 10 seconds to obtain a photo-alignment film. The irradiation amount was 200 mJ / cm ² . Similarly, a photo-alignment layer was formed on a transparent resin mold for lenticular lenses.
The polymerizable liquid crystal composition (4) was applied on the PMMA substrate on which the photo-alignment layer obtained as described above was formed by a spin coating method while being heated to 55 ° C. A transparent resin mold subjected to orientation treatment was pressure-bonded onto the obtained coating film and cooled to room temperature. At that time, the substrate was disposed so that the alignment direction of the alignment-treated substrate and the alignment direction of the mold were parallel. Thereafter, using a high-pressure mercury lamp, ultraviolet light was irradiated for 25 seconds at an intensity of 40 mW / cm ² to obtain a lenticular lens (4). The lenticular lens (4) had no defects and good orientation. The characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 4.

(Example 5)
A PMMA film with a thickness of 125 μm as a substrate is coated with a polymerizable liquid crystal composition (5) with a spin coater, dried at 70 ° C. for 2 minutes, and then irradiated uniformly with 1 J / cm ² of ultraviolet light in a nitrogen atmosphere. A positive C plate type retardation film (5) was obtained. The characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 4.

(Example 6)
The polymerizable liquid crystal composition (6) is used instead of the polymerizable liquid crystal composition (2), and a silane coupling material (manufactured by JNC: DMOAP) is applied as an alignment film by a spin coat method and baked at 70 ° C. for 1 hour. Thus, a positive C plate type retardation film (6) was obtained in the same manner as in Example 2 except for the above. The characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 4.

(Example 7)
Using the polymerizable liquid crystal composition (7) in place of the polymerizable liquid crystal composition (2), a negative C plate type retardation film (7) was obtained in the same manner as in Example 2 except for the other conditions. The characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 4.

(Example 8)
The polymerizable liquid crystal composition (8) was used in place of the polymerizable liquid crystal composition (2), and the other conditions were the same as in Example 2, and the director of the polymerizable liquid crystal composition on the PMMA substrate side was substantially on the substrate surface. A hybrid type retardation film (8) was obtained which was parallel and substantially perpendicular to the interface on the air interface side. The characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 4.

Example 9
A polymerizable liquid crystal composition (9) was used instead of the polymerizable liquid crystal composition (1), and a pattern retarder (9) was obtained in the same manner as in Example 1 except for the other conditions. The characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 4.

(Example 10)
The polymerizable liquid crystal composition (10) is used in place of the polymerizable liquid crystal composition (1), and the photoresponsive liquid crystal alignment material solution 2 is used in place of the photoresponsive liquid crystal alignment material solution 1. A pattern retarder (10) was obtained in the same manner as in Example 1. The characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 4.

(Example 11)
A polymerizable liquid crystal composition (11) was used instead of the polymerizable liquid crystal composition (2), and an A plate type retardation film (11) was obtained in the same manner as in Example 2 except for the other conditions. The characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 4.

Example 12
The polymerizable liquid crystal composition (12) is used in place of the polymerizable liquid crystal composition (2), the photoresponsive liquid crystal alignment material solution 2 is used in place of the photoresponsive liquid crystal alignment material solution 1, and other conditions are used. In the same manner as in No. 2, an A-plate type retardation film (12) was obtained. The characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 4.

(Example 13)
Instead of the polymerizable liquid crystal composition (2), the polymerizable liquid crystal composition (13) was used, respectively, and an A plate type retardation film (13) was obtained in the same manner as in Example 2 except for the above. The characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 4.

(Example 14)
A polymerizable liquid crystal composition (14) was used instead of the polymerizable liquid crystal composition (5), and a positive C plate type retardation film (14) was obtained in the same manner as in Example 5 except for the other conditions. The characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 4.

(Example 15)
A polymerizable liquid crystal composition (15) was used in place of the polymerizable liquid crystal composition (1), and a pattern retarder (15) was obtained in the same manner as in Example 1 except for the other conditions. The characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 4.

(Example 16)
A lenticular lens (16) was obtained in the same manner as in Example 4 except that the polymerizable liquid crystal composition (16) was used in place of the polymerizable liquid crystal composition (4). The characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 4.

(Example 17)
Using the polymerizable liquid crystal composition (17) instead of the polymerizable liquid crystal composition (6), a positive C plate type retardation film (17) was obtained in the same manner as in Example 6 except for the above. The characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 4.

(Example 18)
A polymerizable liquid crystal composition (18) was used instead of the polymerizable liquid crystal composition (6), and a positive C plate type retardation film (18) was obtained in the same manner as in Example 6 except for the other conditions. The characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 4.

(Example 19)
Using the polymerizable liquid crystal composition (19) in place of the polymerizable liquid crystal composition (6), a positive C plate type retardation film (18) was obtained in the same manner as in Example 6 except for the above. The characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 4.

(Example 20)
The polymerizable liquid crystal composition (20) is used in place of the polymerizable liquid crystal composition (1), and the photoresponsive liquid crystal alignment material solution 2 is used in place of the photoresponsive liquid crystal alignment material solution 1. The pattern retarder (20) was obtained in the same manner as in Example 1. The characteristics were evaluated by a transparency test, an orientation appearance test, and an adhesion test. The results are shown in Table 4.

(Comparative Example 1)
A polymerizable liquid crystal composition (21) was used in place of the polymerizable liquid crystal composition (1), and a pattern retarder (C1) was obtained in the same manner as in Example 1 except for the other conditions. The characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 4.

(Comparative Example 2)
A lenticular lens (C2) was obtained in the same manner as in Example 4 except that the polymerizable liquid crystal composition (22) was used instead of the polymerizable liquid crystal composition (4). The characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 4.

(Comparative Example 3)
A polymerizable liquid crystal composition (23) was used instead of the polymerizable liquid crystal composition (6), and a positive C plate type retardation film (C3) was obtained in the same manner as in Example 6 except for the other conditions. The characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 4.

(Comparative Example 4)
Using the polymerizable liquid crystal composition (24) instead of the polymerizable liquid crystal composition (7), a negative C plate type retardation film (C4) was obtained in the same manner as in Example 7 except for the other conditions. The characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 4.

(Comparative Example 5)
A polymerizable liquid crystal composition (25) was used in place of the polymerizable liquid crystal composition (9), and a pattern retarder (C5) was obtained in the same manner as in Example 9 except for the other conditions. The characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 4.

(Comparative Example 6)
A polymerizable liquid crystal composition (26) was used instead of the polymerizable liquid crystal composition (10), and a pattern retarder (C6) was obtained in the same manner as in Example 10 except for the other conditions. The characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 4.

(Comparative Example 7)
A polymerizable liquid crystal composition (27) was used instead of the polymerizable liquid crystal composition (11), and an A plate type retardation film (C7) was obtained in the same manner as in Example 11 except for the other conditions. The characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 4.

(Example 21)
A pattern retarder (21) was obtained in the same manner as in Example 1 except that a polycarbonate (PC) film having a thickness of 100 μm (Carbo Glass C110C, manufactured by Asahi Glass Co., Ltd.) was used as the substrate instead of the PMMA film. The pattern retarder had no defects and good orientation. In particular, there was little alignment disorder in the boundary region between patterns with different alignment directions, and the pattern retarder became high definition. The characteristics of the obtained pattern retarder were evaluated in the same manner as in Example 1. The results are shown in Table 5.

(Example 22)
A retardation film (22) was obtained in the same manner as in Example 2 except that a polycarbonate (PC) film having a thickness of 100 μm (Carbo Glass C110C, manufactured by Asahi Glass Co., Ltd.) was used instead of the PMMA film. The retardation was 270 nm. The characteristics of the obtained pattern retarder were evaluated in the same manner as in Example 1. The results are shown in Table 5.

(Example 23)
A pattern retarder (23) was obtained in the same manner as in Example 3 except that a polycarbonate (PC) film having a thickness of 100 μm (Carbo Glass C110C, manufactured by Asahi Glass Co., Ltd.) was used as the substrate instead of the PMMA film. The characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 5.

(Example 24)
A lenticular lens (24) was obtained in the same manner as in Example 4 except that a polycarbonate (PC) film having a thickness of 100 μm (Carbo Glass C110C, manufactured by Asahi Glass Co., Ltd.) was used instead of the PMMA film. The lenticular lens (20) had no defects and good orientation. The characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 5.

(Example 25)
As a substrate, a 100 μm thick polycarbonate (PC) film (Carbo Glass C110C, manufactured by Asahi Glass Co., Ltd.) was used instead of the PMMA film, and the other conditions were the same as in Example 5, and a positive C plate type retardation film (25) Got. The characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 5.

(Example 26)
As a substrate, a polycarbonate (PC) film having a thickness of 100 μm (Carbo Glass C110C, manufactured by Asahi Glass Co., Ltd.) was used instead of the PMMA film, and the other conditions were the same as in Example 6, and a positive C plate type retardation film (26) Got. The characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 5.

(Example 27)
As a substrate, a polycarbonate (PC) film having a thickness of 100 μm (Carbo Glass C110C, manufactured by Asahi Glass Co., Ltd.) was used instead of the PMMA film, and the other conditions were the same as in Example 7, and a negative C plate type retardation film (27) Got. The characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 5.

(Example 28)
As a substrate, a polycarbonate (PC) film (Carbo Glass C110C, manufactured by Asahi Glass Co., Ltd.) having a thickness of 100 μm is used instead of the PMMA film, and the director of the polymerizable liquid crystal composition is used on the PC substrate side in the same manner as in Example 8. A hybrid type retardation film (28) was obtained which was substantially parallel to the substrate surface and substantially perpendicular to the interface on the air interface side. The characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 5.

(Example 29)
A pattern retarder (29) was obtained in the same manner as in Example 9 except that a polycarbonate (PC) film having a thickness of 100 μm (Carbo Glass C110C, manufactured by Asahi Glass Co., Ltd.) was used as the substrate instead of the PMMA film. The characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 5.

(Example 30)
A pattern retarder (30) was obtained in the same manner as in Example 10 except that a polycarbonate (PC) film having a thickness of 100 μm (Carbo Glass C110C, manufactured by Asahi Glass Co., Ltd.) was used as the substrate instead of the PMMA film. The characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 5.

(Example 31)
A 100 μm-thick polycarbonate (PC) film (Carbo Glass C110C, manufactured by Asahi Glass Co., Ltd.) was used as the substrate instead of the PMMA film, and the A plate type retardation film (31) was prepared in the same manner as in Example 11 except for the above. Obtained. The characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 5.

(Example 32)
A 100 μm-thick polycarbonate (PC) film (Carbo Glass C110C, manufactured by Asahi Glass Co., Ltd.) was used as the substrate instead of the PMMA film, and the A plate type retardation film (32) was prepared in the same manner as in Example 12 except for that. Obtained. The characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 5.

(Example 33)
A retardation film (33) was obtained in the same manner as in Example 13 except that a polycarbonate (PC) film having a thickness of 100 μm (Carbo Glass C110C, manufactured by Asahi Glass Co., Ltd.) was used instead of the PMMA film. The characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 5.

(Example 34)
As a substrate, a polycarbonate (PC) film having a thickness of 100 μm (Carbo Glass C110C, manufactured by Asahi Glass Co., Ltd.) was used instead of the PMMA film, and the other conditions were the same as in Example 14, and a positive C plate type retardation film (34) Got. The characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 5.

(Example 35)
A positive C plate type retardation film (35) was used in the same manner as in Example 15 except that a polycarbonate (PC) film (Carbo Glass C110C, manufactured by Asahi Glass Co., Ltd.) having a thickness of 100 μm was used instead of the PMMA film. Obtained. The characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 5.

(Example 36)
A lenticular lens (36) was obtained in the same manner as in Example 16 except that a polycarbonate (PC) film having a thickness of 100 μm (Carbo Glass C110C, manufactured by Asahi Glass Co., Ltd.) was used as the substrate instead of the PMMA film. The characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 5.

(Example 37)
As a substrate, a polycarbonate (PC) film having a thickness of 100 μm (Carbo Glass C110C, manufactured by Asahi Glass Co., Ltd.) was used instead of the PMMA film, and the other conditions were the same as in Example 17, and a positive C plate type retardation film (37) Got. The characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 5.

(Example 38)
As a substrate, a polycarbonate (PC) film having a thickness of 100 μm (Carbo Glass C110C, manufactured by Asahi Glass Co., Ltd.) is used instead of the PMMA film, and the other conditions are the same as in Example 18, and a positive C plate type retardation film (38) Got. The characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 5.

(Example 39)
As a substrate, a polycarbonate (PC) film having a thickness of 100 μm (Carbo Glass C110C, manufactured by Asahi Glass Co., Ltd.) was used instead of the PMMA film, and the other conditions were the same as in Example 19, and a positive C plate type retardation film (39) Got. The characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 5.

(Example 40)
A pattern retarder (40) was obtained in the same manner as in Example 20 except that a polycarbonate (PC) film having a thickness of 100 μm (Carbo Glass C110C, manufactured by Asahi Glass Co., Ltd.) was used as the substrate instead of the PMMA film. The pattern retarder had no defects and good orientation. In particular, there was little alignment disorder in the boundary region between patterns with different alignment directions, and the pattern retarder became high definition. The characteristics of the obtained pattern retarder were evaluated in the same manner as in Example 1. The results are shown in Table 5.

(Comparative Example 8)
A pattern retarder (C8) was obtained in the same manner as in Comparative Example 1 except that a polycarbonate (PC) film having a thickness of 100 μm (Carbo Glass C110C, manufactured by Asahi Glass Co., Ltd.) was used as the substrate instead of the PMMA film. The characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 5.

(Comparative Example 9)
A lenticular lens (C9) was obtained in the same manner as in Comparative Example 2 except that a polycarbonate (PC) film having a thickness of 100 μm (Carbo Glass C110C, manufactured by Asahi Glass Co., Ltd.) was used as the substrate instead of the PMMA film. The characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 5.

(Comparative Example 10)
A polycarbonate (PC) film (Carbo Glass C110C, manufactured by Asahi Glass Co., Ltd.) having a thickness of 100 μm is used as the substrate instead of the PMMA film, and other conditions are the same as in Comparative Example 3, and a positive C plate type retardation film (C10) Got. The characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 5.

(Comparative Example 11)
A 100 μm thick polycarbonate (PC) film (Carbo Glass C110C, manufactured by Asahi Glass Co., Ltd.) was used as the substrate instead of the PMMA film, and the other conditions were the same as in Comparative Example 4, and a negative C plate type retardation film (C11) Got. The characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 5.

(Comparative Example 12)
A pattern retarder (C12) was obtained in the same manner as in Comparative Example 5 except that a polycarbonate (PC) film having a thickness of 100 μm (Carbo Glass C110C, manufactured by Asahi Glass Co., Ltd.) was used as the substrate instead of the PMMA film. The characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 5.

(Comparative Example 13)
A pattern retarder (C13) was obtained in the same manner as in Comparative Example 6 except that a polycarbonate (PC) film having a thickness of 100 μm (Carbo Glass C110C, manufactured by Asahi Glass Co., Ltd.) was used instead of the PMMA film. The characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 5.

(Comparative Example 14)
A retardation film (C14) was obtained in the same manner as in Comparative Example 7 except that a polycarbonate (PC) film having a thickness of 100 μm (Carbo Glass C110C, manufactured by Asahi Glass Co., Ltd.) was used instead of the PMMA film. The characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 5.

Comparing the examples of Table 4 and Table 5 with the comparative examples, the examples are superior in any of the evaluation items of transparency, orientation, adhesion, and contrast, and this is the case for both the PMMA substrate and the PC substrate. It shows that the composition design based on the structural parameter S proposed in the invention is effective.

Claims (6)

A polymer obtained by polymerizing a polymerizable liquid crystal composition, and an optical anisotropic body including a polymethyl methacrylate resin substrate or a polycarbonate resin substrate, wherein the polymerizable liquid crystal composition has at least one polymerizable functional group And S = LR / (LR + LM)
(LM represents the number of atoms from the end of the ring structure at one end of the mesogenic group of the liquid crystal compound to the end of the ring structure at the other end, provided that a hydrogen atom and a substituent atom added in the lateral direction of the ring structure. LR represents the number of atoms from the molecular end of the liquid crystal compound to the atom bonded to the closest mesogen base end, and the portion from the molecular end to the atom bonded to the closest mesogenic base end If there is a plurality, the sum of all of them is included, and the substituents of the mesogenic group are also included, but the number of hydrogen atoms is not included.)
An optical anisotropic body containing 85% by mass or more of one or more liquid crystal compounds satisfying 0.22 <S <0.6 in the molecular structure parameter S represented by: The optical anisotropic body according to claim 1, wherein the liquid crystal compound is a rod-like liquid crystal compound. The liquid crystal compound has the general formula (II)

(In the formula, P ² represents a polymerizable functional group, S ¹ represents an alkylene group having 1 to 18 carbon atoms (the hydrogen atom in the alkylene group is one or more halogen atoms, CN group, or polymerized). It may be substituted by an alkyl group having 1 to 8 carbon atoms having a sexual functional groups, independently of each one CH ₂ group or not adjoining two or more CH ₂ groups existing in the groups to each other And X ¹ is —O—, —S—, —OCH ₂ —, —CH ₂ O, which may be replaced by —O—, —COO—, —OCO— or —OCO—O—. -, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -SCH _{2- , -CH 2 S -, - CF} 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - CH = H-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH ₂ —COO—, —CH ₂ CH ₂ —OCO—, —COO—CH ₂ —, —OCO—CH ₂ —, —CH ₂ —COO—, —CH ₂ —OCO—, —CH═CH—, — N═N—, —CH═N—N═CH—, —CF═CF—, —C≡C— or a single bond (where P ² —S ¹ and S ¹ —X ¹ are —O -O-, -O-NH-, -S-S- and -O-S- groups are not included.), Q1 represents 0 or 1, MG represents a mesogenic group, R ² represents a hydrogen atom, Represents a halogen atom, a cyano group, or a linear or branched alkyl group having 1 to 12 carbon atoms, and the alkyl group is linear; May be branched, the alkyl group is one -CH ₂ - or nonadjacent two or more -CH ₂ - are each independently -O -, - S -, - CO -, - COO -, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-COO-, -CH = CH —OCO—, —COO—CH═CH—, —OCO—CH═CH—, —CH═CH—, —CF═CF— or —C≡C— may be substituted, or R ² may be Formula (II-a)

(Wherein P ³ represents a polymerizable functional group, S ² represents the same as defined in S ¹ , and X ² represents the same as defined in X ¹ ( Provided that P ³ —S ² and S ² —X ² do not include —O—O—, —O—NH—, —S—S— and —O—S— groups.), Q ² is 0 Or 1).
The mesogenic group represented by MG has the general formula (II-b)

(In the formula, B1, B2 and B3 are each independently 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group, 1, 3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene-2,6-diyl group, pyridine- 2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group-, 1,2,3,4-tetrahydronaphthalene-2,6- Diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4,4a, 9,10a-octahydrofetal Nantes -2,7-diyl group, 1,4-naphthylene group, benzo [1,2-b: 4,5-b ′] dithiophene-2,6-diyl group, benzo [1,2-b: 4, 5-b ′] diselenophen-2,6-diyl group, [1] benzothieno [3,2-b] thiophene-2,7-diyl group, [1] benzoselenopheno [3,2-b] selenophene-2 , 7-diyl group, or fluorene-2,7-diyl group, and one or more F, Cl, CF ₃ , OCF ₃ , CN groups, alkyl groups having 1 to 8 carbon atoms, carbon atoms as substituents An alkoxy group having 1 to 8 carbon atoms, an alkanoyl group having 1 to 8 carbon atoms, an alkanoyloxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, Alkenyloxy group having 2 to 8 carbon atoms, 2 carbon atoms -8 alkenoyl group, alkenoyloxy group having 2 to 8 carbon atoms, and / or formula (II-c)

(Wherein P ⁴ represents a reactive functional group,
S ³ represents the same as defined in S ¹ , and X ³ represents —O—, —COO—, —OCO—, —OCH ₂ —, —CH ₂ O—, —CH ₂ CH _{2. OCO -, - COOCH 2 CH 2} -, - OCOCH 2 CH 2 -, or a single bond, ^{q 3} is 0 or 1, ^{q 4} represents 0 or 1. (However, P ⁴ —S ³ and S ³ —X ³ do not include —O—O—, —O—NH—, —S—S—, and —O—S— groups). Z1 and Z2 are each independently —COO—, —OCO—, —CH ₂ CH ₂ —, —OCH ₂ —, —CH ₂ O—, —CH═CH—, —C≡C. -, - CH = CHCOO -, - OCOCH = CH -, - CH 2 CH 2 COO -, - CH 2 CH 2 OCO -, - COOCH 2 CH 2 -, - OCOCH 2 CH 2 -, - C = N-, —N═C—, —CONH—, —NHCO—, —C (CF ₃ ) ₂ —, an alkyl group having 2 to 10 carbon atoms which may have a halogen atom, or a single bond; In the case where a plurality of B1 and Z1 are present, they may be the same or different. The optically anisotropic body according to claim 1 or 2, which is a compound represented by the formula: The optical anisotropic body according to claim 1, wherein the liquid crystal compound is a discotic liquid crystal compound. At least one polymerized discotic liquid crystal compound having a benzene derivative, a triphenylene derivative, a truxene derivative, a phthalocyanine derivative or a cyclohexane derivative as a core at the center of the molecule, a linear alkyl group, a linear alkoxy group, or a substituted benzoyloxy group The optically anisotropic body according to claim 4, wherein is a structure in which the side chain is radially substituted as its side chain. A polymerizable liquid crystal composition used for the optical anisotropic body according to claim 1.