JP2012163945A - Composition for liquid crystal alignment layer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition for liquid crystal alignment layer which has liquid crystal alignment properties to enable control of alignment with a small ultraviolet irradiation amount, can obtain any pretilt angle and has excellent light stability; a liquid crystal alignment layer, using the composition, which is photo-alignable and free from corrosion by a solvent or the like; and a liquid crystal display element and an optical anisotropic body such as optical compensation film using the liquid crystal alignment layer.SOLUTION: Provided is a composition for liquid crystal alignment layer including (a) a polymer having a photochemically isomerizable site and (b) a polymer having a photochemically crosslinkable site, in which the (a) and (b) have different structures from each other. There is also provided a liquid crystal alignment layer using the composition.

Description

  The present invention relates to a material for aligning liquid crystal, and is useful for a material for manufacturing a liquid crystal alignment layer in a liquid crystal display element or an optical anisotropic film used for optical compensation of a liquid crystal display element. It relates to an optical anisotropic body.

The alignment layer for aligning the liquid crystal is important for maintaining the order of the liquid crystal alignment and expressing the optical properties based on the refractive index anisotropy of the liquid crystal molecules, and is essential for constituting the liquid crystal display element. It is a constituent member. In the liquid crystal display element, the alignment of the liquid crystal has a great influence on the display characteristics, and various methods have been studied. The liquid crystal display element can be roughly classified into a vertical alignment type and a horizontal alignment type.
A liquid crystal display device using a vertical alignment type liquid crystal layer (sometimes referred to as a VA mode liquid crystal display device) is widely used for a display because of excellent display characteristics such as high contrast. However, the viewing angle characteristics are not always sufficient, and various methods have been studied for improvement. As a method for improving the viewing angle characteristics, a multi-domain vertical alignment method (MVA method) in which a plurality of liquid crystal domains having different alignment directions are formed in one pixel (introducing an alignment division structure) has become common. In the MVA method, in order to form an alignment division structure, it is necessary to control the tilt alignment of liquid crystal molecules. As a method for this, a slit (opening) or a rib (projection structure) provided in an electrode is used. The installation method is used. However, when slits and ribs are used, unlike the case where the pretilt direction is defined by the alignment film used in the conventional TN mode, the slits and ribs are linear, so that the alignment regulating force on the liquid crystal molecules is within the pixel. This causes a problem that the response speed is distributed. Furthermore, since the light transmittance of the area where the slits and ribs are provided is lowered, there is also a problem that the display luminance is lowered.

As another method for controlling the tilt alignment, a monomer that can be polymerized by light or heat is mixed in the liquid crystal, and the tilt direction of the liquid crystal molecule is memorized by polymerizing the monomer while the liquid crystal molecule is tilted by applying a voltage. A polymer oriented alignment (PSA) technique has been disclosed (see Patent Document 1). This method can solve the problem of response speed distribution and light transmittance reduction in the method of providing slits and ribs. However, this method has problems such as changes in characteristics due to mixing of monomers into the liquid crystal material, difficulty in process control, and adverse effects of residual monomers.
In order to avoid these problems, it is preferable to form an alignment division structure in the VA mode liquid crystal display device by controlling the tilt alignment with the alignment film. There is a rubbing method as a method of imparting a tilt alignment control force to the vertical alignment film. An alignment film made of polyimide or the like is applied on a substrate, and the alignment film is rubbed with a rubbing cloth to determine the alignment direction and pretilt. Corner control is performed. However, it is difficult to form a precise alignment division structure by the rubbing method, and there is a problem of generation of static electricity and impurity components due to friction.

On the other hand, an IPS mode liquid crystal display device is an example of a liquid crystal display device using a horizontal alignment type liquid crystal layer. IPS mode liquid crystal display devices have a small viewing angle dependency such as contrast and color, and are widely used for displays because of their excellent display characteristics. In the IPS mode, in order to reduce the viewing angle dependency and color reproducibility in black display, it is required that the electrode surface has a low pretilt angle of 1 degree or less. Even when the horizontal alignment is achieved, a rubbing method is used as a general alignment method. However, when the horizontal alignment process is performed by the rubbing process of the polyimide alignment film, the pretilt angle given to the liquid crystal molecules exceeds 1 degree, and there is a problem that the display characteristics deteriorate.
Because of these problems, in both the vertical alignment type and the horizontal alignment type, control of the alignment direction and the pretilt angle using the alignment film is important for improving display characteristics. As a method for controlling the tilt alignment by the alignment film, a photo-alignment method is known in addition to the rubbing process (see Patent Document 2). In the photo-alignment method, a precise alignment division structure can be easily formed by changing the light irradiation pattern, and compared to the rubbing process, the alignment film can be processed in a non-contact manner. Impurities are unlikely to occur. However, the photo-alignment film must have various characteristics such as reliability that can control the tilt alignment of liquid crystals with a small amount of light irradiation and can be used in active matrix driving. There has been a need for a photo-alignment layer.

  By the way, as a method for improving the viewing angle characteristics in the liquid crystal display element, by using an optical compensation film, a retardation film, etc., the phase difference between the front direction and the oblique direction of the liquid crystal display element is adjusted, so that the light is transmitted to the liquid crystal display element. A method of eliminating the phase difference between the front direction and the diagonal direction that occurs when passing through the door is also widely used. In such applications, stretched films are widely used as optical compensation films. However, stretched films are limited in the direction of stretching, and it is difficult to precisely control the phase difference. Therefore, with the widespread use of liquid crystal televisions and the like, it is not possible to meet the demand for sophisticated performance. Yes.

  On the other hand, as an optical compensation film, an optically anisotropic film composed of a polymerized optical anisotropic body is used after orienting a polymerizable liquid crystal composition, but the film has a precise retardation. This technique is superior to stretched films in that it can be controlled. In general, an optically anisotropic body obtained by polymerizing a polymerizable liquid crystal composition can be obtained by curing in a state where the polymerizable liquid crystal is aligned. In this case, a liquid crystal alignment layer is used to align the polymerizable liquid crystal. Is done. Conventionally, a liquid crystal alignment layer produced by a rubbing method has been used as the liquid crystal alignment layer. However, in the rubbing method, fine scratches on the surface of the polymer film due to mechanical rubbing may cause liquid crystal alignment defects, and uneven alignment may occur due to non-uniform pressing pressure during rubbing. Further, there is a problem that the definition of the liquid crystal display element is lowered, and further there is a problem that impurities due to friction are generated.

In recent years, the demand for viewing angle control has become more sophisticated, and the optical compensation film is required to have a wider wavelength band and higher viewing angle stability. For example, an optical anisotropy film having various characteristics such as a laminate of a quarter-wave plate and a half-wave plate, or a laminate of an A-plate and a C-plate. Film is in demand on the market. However, in order to produce a laminate having such a complicated structure, it is necessary to repeat the process of curing the polymerizable liquid crystal layer after forming the liquid crystal alignment layer. In this case, application of the liquid crystal alignment layer and rubbing must be repeated, and such a manufacturing method has a problem that the apparatus becomes very large and cannot be continuously formed.
As a method for solving such problems, the photo-alignment method is expected to be put to practical use because it is excellent in mass productivity and can be applied to a large substrate.

As a material that can be a photo-alignment layer for the liquid crystal display element or optical anisotropic body, a compound having a photochemically isomerizable site such as an azobenzene derivative (see Patent Document 3) is known. An important characteristic for using the photo-alignment layer is how much anisotropy of the irradiation dose is used for re-orientation (hereinafter referred to as sensitivity). Light using a compound having an azo group The alignment layer is excellent in sensitivity and exhibits liquid crystal alignment ability at a low irradiation amount of about 500 mJ / cm ² .
However, since the photo-alignment layer using a compound having an azo group is a low-molecular compound, problems such as being washed away in a cleaning process or being attacked by an adhesive member such as a sealing agent occur in the liquid crystal cell manufacturing stage. There was a thing. In the production of an optical anisotropic body, when producing a laminated optical anisotropic body that repeats the lamination of a photo-alignment layer and a polymerizable liquid crystal layer, a polymerizable liquid crystal composition solution is applied on the photo-alignment layer. The process and the step of applying the composition solution for the photo-alignment film on the polymerizable liquid crystal layer, but the already prepared liquid crystal alignment layer and the polymerizable liquid crystal layer are affected by the solvent used in the coating solution. In some cases, the film peels off, or uniform optical characteristics cannot be obtained.

Further, as materials that can be used as a photo-alignment layer, compounds having a photochemically crosslinkable site such as cinnamic acid derivatives, coumarin derivatives, chalcone derivatives, and compounds that cause anisotropic photolysis such as polyimide derivatives are known. (See Patent Documents 4, 5 and 6).
However, the photo-alignment layer composed of a compound having a photochemically crosslinkable site such as cinnamic acid derivatives is inferior to a compound having an azo group in terms of sensitivity, and has strong anisotropy during photo-alignment. Light irradiation was required, and the apparatus became large and practical application was not easy.
On the other hand, polymer compounds having an azo group as a skeleton having a photochemically isomerizable moiety and a cinnamate skeleton as a skeleton having a photochemically crosslinkable moiety have already been disclosed (patents). Reference 7). However, in the cited document, the polymer compound is used as an optical nonlinear polymer, and there is no suggestion about using it as an optical anisotropic body. It was not clear whether it had.

  As described above, development of a material for a photo-alignment layer that has high sensitivity and is not eroded by a solvent or the like has been demanded.

JP 2003-149647 A Japanese Patent No. 2682771 Japanese Patent Laid-Open No. 5-232473 JP-A-6-287453 Japanese Patent Laid-Open No. 10-310613 Special table 2002-517605 gazette Japanese Patent Publication No. 6-509889

  The object of the present invention is to provide a liquid crystal orientation capable of controlling the orientation with a small amount of ultraviolet irradiation, without solving or exacerbating the above-mentioned problems, and can obtain an arbitrary pretilt angle, Provided is a liquid crystal alignment layer having excellent stability and a liquid crystal alignment layer capable of photo-alignment using the composition that is not eroded by a solvent and the like, and further, a liquid crystal display element and optical compensation using the liquid crystal alignment layer The object is to provide an optical anisotropic body such as a film.

As a result of intensive investigations to solve the above problems, the present inventors have found a composition for a liquid crystal alignment layer capable of photoalignment that can solve the above problems using a polymer having two characteristic structures. Completed.
The present invention includes (a) a polymer having a photochemically isomerizable moiety and (b) a polymer having a photochemically crosslinkable moiety, and (a) and (b) are not the same structure. Provided is a liquid crystal alignment layer capable of photo-alignment using the liquid crystal alignment layer material and the alignment layer material composition.

  The liquid crystal alignment layer composition of the present invention can be produced with a small amount of optically anisotropic light, can obtain an arbitrary pretilt angle, has excellent light stability, a solvent, etc. Therefore, it is useful for controlling the alignment of liquid crystal in a liquid crystal display element and for optical compensation using an optical anisotropic body.

It is sectional drawing which shows an example of the optical anisotropic body using the composition for alignment layers of the liquid crystal of this invention. It is sectional drawing which shows an example of the optical anisotropic body using the composition for alignment layers of the liquid crystal of this invention. It is sectional drawing which shows an example of the optical anisotropic body using the composition for alignment layers of the liquid crystal of this invention. It is a figure which shows the definition of a pretilt angle.

1a, 1b, 1c, 1d, 1e Optically anisotropic layers 2a, 2b, 2c, 2d Liquid crystal alignment layers 3a, 3b, 3c capable of photo-alignment Substrate 4 Optical axis 5 Orthographic projection of optical axis onto substrate surface 6 Pretilt angle (Θ)

  The composition for an alignment layer of a liquid crystal used in the present invention comprises (a) a polymer having a photochemically isomerizable moiety, and (b) a polymer having a photochemically crosslinkable moiety, and (a) And (b) are not the same structure. Here, (a) may or may not be photochemically crosslinked at the isomerizable site, but may be photochemically crosslinked at the isomerizable site. What does not react is preferable. The composition for alignment layer of liquid crystal used in the present invention may contain at least one additional monomer or polymer, or may contain two or more polymers having photochemically isomerizable sites, Two or more polymers having a crosslinkable site may be contained. In the composition for a liquid crystal alignment layer used in the present invention, polymers having photochemically isomerizable sites are represented by the following general formulas (Ia-1) to (Id-2), (If-1) to (Ii -3) and (Im-1) to (Ip-2)

（式中、Maはポリマーのモノマー単位を表し、S_a及びS_aaは各々同一であっても異なっていても良いスペーサー単位を表し、Pは光化学的に異性化可能であり、かつ光化学的に架橋されない部位を表し、Vは側鎖末端を表す。）、

(In the formula, Ma represents a monomer unit of the polymer, S _a and S _aa each represents a spacer unit which may be the same or different, P is photochemically isomerizable, and photochemically Represents a site not cross-linked, V represents a side chain end)

（式中、S_a、S_aa、S_aaaは各々同一であっても異なっていても良いスペーサー単位、Dは光化学的に架橋可能な部位を表し、Ma、P及びV、は一般式（Ia-1）と同じ意味を表す。）、

(In the formula, S _a , S _{aa and} S _aaa are the same or different spacer units, D represents a photochemically crosslinkable site, and Ma, P and V represent general formulas (Ia -1) means the same)),

（式中、S_a、S_aa、S_aaa、D、Ma、P及びVは一般式（Ib-1）と同じ意味を表す。）、

(In the formula, S _a , S _aa, S _aaa , D, Ma, P and V represent the same meaning as in the general formula (Ib-1)).

（式中、Ma及びMbは各々同一であっても異なっていても良いポリマーのモノマー単位を表し、S_a、S_aa、S_b、S_bbは各々同一であっても異なっていても良いスペーサー単位を表し、Va及びVbは側鎖末端を表し、D及びPは一般式（Ib-1）と同じ意味を表す。）、

(In the formula, Ma and Mb each represent a monomer unit of a polymer which may be the same or different, and S _a , S _aa, S _b and S _bb may be the same or different spacers, respectively. Unit represents, Va and Vb represent side chain ends, and D and P represent the same meaning as in the general formula (Ib-1)).

（式中、M_a及びM_cは、各々同一であっても異なっていても良いポリマーのモノマー単位を表し、S_a及びS_cは各々同一であっても異なっていても良いスペーサー単位を表し、Ｖ_ｃは側鎖末端を表し、Ｐは、一般式（Ia-1）と同じ意味を表す。）、

(In the formula, M _a and M _c each represent a monomer unit of a polymer that may be the same or different, and S _a and S _c each represent a spacer unit that may be the same or different. , V _c represents a side chain end, and P represents the same meaning as in the general formula (Ia-1)).

（式中、M_a及びM_cは、各々同一であっても異なっていても良いポリマーのモノマー単位を表し、S_a、S_aa及びS_cは各々同一であっても異なっていても良いスペーサー単位を表し、Ｖ_ｃは側鎖末端を表し、Ｐ及びＤは、一般式（Ib-1）と同じ意味を表す。）、

(In the formula, M _a and M _c each represents a monomer unit of a polymer which may be the same or different, and S _a , S _aa and S _c may be the same or different, respectively. Represents a unit, V _c represents a side chain end, and P and D represent the same meaning as in the general formula (Ib-1)).

（式中、M_a及びM_cは、各々同一であっても異なっていても良いポリマーのモノマー単位を表し、S_a、S_aa及びS_cは各々同一であっても異なっていても良いスペーサー単位を表し、Ｖ_ｃは側鎖末端を表し、Ｐ及びＤは、一般式（Ib-1）と同じ意味を表す。）、

(In the formula, M _a and M _c each represents a monomer unit of a polymer which may be the same or different, and S _a , S _aa and S _c may be the same or different, respectively. Represents a unit, V _c represents a side chain end, and P and D represent the same meaning as in the general formula (Ib-1)).

（式中、M_a、M_b及びM_cは、各々同一であっても異なっていても良いポリマーのモノマー単位を表し、S_a、S_b及びS_cは各々同一であっても異なっていても良いスペーサー単位を表し、Ｖ_ｃは側鎖末端を表し、Ｐ及びＤは、一般式（Ib-1）と同じ意味を表す。）、

(In the formula, M _a , M _b and M _c each represent a monomer unit of a polymer which may be the same or different, and S _a , S _b and S _c may be the same or different, respectively. Represents a good spacer unit, V _c represents a side chain end, and P and D represent the same meaning as in the general formula (Ib-1)).

（式中、S_aはスペーサー単位、Ma及びPは一般式（Ia-1）と同じ意味を表す。）、

(Wherein, S _a spacer unit, Ma and P have the same meanings as those in formula (Ia-1).),

（式中、S_a、S_aa、D、Ma及びPは一般式（Ib-1）と同じ意味を表す。）、

( _Wherein , S _a , S _aa, D, Ma and P represent the same meaning as in general formula (Ib-1)).

（式中、S_a、S_aa、D、Ma及びPは一般式（Ib-1）と同じ意味を表す。）、

( _Wherein , S _a , S _aa, D, Ma and P represent the same meaning as in general formula (Ib-1)).

（式中、M_a及びM_bは、各々同一であっても異なっていても良いポリマーのモノマー単位を表し、S_a及びS_bは各々同一であっても異なっていても良いスペーサー単位を表し、Ｐ及びＤは、一般式（Ib-1）と同じ意味を表す。）からなる群より選ばれるモノマーの硬化物を含むのが好ましい。
該光化学的に異性化可能な部位を有するポリマーは、
下記一般式(Ia)〜(Id) 、(If)〜(Ii)及び(Im)〜(Ip)

(In the formula, M _a and M _b each represent a monomer unit of a polymer that may be the same or different, and S _a and S _b each represent a spacer unit that may be the same or different. , P and D preferably represent a cured product of a monomer selected from the group consisting of general formula (Ib-1).
The polymer having a photochemically isomerizable moiety is
The following general formulas (Ia) to (Id), (If) to (Ii) and (Im) to (Ip)

（式中、Ma及びMdは各々同一であっても異なっていても良いポリマーのモノマー単位を表し、Mdのモノマー単位は１種類でも２種類以上の異なる単位からなっていても良く、S_a及びS_aaは各々同一であっても異なっていても良いスペーサー単位を表し、Pは光化学的に異性化可能であり、かつ光化学的に架橋されない部位を表し、Vは側鎖末端を表し、x及びwはコポリマーのモル分率を表すものであって、いずれの場合にも0＜ｘ≦１かつ０≦w＜１であり、nは4〜1000000を表す。）、

(In the formula, Ma and Md each represent a monomer unit of a polymer which may be the same or different, and the monomer unit of Md may be composed of one type or two or more different units, and S _a and S _aa represents a spacer unit that may be the same or different, P represents a site that is photochemically isomerizable and not photochemically crosslinked, V represents a side chain end, x and w represents the molar fraction of the copolymer, and in each case 0 <x ≦ 1 and 0 ≦ w <1, and n represents 4 to 1000000).

（式中、S_a、S_aa、S_aaaは各々同一であっても異なっていても良いスペーサー単位、Dは光化学的に架橋可能な部位を表し、Ma、Md、P、V、x、w及びnは一般式（Ia）と同じ意味を表す。）、

(In the formula, S _a , S _{aa and} S _aaa are the same or different spacer units, D represents a photochemically crosslinkable site, and Ma, Md, P, V, x, w And n represent the same meaning as in the general formula (Ia).

（式中、S_a、S_aa、S_aaa、D、Ma、Md、P、V、x、w及びnは一般式（Ib）と同じ意味を表す。）、

( _Wherein , S _a , S _aa, S _aaa , D, Ma, Md, P, V, x, w and n represent the same meaning as in general formula (Ib)).

（式中、Ma、Mb及びMdは各々同一であっても異なっていても良いポリマーのモノマー単位を表し、Ma、Mb及びMdの並びは式と同一であっても異なっていても良く、Mdのモノマー単位は１種類でも２種類以上の異なる単位からなっていても良く、S_a、S_aa、S_b、S_bbは各々同一であっても異なっていても良いスペーサー単位を表し、Va及びVbは側鎖末端を表し、x、y及びwはコポリマーのモル分率を表すものであって、いずれの場合にも0＜ｘ＜１かつ０＜ｙ＜１かつ０≦ｗ＜１であり、D、P及びnは一般式（Ib）と同じ意味を表す。）、

(In the formula, Ma, Mb and Md each represent a monomer unit of a polymer which may be the same or different, and the arrangement of Ma, Mb and Md may be the same as or different from the formula. The monomer unit may be composed of one type or two or more different units, and S _a , S _aa, S _b and S _bb each represents a spacer unit which may be the same or different, and Va and Vb represents the end of the side chain, x, y and w represent the mole fraction of the copolymer, and in each case 0 <x <1, 0 <y <1, and 0 ≦ w <1 , D, P and n represent the same meaning as in general formula (Ib)).

（式中、M_a、M_c及びM_dは、各々同一であっても異なっていても良いポリマーのモノマー単位を表し、M_a、M_c及びM_dの並びは式と同一であっても異なっていても良く、M_dのモノマー単位は１種類でも２種類以上の異なる単位からなっていても良く、ｘ、ｚ及びｗは、コポリマーのモル分率を表すものであって、０＜ｘ＜１かつ、０＜ｚ＜１かつ、０≦ｗ＜１を満たし、S_a及びS_cは各々同一であっても異なっていても良いスペーサー単位を表し、Ｖ_ｃは側鎖末端を表し、Ｐ及びｎは、一般式（Ia）と同じ意味を表す。）、

(In the formula, M _a , M _c and M _d each represent a monomer unit of a polymer which may be the same or different, and the arrangement of M _a , M _c and M _d may be the same as the formula The monomer units of M _d may be different from one another or may be composed of two or more different units, and x, z and w represent the mole fraction of the copolymer, and 0 <x <1 and 0 <z <1 and satisfies 0 ≦ w <1, represents the S _a and S _c good spacer unit are each independently selected from a same, V _c represents the side chain end, P and n represent the same meaning as in the general formula (Ia)).

（式中、M_a、M_c及びM_dは、各々同一であっても異なっていても良いポリマーのモノマー単位を表し、M_a、M_c及びM_dの並びは式と同一であっても異なっていても良く、M_dのモノマー単位は１種類でも２種類以上の異なる単位からなっていても良く、ｘ、ｚ及びｗは、コポリマーのモル分率を表すものであって、０＜ｘ＜１かつ、０＜ｚ＜１かつ、０≦ｗ＜１を満たし、S_a、S_aa及びS_cは各々同一であっても異なっていても良いスペーサー単位を表し、Ｖ_ｃは側鎖末端を表し、Ｐ、Ｄ及びｎは、一般式（Ib）と同じ意味を表す。）、

(In the formula, M _a , M _c and M _d each represent a monomer unit of a polymer which may be the same or different, and the arrangement of M _a , M _c and M _d may be the same as the formula The monomer units of M _d may be different from one another or may be composed of two or more different units, and x, z and w represent the mole fraction of the copolymer, and 0 <x <1 and 0 <z <1 and 0 ≦ w <1 are satisfied, S _a , S _aa and S _c each represents a spacer unit which may be the same or different, and V _c represents a side chain terminal P, D and n represent the same meaning as in general formula (Ib)).

（式中、M_a、M_c及びM_dは、各々同一であっても異なっていても良いポリマーのモノマー単位を表し、M_a、M_c及びM_dの並びは式と同一であっても異なっていても良く、M_dのモノマー単位は１種類でも２種類以上の異なる単位からなっていても良く、ｘ、ｚ及びｗは、コポリマーのモル分率を表すものであって、０＜ｘ＜１かつ、０＜ｚ＜１かつ、０≦ｗ＜１を満たし、S_a、S_aa及びS_cは各々同一であっても異なっていても良いスペーサー単位を表し、Ｖ_ｃは側鎖末端を表し、Ｐ、Ｄ及びｎは、一般式（Ib）と同じ意味を表す。）、

(In the formula, M _a , M _c and M _d each represent a monomer unit of a polymer which may be the same or different, and the arrangement of M _a , M _c and M _d may be the same as the formula The monomer units of M _d may be different from one another or may be composed of two or more different units, and x, z and w represent the mole fraction of the copolymer, and 0 <x <1 and 0 <z <1 and 0 ≦ w <1 are satisfied, S _a , S _aa and S _c each represents a spacer unit which may be the same or different, and V _c represents a side chain terminal P, D and n represent the same meaning as in general formula (Ib)).

（式中、M_a、M_b、M_c及びM_dは、各々同一であっても異なっていても良いポリマーのモノマー単位を表し、M_a、M_b、M_c及びM_dの並びは式と同一であっても異なっていても良く、M_dのモノマー単位は１種類でも２種類以上の異なる単位からなっていても良く、ｘ、y、ｚ及びｗは、コポリマーのモル分率を表すものであって、０＜ｘ＜１かつ、０＜ｙ＜１かつ、０＜ｚ＜１かつ、０≦ｗ＜１を満たし、S_a、S_b及びS_cは各々同一であっても異なっていても良いスペーサー単位を表し、Ｖ_ｃは側鎖末端を表し、Ｐ、Ｄ及びｎは、一般式（Ib）と同じ意味を表す。）、

(In the formula, M _a , M _b , M _c and M _d each represent a monomer unit of a polymer which may be the same or different, and the arrangement of M _a , M _b , M _c and M _d is the formula May be the same as or different from each other, the monomer unit of M _d may be composed of one kind or two or more kinds of different units, and x, y, z and w represent the molar fraction of the copolymer. 0 <x <1, 0 <y <1, 0 <z <1, and 0 ≦ w <1, and S _a , S _b and S _c are the same or different represents an spacer unit even though, V _c represents the side chain terminal, P, D and n are. represents the same meaning as in formula (Ib)),

（式中、S_aはスペーサー単位、Ma、Md、P、x、w及びnは一般式（Ia）と同じ意味を表す。）、

(Wherein, S _a spacer unit, Ma, Md, P, x , w and n have the same meanings as those in formula (Ia).),

（式中、S_a、S_aa、D、Ma、Md、P、x、w及びnは一般式（Ib）と同じ意味を表す。）、

(In the formula, S _a , S _aa, D, Ma, Md, P, x, w and n represent the same meaning as in the general formula (Ib)).

（式中、S_a、S_aa、D、Ma、Md、P、x、w及びnは一般式（Ib）と同じ意味を表す。）、

(In the formula, S _a , S _aa, D, Ma, Md, P, x, w and n represent the same meaning as in the general formula (Ib)).

（式中、M_a、M_b及びM_dは、各々同一であっても異なっていても良いポリマーのモノマー単位を表し、M_a、M_b及びM_dの並びは式と同一であっても異なっていても良く、M_dのモノマー単位は１種類でも２種類以上の異なる単位からなっていても良く、ｘ、y及びｗは、コポリマーのモル分率を表すものであって、０＜ｘ＜１かつ、０＜y＜１かつ、０≦ｗ＜１を満たし、S_a及びS_bは各々同一であっても異なっていても良いスペーサー単位を表し、Ｐ、Ｄ及びｎは、一般式（Ib）と同じ意味を表す。）
からなる群より選ばれるポリマーを含むことが好ましい。

(In the formula, M _a , M _b and M _d each represent a monomer unit of a polymer which may be the same or different, and the arrangement of M _a , M _b and M _d may be the same as the formula The monomer units of M _d may be different from one another or may be composed of two or more different units, and x, y and w represent the mole fraction of the copolymer, and 0 <x <1 and 0 <y <1 and satisfies 0 ≦ w <1, represents the S _a and S _b good spacer unit are each independently selected from a same, P, D and n have the general formula (It has the same meaning as (Ib).)
It is preferable to include a polymer selected from the group consisting of:

  In the polymer contained in the photoalignable liquid crystal alignment layer, the compound having a photochemically isomerizable moiety is preferably a compound having an azo group. The polymer having a photochemically isomerizable site is more preferably a homopolymer having an azo group. In the composition for liquid crystal alignment layer used in the present invention, the polymer having a photochemically crosslinkable moiety is represented by the general formula (Ie-1)

（式中、Maはポリマーのモノマー単位を表し、S_a及びS_aaは各々同一であっても異なっていても良いスペーサー単位を表し、Dは光化学的に架橋可能な部位を表し、Vは側鎖末端を表す。）で表されるモノマーの硬化物、一般式(Ij-1)及び一般式(Ij-2)

(In the formula, Ma represents a monomer unit of the polymer, S _a and S _aa each represents a spacer unit which may be the same or different, D represents a photochemically crosslinkable site, and V represents a side. Cured product of monomer represented by general formula (Ij-1) and general formula (Ij-2)

（式中、M_a及びM_cは各々同一であっても異なっていても良いポリマーのモノマー単位を表し、S_a及びS_cは各々同一であっても異なっていても良いスペーサー単位を表し、Ｄは光化学的に架橋可能な部位を表し、Ｖ_ｃは側鎖末端を表す。）で表されるモノマーの硬化物、又は一般式(Iq-1)

(Wherein, M _a and M _c each represent a monomer unit of a polymer that may be the same or different, and S _a and S _c each represent a spacer unit that may be the same or different, D represents a photochemically crosslinkable site, and V _c represents a side chain end.) Or a cured product of the monomer represented by the general formula (Iq-1)

（式中、Maポリマーのモノマー単位を表し、S_aはスペーサー単位を表し、Dは光化学的に架橋可能な部位を表す。）で表されるモノマーの硬化物を含むのが好ましい。

(In the formula, it represents a monomer unit of Ma polymer, Sa represents _a spacer unit, and D represents a photochemically crosslinkable site).

  The polymer having a photochemically crosslinkable moiety has the general formula (Ie)

（式中、Ma及びMdは各々同一であっても異なっていても良いポリマーのモノマー単位を表し、M_dのモノマー単位は１種類でも２種類以上の異なる単位からなっていても良く、S_a及びS_aaは各々同一であっても異なっていても良いスペーサー単位を表し、Dは光化学的に架橋可能な部位を表し、Vは側鎖末端を表し、x及びwはコポリマーのモル分率を表すものであって、いずれの場合にも0＜ｘ≦１かつ０≦w＜１であり、nは4〜1000000を表す。）で表わされるポリマー、一般式(Ij)

(Wherein, Ma and Md each represents a monomer unit may be different even in the same polymer, monomer units M _d may be composed of two or more different units in one, S _a And S _aa each represents a spacer unit, which may be the same or different, D represents a photochemically crosslinkable site, V represents a side chain end, x and w represent the mole fraction of the copolymer. A polymer represented by the general formula (Ij): 0 <x ≦ 1 and 0 ≦ w <1, and n represents 4 to 1000000.

（式中、M_a、M_c及びM_dは各々同一であっても異なっていても良いポリマーのモノマー単位を表し、M_a、M_c及びM_dの並びは式と同一であっても異なっていても良く、M_dのモノマー単位は１種類でも２種類以上の異なる単位からなっていても良く、ｘ、ｚ及びｗは、コポリマーのモル分率を表すものであって、０＜ｘ＜１かつ、０＜ｚ＜１かつ、０≦ｗ＜１を満たし、S_a及びS_cは各々同一であっても異なっていても良いスペーサー単位を表し、Ｄは光化学的に架橋可能な部位を表し、Ｖ_ｃは側鎖末端を表し、nは4〜1000000を表す。）で表されるポリマー、又は一般式(Iq)

(In the formula, M _a , M _c, and M _d each represent a monomer unit of a polymer that may be the same or different, and the arrangement of M _a , M _c, and M _d is the same as or different from the formula The monomer unit of M _d may be composed of one kind or two or more kinds of different units, and x, z and w represent the mole fraction of the copolymer, and 0 <x < 1 and 0 <z <1 and satisfies 0 ≦ w <1, represents the S _a and S _c good spacer unit are each independently selected from a same, D is a photochemically crosslinkable site represents, V _c represents the side chain end, n represents a polymer represented by the representative.) the 4-1,000,000, or the general formula (Iq)

（式中、Ma,及びMdは各々同一であっても異なっていても良いポリマーのモノマー単位を表し、M_dのモノマー単位は１種類でも２種類以上の異なる単位からなっていても良く、S_aはスペーサー単位を表し、Dは光化学的に架橋可能な部位を表し、x及びwはコポリマーのモル分率を表すものであって、いずれの場合にも0＜ｘ≦１かつ０≦w＜１であり、nは4〜1000000を表す。）で示されるポリマーを含むことが好ましい。
また、一般式(Ik−１)

(In the formula, Ma and Md each represent a monomer unit of a polymer which may be the same or different, and the monomer unit of M _d may be composed of one type or two or more different units, and S _a represents _a spacer unit, D represents a photochemically crosslinkable site, x and w represent the molar fraction of the copolymer, and in each case 0 <x ≦ 1 and 0 ≦ w < 1 and n represents 4 to 1,000,000).
Further, the general formula (Ik-1)

（式中、M_cはポリマーのモノマー単位を表し、S_cはスペーサー単位を表し、V_cは側鎖末端を表す。）で表されるモノマーの硬化物を含むことができる。

(Wherein, M _c represents a monomer unit of the polymer, S _c represents a spacer unit, and V _c represents a side chain end).

  General formula (Ik)

（式中、M_c及びM_dは各々同一であっても異なっていても良いポリマーのモノマー単位を表し、M_dのモノマー単位は１種類でも２種類以上の異なる単位からなっていても良く、S_cはスペーサー単位を表し、V_cは側鎖末端を表し、z及びwはコポリマーのモル分率を表すものであって、いずれの場合にも0＜z≦１かつ０≦w＜１であり、nは4〜1000000を表す。）で表されるポリマーを含むことができる。
一般式(Ia)〜(Ik)、(Im)〜(Iq)、(Ia-1)〜(Id-2) 、(If-1)〜(Ii-3)、(Ik-1)及び(Im-1)〜(Ip-2)において、光化学的に架橋可能な部位Dが、式（II-1）から式（II-8）

(In the formula, M _c and M _d each represent a monomer unit of a polymer which may be the same or different, and the monomer unit of M _d may consist of one type or two or more different units, S _c represents a spacer unit, V _c represents a side chain end, z and w represent the molar fraction of the copolymer, and in each case 0 <z ≦ 1 and 0 ≦ w <1 And n represents 4 to 1000000).
General formulas (Ia) to (Ik), (Im) to (Iq), (Ia-1) to (Id-2), (If-1) to (Ii-3), (Ik-1) and (Im -1) to (Ip-2), the photochemically crosslinkable site D is represented by formula (II-1) to formula (II-8)

(式中、破線はSa、Saa、Saaa、Sb、又はSbbへの結合を表し、それぞれの構造中の任意の水素原子はフッ素原子、塩素原子、メチル基又はメトキシ基によって置換されていてもよい)からなる群より選ばれる何れかの基を有する化合物であることが好ましく、式（II-1）、（II-3）、（II-4）、（II-6）、（II-7）又は（II-8）がより好ましく、（II-6）、（II-7）又は（II-8）が特に好ましい。

(In the formula, a broken line represents a bond to Sa, Saa, Saaa, Sb, or Sbb, and any hydrogen atom in each structure may be substituted with a fluorine atom, a chlorine atom, a methyl group, or a methoxy group. And a compound having any group selected from the group consisting of: (II-1), (II-3), (II-4), (II-6), (II-7) Or (II-8) is more preferred, and (II-6), (II-7) or (II-8) is particularly preferred.

In order to improve the thermal stability of the photo-alignment film, the formula (II-1), (II-3), (II-4), (II-6), (II-7) or (II-8) preferable. In addition, (II-1), (II-2) or (II-5) is preferred in order to perform photo-alignment with longer wavelength light. In order to align the photo-alignment film with a smaller amount of light irradiation, the formula (II-3), (II-4), (II-6), (II-7) or (II-8) is preferred, Of these, (II-6), (II-7) or (II-8) is particularly preferred.
In the general formulas (Ia) to (Ik), (Im) to (Iq), (Ia-1) to (Ik-1) and (Im-1) to (Iq-1), Ma, Mb and Mc are Each independently of formula (III-1) to formula (III-17)

(式中、破線はSa、Sb又はScへの結合を表し、Ｒは独立して水素又は炭素原子数１から５のアルキル基を表し、それぞれの構造中の任意の水素原子はフッ素原子、塩素原子、メチル基又はメトキシ基によって置換されていてもよい)からなる群より選ばれる何れかの基を有する化合物であることが好ましく、式（III-1）、（III-2）、（III-3）、（III-4）、（III-6）、（III-7）、（III-8）、（III-9）、（III-10）、（III-11）、（III-13）、（III-16）又は（III-17）が好ましく、式（III-1）、（III-2）、（III-3）、（III-6）、（III-7）、（III-8）、（III-13）、（III-16）又は（III-17）がより好ましく、式（III-1）、（III-2）、（III-3）、（III-6）、（III-7）又は（III-13）が特に好ましい。

(In the formula, a broken line represents a bond to Sa, Sb or Sc, R independently represents hydrogen or an alkyl group having 1 to 5 carbon atoms, and an arbitrary hydrogen atom in each structure represents a fluorine atom, chlorine A compound having any group selected from the group consisting of (which may be substituted by an atom, a methyl group or a methoxy group) is preferred, and is represented by the formula (III-1), (III-2), (III- 3), (III-4), (III-6), (III-7), (III-8), (III-9), (III-10), (III-11), (III-13) , (III-16) or (III-17) are preferred, and the formulas (III-1), (III-2), (III-3), (III-6), (III-7), (III-8) are preferred. ), (III-13), (III-16) or (III-17) are more preferred, and are represented by the formulas (III-1), (III-2), (III-3), (III-6), (III -7) or (III-13) is particularly preferred.

  In order to improve the solubility of the polymer, the formulas (III-1), (III-2), (III-3), (III-6), (III-7), (III-8), (III- 10), (III-12), (III-14), (III-16) or (III-17) are preferred, and among them, the formulas (III-1), (III-2), (III-10), ( III-12) or (III-17) is particularly preferred. In order to improve the polymerization rate, the formulas (III-3), (III-8), (III-10), (III-12), (III-13), (III-14), (III- 15), (III-16) or (III-17) is preferable, and among them, the formula (III-3), (III-8), (III-10), (III-12) or (III-17) is more preferable. preferable. In order to narrow the molecular weight distribution of the polymer, the formula (III-2), (III-10), (III-11) or (III-12) is preferable. In order to improve the stability of the orientation, the formulas (III-2), (III-4), (III-5), (III-7), (III-9), (III-13), ( III-14) or (III-15) is preferred. In order to improve the adhesion to the substrate, the formulas (III-1), (III-6), (III-7), (III-8), (III-9), (III-10), (III-12), (III-13) or (III-17) is preferred, and of these, formula (III-6), (III-7), (III-8) or (III-13) is particularly preferred.

The monomer unit M _d may be the same as or different from the monomer units M _a , M _b and _Mc, and a known monomer unit can be used without any particular limitation. Further, there is no particular limitation on the order of arrangement and randomness of the monomer units M _a , M _b , M _c and M _{d in} the polymer. Further, as the monomer unit _Md , one type of monomer unit or a combination of two or more types of monomer units can be used, but (a) a site that can be photochemically isomerized and is not photochemically crosslinked, It is desirable to use b) a site that can be cross-linked photochemically and (c) a site that stabilizes vertical alignment to such an extent that the effect of each site is not impaired. The monomer unit M _d is preferably an acrylate, methacrylate, acrylamide, methacrylamide, maleic acid derivative, siloxane or epoxide, or an acryloyloxy group, a methacryloyloxy group, a 2-chloroacryloyloxy group, 2 -Phenylacryloyloxy group, 2-phenyloxyacryloyloxy group, acrylamide group, methacrylamide group, 2-chloromethacrylamide group, 2-phenylacrylamide group, vinyloxy group, styryl group, vinyloxycarbonyl group, maleimide group, maleic acid Examples thereof include esters, fumaric acid esters, siloxanes, vinyl groups, and epoxy groups. Specifically, monomer units represented by formulas (MdIII-1) to (MdIII-17) can be used.

(式中、破線は、一価の有機基への結合を表わし、Ｒは独立して水素又は炭素原子数１から５のアルキル基を表し、それぞれの構造中の任意の水素原子はフッ素原子、塩素原子、メチル基又はメトキシ基によって置換されていてもよい。)
一価の有機基としては、水素、炭素原子数１から１２のアルキル基（該アルキル基中の任意の水素原子はフッ素原子、塩素原子、メチル基又はメトキシ基によって置換されていてもよく、また該アルキル基中の1つのCH₂基又は２以上の非隣接CH₂基は、-O-、-CO-O-、-O-CO-及び／又は-CH=CH-で置換されていても良い。）を例示することができる。また、トランス−１，４−シクロヘキシレン基、トランス−１，３−ジオキサン−２，５−イル基、１，４−ナフチレン基、２，６−ナフチレン基、２，５−ピリジル基、２，５−ピリミジル基、２，５−チオフェニレン基、２，５−フラニレン基又は１，４−フェニレン基（それぞれの構造中の任意の水素原子はフッ素原子、塩素原子、メチル基又はメトキシ基によって置換されていてもよい）を例示することができる。

(In the formula, a broken line represents a bond to a monovalent organic group, R independently represents hydrogen or an alkyl group having 1 to 5 carbon atoms, and an arbitrary hydrogen atom in each structure represents a fluorine atom, (It may be substituted by a chlorine atom, a methyl group or a methoxy group.)
Examples of the monovalent organic group include hydrogen, an alkyl group having 1 to 12 carbon atoms (any hydrogen atom in the alkyl group may be substituted with a fluorine atom, a chlorine atom, a methyl group, or a methoxy group, One CH ₂ group or two or more non-adjacent CH ₂ groups in the alkyl group may be substituted with —O—, —CO—O—, —O—CO— and / or —CH═CH—. Good)). In addition, trans-1,4-cyclohexylene group, trans-1,3-dioxane-2,5-yl group, 1,4-naphthylene group, 2,6-naphthylene group, 2,5-pyridyl group, 2, 5-pyrimidyl group, 2,5-thiophenylene group, 2,5-furylene group or 1,4-phenylene group (any hydrogen atom in each structure is replaced by fluorine atom, chlorine atom, methyl group or methoxy group) May be exemplified).

In the general formulas (Ia) to (Ik), (Im) to (Iq), (Ia-1) to (Ik-1) and (Im-1) to (Iq-1), S _a , S _aa , S _aaa , S _b , S _bb and S _c are each represented by the following general formula (IV)

（式中、破線はMa、Mb、Mc、P、V、Va、Vb、Vc又はDへの結合を表し；
Z¹、Z²及びZ³は、それぞれ独立的に単結合、−(ＣＨ_２)_u−、−ＯＣＨ_２−、−ＣＨ_２Ｏ−、―ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＦ_２ＣＦ_２−又は−Ｃ≡Ｃ−を表し、uは１〜２０を表し、ここでアルキル基の非隣接ＣＨ_２基の内の１つ以上が独立してＱによって置換されることができ、ここでＱは、−Ｏ−、−ＣＯ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−、−Ｓｉ（ＣＨ３）_２−Ｏ−Ｓｉ（ＣＨ_３）_２―、−ＮＲ−、−ＮＲ−ＣＯ−、−ＣＯ−ＮＲ−、−ＮＲ−ＣＯ−Ｏ−、−Ｏ−ＣＯ−ＮＲ−、−ＮＲ−ＣＯ−ＮＲ−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−Ｏ−ＣＯ−Ｏ−を表し、Ｒは独立して水素又は炭素原子数１から５のアルキル基を表し；
A¹及びA²は、それぞれ独立的にトランス−１，４−シクロヘキシレン基、トランス−１，３−ジオキサン−２，５−イル基、１，４−ナフチレン基、２，６−ナフチレン基、２，５−ピリジル基、２，５−ピリミジル基、２，５−チオフェニレン基、２，５−フラニレン基又は１，４−フェニレン基を表し、これらは無置換であるか１個以上水素原子がフッ素原子、塩素原子、メチル基又はメトキシ基によって置換されていてもよく；
p及びqは、０又は１を表す。）
で表される構造であることが好ましく、Z¹、Z²及びZ³は、それぞれ独立して単結合、−(ＣＨ_２)_u−（式中、uは１〜１２を表し、非隣接のＣＨ_２基の一つ以上は独立して、−Ｏ−、−ＣＯ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−、−ＮＲ−、−ＮＲ−ＣＯ−、−ＣＯ−ＮＲ−、−ＮＲ−ＣＯ−ＮＲ−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−又は−Ｏ−ＣＯ−Ｏ−を表し、Ｒは水素、メチル基又はエチル基を表す。）、−ＯＣＨ_２−、−ＣＨ_２Ｏ−、―ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−又は−Ｃ≡Ｃ−が好ましく、A¹及びA²は、それぞれ独立してトランス−１，４−シクロヘキシレン基、トランス−１，３−ジオキサン−２，５−ジイル基、１，４−ナフチレン基、２，６−ナフチレン基、ピリジン−２，５−ジイル基、ピリミジン−２，５−ジイル基又は１，４−フェニレン基を表し、これらは無置換であるか又は一個以上の水素原子がフッ素原子、塩素原子、メチル基又はメトキシ基によって置換されていることが好ましく、Z¹、Z²及びZ³は、それぞれ独立して単結合、−(ＣＨ_２)_u−（式中、uは１〜１０を表し、非隣接のＣＨ_２基の一つ以上は独立して、−Ｏ−、−ＣＯ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−、−ＮＲ−、−ＮＲ−ＣＯ−、−ＣＯ−ＮＲ−、−ＣＨ＝ＣＨ−又は−Ｃ≡Ｃ−を表し、Ｒは水素、メチル基又はエチル基を表す。）、−ＯＣＨ_２−、−ＣＨ_２Ｏ−、―ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−、又は−Ｃ≡Ｃ−がより好ましく、A¹及びA²は、それぞれ独立してトランス−１，４−シクロヘキシレン基、２，６−ナフチレン基、又は１，４−フェニレン基を表し、これらは無置換であるか又は一個以上の水素原子がフッ素原子、塩素原子、メチル基又はメトキシ基によって置換されていることがより好ましく、Z¹、Z²及びZ³は、それぞれ独立して単結合、−(ＣＨ_２)_u−（式中、uは１〜６を表し、非隣接のＣＨ_２基の一つ以上は独立して、−Ｏ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−、−ＣＨ＝ＣＨ−又は−Ｃ≡Ｃ−を表す。）、−ＯＣＨ_２−、−ＣＨ_２Ｏ−、―ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−、又は−Ｃ≡Ｃ−が特に好ましく、A¹及びA²は、それぞれ独立してトランス−１，４−シクロヘキシレン基、２，６−ナフチレン基、又は１，４−フェニレン基を表し、これらは無置換であるか又は一個以上の水素原子がフッ素原子、メチル基又はメトキシ基によって置換されていることが特に好ましい。

(Where the dashed line represents binding to Ma, Mb, Mc, P, V, Va, Vb, Vc or D;
Z ¹ , Z ² and Z ³ are each independently a single bond, — (CH ₂ ) _u —, —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CH═CH—, _{-CF = CF -, - CF 2} O -, - OCF 2 -, - CF 2 CF 2 - or an -C≡C-, u represents 1 to 20, wherein non-adjacent CH ₂ groups of an alkyl group Can be independently substituted by Q, where Q is —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—, —O—CO—O—, wherein R independently represents hydrogen or an alkyl group having 1 to 5 carbon atoms;
A ¹ and A ² are each independently a trans-1,4-cyclohexylene group, a trans-1,3-dioxane-2,5-yl group, a 1,4-naphthylene group, a 2,6-naphthylene group, 2,5-pyridyl group, 2,5-pyrimidyl group, 2,5-thiophenylene group, 2,5-furanylene group or 1,4-phenylene group, which are unsubstituted or one or more hydrogen atoms May be substituted by a fluorine atom, a chlorine atom, a methyl group or a methoxy group;
p and q represent 0 or 1. )
Z ¹ , Z ² and Z ³ are each independently a single bond, — (CH ₂ ) _u — (wherein u represents 1 to 12, One or more of the CH ₂ groups are independently —O—, —CO—, —CO—O—, —O—CO—, —NR—, —NR—CO—, —CO—NR—, —NR. —CO—NR—, —CH═CH—, —C≡C— or —O—CO—O—, wherein R represents hydrogen, a methyl group or an ethyl group.), —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CH═CH—, —CF ₂ O—, —OCF ₂ — or —C≡C— are preferred, and A ¹ and A ² are each independently trans-1 , 4-cyclohexylene group, trans-1,3-dioxane-2,5-diyl group, 1,4-naphthylene group, 2,6-naphthylene group, pyridine-2,5-di Represents a ru group, a pyrimidine-2,5-diyl group or a 1,4-phenylene group, which are unsubstituted or substituted with one or more hydrogen atoms by fluorine, chlorine, methyl or methoxy groups. Z ¹ , Z ² and Z ³ are each independently a single bond, — (CH ₂ ) _u — (wherein _u represents 1 to 10, and one of non-adjacent CH ₂ groups The above is independently -O-, -CO-, -CO-O-, -O-CO-, -NR-, -NR-CO-, -CO-NR-, -CH = CH- or -C. ≡C—, R represents hydrogen, methyl group or ethyl group.), —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CH═CH—, or —C≡C -Is more preferable, and A ¹ and A ² are each independently a trans-1,4-cyclohexylene group or 2,6-naphthylene. Or a 1,4-phenylene group, which are unsubstituted or more preferably one or more hydrogen atoms are substituted by fluorine, chlorine, methyl or methoxy groups, Z ¹ , Z ² and Z ³ are each independently a single bond, — (CH ₂ ) _u — (wherein _u represents 1 to 6, and one or more of non-adjacent CH ₂ groups are independently —O -, - COO -, - OCO -, - CH = CH- or an _{-C≡C-), -. OCH 2 -} , - CH 2 O -, - COO -, - OCO -, - CH═CH— or —C≡C— is particularly preferable, and A ¹ and A ² are each independently a trans-1,4-cyclohexylene group, a 2,6-naphthylene group, or a 1,4-phenylene group. These are unsubstituted or one or more hydrogen atoms are replaced by fluorine atom, methyl group or methoxy group It is particularly preferably substituted me.

In general formula (IV), Z ¹ , Z ^2, and Z ³ are each independently a single bond for improving the liquid crystal orientation, and — (CH ₂ ) _u — (wherein u represents 1 to 8). , One or two of the non-adjacent CH ₂ groups are independently —O—, —CO—O—, —O—CO—, —Si (CH ₃ ) ₂ —O—Si (CH ₃ ) _2. —, —CH═CH—, —C≡C—), —COO—, —OCO—, —CH═CH—, —CF═CF— or —C≡C— are preferred, and A ¹ and A ² are each independently trans-1,4-cyclohexylene group, trans-1,3-dioxane-2,5-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, A 2,5-thiophenylene group or a 1,4-phenylene group is preferred. In order to improve thermal stability of orientation, Z ¹ , Z ² and Z ³ are each independently -NR-CO-, -CO-NR-, -NR-CO-O-, -O-CO. -NR-, -NR-CO-NR-, or -O-CO-O- is preferable, and A ¹ and A ² are each independently 1,4-naphthylene group, 2,6-naphthylene group, pyridine- 2,5-diyl group, pyrimidine-2,5-diyl group, 2,5-thiophenylene group, 2,5-furylene group or 1,4-phenylene group is preferred. In order to improve the solubility of the polymer, Z ¹ , Z ² and Z ³ are each independently —OCH ₂ —, —CH ₂ O—, —CF ₂ O—, —OCF ₂ —, —CF _2. CF ₂ —, —NR— or —CO— is preferable, and A ¹ and A ² are each independently a trans-1,4-cyclohexylene group, 1,4-naphthylene group, 2,6-naphthylene group or 2 , 5-furanylene groups are preferred.
The general formula (IV) includes many compounds. Specifically, the following formulas (Sa-1) to (S-ad-9)

で表される化合物が特に好ましい。

Is particularly preferred.

Among these, formulas (Sa-6) to (Sa-16), formulas (Sb-3) to (Sb-10), formulas (Sc-3) to (Sc-10), formulas (Sd-3) to (Sd-12), formula (Sk-4) to (Sk-7), formula (Sl-13) to (Sl-17), formula (So-3) to (So-14), formula (Sp-2 ) To (Sp-13), formulas (Ss-1) to (Ss-8), formulas (St-1) to (St-8), formulas (Sy-1) to (Sy-9) and formula (S -aa-1) to (S-aa-9) are more preferred.
In the general formulas (Ia) to (Ik), (Im) to (Iq), (Ia-1) to (Ik-1) and (Im-1) to (Iq-1), V, Va, Vb and Vc Is the following general formula (V),

（式中、破線はS_c、S_aa、S_bb又はS_aaaへの結合を表し；
Z⁴、Z⁵、Z⁶及びZ⁷は、それぞれ独立的に単結合、−(ＣＨ_２)_u−、−ＯＣＨ_２−、−ＣＨ_２Ｏ−、―ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＦ_２ＣＦ_２−又は−Ｃ≡Ｃ−を表し、uは１〜２０を表し、ここでアルキル基の非隣接ＣＨ_２基の内の１つ以上が独立してＱによって置換されることができ、ここでＱは、−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−、−Ｏ−ＣＯ−Ｏ−を表し、Ｒは独立して水素又は炭素原子数１から５のアルキル基を表し；
A³、A⁴、A⁵及びA⁶は、それぞれ独立的にトランス−１，４−シクロヘキシレン基、トランス−１，３−ジオキサン−２，５−イル基、１，４−ナフチレン基、２，６−ナフチレン基、２，５−ピリジル基、２，５−ピリミジル基、２，５−チオフェニレン基、２，５−フラニレン基又は１，４−フェニレン基を表し、これらは無置換であるか１個以上水素原子がフッ素原子、塩素原子、メチル基又はメトキシ基によって置換されていてもよく；
ｒ、s、ｔ及びwは、０又は１を表し；
R²は、水素、フッ素、塩素、シアノ基又は炭素数１〜２０のアルキル基（適宜フッ素置換されていてもよく、また適宜1つのCH₂基又は２以上の非隣接CH2基は-O-、-CO-O-、-O-CO-及び／又は-CH=CH-で置換されていても良い）を表す。）
で表される構造であることが好ましい。

(Where the dashed line represents a bond to S _c , S _aa , S _bb or S _aaa ;
Z ⁴ , Z ⁵ , Z ⁶ and Z ⁷ are each independently a single bond, — (CH ₂ ) _u —, —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CH═ CH—, —CF═CF—, —CF ₂ O—, —OCF ₂ —, —CF ₂ CF ₂ — or —C≡C—, where u represents 1 to 20, where non-adjacent of an alkyl group One or more of the CH ₂ groups can be independently replaced by Q, where Q is —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—, —O—CO—O—, wherein R independently represents hydrogen or an alkyl group having 1 to 5 carbon atoms;
A ³ , A ⁴ , A ⁵ and A ⁶ are each independently trans-1,4-cyclohexylene group, trans-1,3-dioxane-2,5-yl group, 1,4-naphthylene group, 2 , 6-naphthylene group, 2,5-pyridyl group, 2,5-pyrimidyl group, 2,5-thiophenylene group, 2,5-furylene group or 1,4-phenylene group, which are unsubstituted Or one or more hydrogen atoms may be substituted by fluorine atom, chlorine atom, methyl group or methoxy group;
r, s, t and w represent 0 or 1;
R ² represents hydrogen, fluorine, chlorine, a cyano group or an alkyl group having 1 to 20 carbon atoms (which may be appropriately substituted with fluorine, and one CH ₂ group or two or more non-adjacent CH 2 groups may be —O— , -CO-O-, -O-CO- and / or -CH = CH-). )
It is preferable that it is a structure represented by these.

Z ⁴ , Z ⁵ , Z ⁶ and Z ⁷ are each independently a single bond, — (CH ₂ ) _u — (wherein _u represents 1 to 12, and one or more of non-adjacent CH ₂ groups are independent. -O-, -CO-, -CO-O-, -O-CO-, -NR-CO-, -CO-NR-, -NR-CO-NR-, -CH = CH-,- C≡C— or —O—CO—O—, and R independently represents hydrogen, a methyl group or an ethyl group.), —OCH ₂ —, —CH ₂ O—, —COO—, —OCO— , —CH═CH—, —CF ₂ O—, —OCF ₂ — or —C≡C— are preferred,
A ³ , A ⁴ , A ⁵ and A ⁶ are each independently trans-1,4-cyclohexylene group, 2,6-naphthylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group. Or a 1,4-phenylene group, which is unsubstituted or preferably one or more hydrogen atoms are substituted by a fluorine atom, a chlorine atom, a methyl group or a methoxy group,
r, s, t and u are preferably such that r + s + t + u is from 0 to 3,
R ² is hydrogen, fluorine, chlorine, a cyano group or an alkyl group having 1 to 18 carbon atoms (one CH ₂ group or two or more non-adjacent CH ₂ groups in the alkyl group are —O—, —CO—O— , —O—CO— and / or —CH═CH— may be substituted.

In order to improve the liquid crystal orientation, Z ⁴ , Z ⁵ , Z ⁶ and Z ⁷ are each independently a single bond, — (CH ₂ ) _u — (wherein u represents 1 to 8, One or two of the CH ₂ groups are independently —O—, —CO—O—, —O—CO—, —Si (CH ₃ ) ₂ —O—Si (CH ₃ ) ₂ —, —CH. ═CH—, —C≡C—), —COO—, —OCO—, —CH═CH—, —CF═CF— or —C≡C— are preferred, and A ³ , A ⁴ , A ⁵ And A ⁶ are each independently a trans-1,4-cyclohexylene group, a trans-1,3-dioxane-2,5-diyl group, a pyridine-2,5-diyl group, or a pyrimidine-2,5-diyl group. 2,5-thiophenylene group or 1,4-phenylene group is preferred.

In order to improve the thermal stability of the orientation, Z ⁴ , Z ⁵ , Z ⁶ and Z ⁷ are each independently —NR—CO—, —CO—NR—, —NR—CO—O—, — O-CO-NR-, -NR-CO-NR-, or -O-CO-O- is preferred, and A ³ , A ⁴ , A ⁵ and A ⁶ are each independently a 1,4-naphthylene group, 2 , 6-naphthylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, 2,5-thiophenylene group, 2,5-furylene group or 1,4-phenylene group is preferable. In order to improve the solubility of the polymer, Z ⁴ , Z ⁵ , Z ⁶ and Z ⁷ are each independently —OCH ₂ —, —CH ₂ O—, —CF ₂ O—, —OCF ₂ —, —CF ₂ CF ₂ —, —NR— or —CO— is preferable, and A ³ , A ⁴ , A ⁵ and A ⁶ are each independently a trans-1,4-cyclohexylene group, 1,4-naphthylene group, A 2,6-naphthylene group or a 2,5-furylene group is preferred.

In order to give a pretilt angle of 80 degrees or more, Z ⁴ , Z ⁵ , Z ⁶ and Z ⁷ are each independently a single bond, —OCH ₂ —, —CH ₂ O—, —COO—, —OCO. -And -C≡C- are preferred, and A ³ , A ⁴ , A ⁵ and A ⁶ are each independently a trans-1,4-cyclohexylene group, trans-1,3-dioxane-2,5-diyl group. And 1,4-phenylene group is preferable, and R ² is preferably an alkyl group having 1 to 10 carbon atoms, an alkoxy group, fluorine, a trifluoromethyl group or a trifluoromethoxy group.

  The general formula (V) includes many compounds, specifically, the following formulas (V-a-1) to (V-q-10)

で表される化合物が特に好ましい。
中でも式(V-a-1)〜(V-a-15)、式(V-b-11)〜(V-b-15)、式(V-c-1)〜(V-c-11)、式(V-d-10)〜(V-d-15)、式(V-f-1)〜(V-f-10)、式(V-g-1)〜(V-g-10)、式(V-h-1)〜(V-h-10)、式(V-j-1)〜(V-j-9)、式(V-l-1)〜(V-l-11)又は式(V-m-1)〜(V-m-11)がさらに好ましい。

Is particularly preferred.
Above all, formula (Va-1) to (Va-15), formula (Vb-11) to (Vb-15), formula (Vc-1) to (Vc-11), formula (Vd-10) to (Vd- 15), formula (Vf-1) to (Vf-10), formula (Vg-1) to (Vg-10), formula (Vh-1) to (Vh-10), formula (Vj-1) to (V Vj-9), formulas (Vl-1) to (Vl-11) or formulas (Vm-1) to (Vm-11) are more preferred.

  In the general formulas (Ia) to (Ik), (Im) to (Iq), (Ia-1) to (Ik-1) and (Im-1) to (Iq-1), P is represented by the following general formula ( VI)

（式中、破線はS_a、S_b、S_aa、及びS_aaaへの結合を表すが、一方の破線のみで結合している場合はもう一方の破線は水素原子に結合しており；
A¹、A²、A³、A⁴及びA⁵は、それぞれ独立的に１，４−ナフチレン基、２，６−ナフチレン基、２，５−ピリジル基、２，５−ピリミジル基、２，５−チオフェニレン基、２，５−フラニレン基又は１，４−フェニレン基を表し、これらは無置換であるか、フッ素原子、塩素原子、臭素原子、メチル基、メトキシ基、ニトロ基、−ＮＲ^１Ｒ^２によって、又は１〜１０個の炭素原子を有する直鎖もしくは分岐アルキル残基によって１置換又は多置換されており、アルキル残基は非置換であるか、フッ素によって１置換又は多置換され、ここで非隣接ＣＨ_２基の内の１つ以上が独立してＱによって置換されることができ、ここでＱは、−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−、−Ｏ−ＣＯ−Ｏ−を表し、R、Ｒ^１及びＲ^２は、独立して水素又は炭素原子数１から５のアルキル基を表し；
p、q、r、s及びtは、それぞれ独立的に０又は１を表すが、0<ｑ＋ｒ＋ｓ＋ｔを表す。）
で表される構造であることが好ましく、A¹、A²、A³、A⁴及びA⁵は、それぞれ独立して１，４−ナフチレン基、２，６−ナフチレン基、ピリジン−２，５−ジイル基、ピリミジン−２，５−ジイル基又は１，４−フェニレン基を表し、これらは無置換であるか、又は一個以上の水素原子がフッ素原子、塩素原子、メチル基、メトキシ基で置換されていることが好ましく、A¹、A²、A³、A⁴及びA⁵は、それぞれ独立して２，６−ナフチレン基、ピリジン−２，５−ジイル基、ピリミジン−２，５−ジイル基又は１，４−フェニレン基を表し、これらは無置換であるか、又は一個以上の水素原子がフッ素原子、塩素原子、メチル基、メトキシ基で置換されていることがより好ましく、ｑ＋ｒ＋ｓ＋ｔは１以上２以下がより好ましく、A¹、A²、A³、A⁴及びA⁵は、それぞれ独立して２，６−ナフチレン基、又は１，４−フェニレン基を表し、これらは無置換であるか、又は一個以上の水素原子がフッ素原子、塩素原子、メチル基、メトキシ基で置換されていることが特に好ましく、ｐ及びｑ＋ｒ＋ｓ＋ｔは１であることが特に好ましい。

(In the formula, a broken line represents a bond to S _a , S _b , S _aa , and S _aaa , but when only one broken line is bonded, the other broken line is bonded to a hydrogen atom;
A ¹ , A ² , A ³ , A ⁴ and A ⁵ are each independently 1,4-naphthylene group, 2,6-naphthylene group, 2,5-pyridyl group, 2,5-pyrimidyl group, 2, Represents a 5-thiophenylene group, a 2,5-furylene group or a 1,4-phenylene group, which are unsubstituted, fluorine atom, chlorine atom, bromine atom, methyl group, methoxy group, nitro group, -NR Monosubstituted or polysubstituted by ¹ R ² or by linear or branched alkyl residues having 1 to 10 carbon atoms, the alkyl residues being unsubstituted or monosubstituted or polysubstituted by fluorine Wherein one or more of the non-adjacent CH ₂ groups can be independently replaced by Q, where Q is —O—, —CO—, —CO—O—, —O—CO _{-, - Si (CH 3)} 2 -O-Si (CH 3) 2 -, - R—, —NR—CO—, —CO—NR—, —NR—CO—O—, —O—CO—NR—, —NR—CO—NR—, —CH═CH—, —C≡C— , -O-CO-O-, wherein R, R ¹ and R ² independently represent hydrogen or an alkyl group having 1 to 5 carbon atoms;
p, q, r, s and t each independently represent 0 or 1, but 0 <q + r + s + t. )
And A ¹ , A ² , A ³ , A ⁴ and A ⁵ are each independently 1,4-naphthylene group, 2,6-naphthylene group, pyridine-2,5. -Represents a diyl group, a pyrimidine-2,5-diyl group or a 1,4-phenylene group, which are unsubstituted or substituted with one or more hydrogen atoms by fluorine, chlorine, methyl or methoxy groups A ¹ , A ² , A ³ , A ⁴ and A ⁵ are each independently 2,6-naphthylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl. Group or a 1,4-phenylene group, which are unsubstituted or more preferably one or more hydrogen atoms are substituted with a fluorine atom, a chlorine atom, a methyl group or a methoxy group, and q + r + s + t is 1 more preferably 2 or less or ^{more, A 1, A 2, A} 3 A ⁴ and A ⁵ are each independently a 2,6-naphthylene group, or 1,4-phenylene group, or they are unsubstituted, or one or more hydrogen atoms are fluorine atom, chlorine atom, methyl It is particularly preferred that the group is substituted with a methoxy group, and p and q + r + s + t are particularly preferably 1.

In order to improve the liquid crystal orientation, A ¹ , A ² , A ³ , A ⁴ and A ⁵ are each independently pyridine-2,5-diyl group, pyrimidine-2,5-diyl group or 1,4- A phenylene group is preferred. In order to improve the solubility of the polymer, A ¹ , A ² , A ³ , A ⁴ and A ⁵ are each independently 1,4-naphthylene group, 2,6-naphthylene group, 2,5- A thiophenylene group or a 2,5-furylene group is preferred. In order to reduce the amount of light irradiation necessary for aligning the liquid crystal, A ¹ , A ² , A ³ , A ⁴ and A ⁵ are pyridine-2,5-diyl group, pyrimidine-2,5-diyl. Group, 2,5-thiophenylene group or 1,4-phenylene group is preferable, and q + r + s + t is preferably 1 to 2. In order to perform photo-alignment at a longer wavelength, A ¹ , A ² , A ³ , A ⁴ and A ⁵ are pyrimidine-2,5-diyl group, 2,5-thiophenylene group, 2,6- A naphthylene group and a 2,5-furylene group are preferable, and q + r + s + t is preferably 1 to 3.
The general formula (VI) includes many compounds. Specifically, the following formulas (Pa-1) to (Pe-7)

で表される化合物が特に好ましい。
中でも式(P-a-1)〜(P-a-9)、式(P-b-1)〜(P-b-8)、式(P-c-1)又は式(P-e-5)で表される化合物がさらに好ましい。

Is particularly preferred.
Of these, compounds represented by formulas (Pa-1) to (Pa-9), formulas (Pb-1) to (Pb-8), formula (Pc-1) or formula (Pe-5) are more preferable.

  In the general formulas (Ia) to (Ik), (Im) to (Iq), (Ia-1) to (Ik-1) and (Im-1) to (Iq-1), D represents the following general formula ( VII)

（式中、破線はS_a、S_aa、S_aaa、S_b及びS_bbへの結合を表すが、一方の破線のみで結合している場合はもう一方の破線は水素原子に結合しており；
Ａ⁷は、それぞれ独立的に１，４−ナフチレン基、２，６−ナフチレン基、２，５−ピリジル基、２，５−ピリミジル基、２，５−チオフェニレン基、２，５−フラニレン基又は１，４−フェニレン基を表し、これらは無置換であるか１個以上水素原子がフッ素原子、塩素原子、メチル基又はメトキシ基によって置換されていてもよく；
X及びYは、それぞれ独立的に水素、フッ素、塩素、シアノ基又は炭素数１〜２０のアルキル基（適宜フッ素置換されていてもよく、また適宜1つのCH₂基又は２以上の非隣接CH₂基は-O-、-CO-O-、-O-CO-及び／又は-CH=CH-で置換されていても良い）を表し；
Zは、単結合、-O-又は-NR¹-（式中、R¹は水素、適宜フッ素又は塩素で置換されていても良い直鎖又は分岐した炭素数１〜２０のアルキル基又は適宜フッ素、塩素、アルキル基又はアルコキシ基で置換されていても良い３〜８の環員数を有するシクロアルキル基である）を表し；
rは、０、１又は２を表す。）
で表される構造であることが好ましく、配向の熱安定性を改善するためにはZは-NR¹-が好ましい。又、液晶配向性を改善するためにはＡ⁷はピリジン−２，５−ジイル基、ピリミジン−２，５−ジイル基又は１，４−フェニレン基が好ましい。又、ポリマーの溶解性を改善するためにはＡ⁷は１，４−ナフチレン基、２，６−ナフチレン基、２，５−チオフェニレン基又は２，５−フラニレン基が好ましい。又、液晶を配向させるために必要な光照射量を少なくするためにはＡ⁷はピリジン−２，５−ジイル基、ピリミジン−２，５−ジイル基、２，５−チオフェニレン基又は１，４−フェニレン基が好ましく、Zは単結合又は-O-が好ましい。又、より長波長での光配向を行うためにはＡ⁷はピリミジン−２，５−ジイル基、２，５−チオフェニレン基、２，６−ナフチレン基、２，５−フラニレン基が好ましく、X及びYはフッ素原子、塩素原子又はシアノ基が好ましい。

(In the formula, the broken line represents the bond to S _a , S _aa , S _aaa , S _b and S _bb , but when only one broken line is bonded, the other broken line is bonded to a hydrogen atom. ;
A ⁷ is independently 1,4-naphthylene group, 2,6-naphthylene group, 2,5-pyridyl group, 2,5-pyrimidyl group, 2,5-thiophenylene group, 2,5-furylene group. Or a 1,4-phenylene group, which is unsubstituted or one or more hydrogen atoms may be substituted by a fluorine atom, a chlorine atom, a methyl group or a methoxy group;
X and Y are each independently hydrogen, fluorine, chlorine, a cyano group or an alkyl group having 1 to 20 carbon atoms (which may be appropriately substituted with fluorine, and optionally one CH ₂ group or two or more non-adjacent CH ₂ groups represent -O-, -CO-O-, -O-CO- and / or -CH = CH-);
Z is a single bond, —O— or —NR ¹ — (wherein R ¹ is hydrogen, a linear or branched alkyl group having 1 to 20 carbon atoms optionally substituted with fluorine or chlorine, or optionally fluorine , A cycloalkyl group having 3 to 8 ring members which may be substituted with chlorine, an alkyl group or an alkoxy group);
r represents 0, 1 or 2. )
In order to improve the thermal stability of the orientation, Z is preferably —NR ¹ —. In order to improve the liquid crystal orientation, A ⁷ is preferably a pyridine-2,5-diyl group, a pyrimidine-2,5-diyl group or a 1,4-phenylene group. In order to improve the solubility of the polymer, A ⁷ is preferably a 1,4-naphthylene group, a 2,6-naphthylene group, a 2,5-thiophenylene group or a 2,5-furylene group. In order to reduce the amount of light irradiation necessary for aligning the liquid crystal, A ⁷ is pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, 2,5-thiophenylene group, A 4-phenylene group is preferred, and Z is preferably a single bond or —O—. In order to perform photo-alignment at a longer wavelength, A ⁷ is preferably a pyrimidine-2,5-diyl group, a 2,5-thiophenylene group, a 2,6-naphthylene group, or a 2,5-furylene group. X and Y are preferably a fluorine atom, a chlorine atom or a cyano group.

  The general formula (VII) includes a large number of compounds, but the following formulas (D-a-1) to (D-d-7)

で表される化合物が特に好ましい。
中でも式(D-a-1)〜(D-a-10)又は式(D-b-1)〜(D-b-10)で表される化合物がさらに好ましい。

Is particularly preferred.
Of these, compounds represented by formulas (Da-1) to (Da-10) or formulas (Db-1) to (Db-10) are more preferable.

  The composition for a liquid crystal alignment layer of the present invention preferably contains (c) a compound that stabilizes vertical alignment as at least one further substance. Examples of the compound that stabilizes the vertical alignment include the general formula (V),

（式中、破線はS_c、S_aa、S_bb又はS_aaaへの結合を表し；
Z⁴、Z⁵、Z⁶及びZ⁷は、それぞれ独立的に単結合、−(ＣＨ_２)_u−、−ＯＣＨ_２−、−ＣＨ_２Ｏ−、―ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＦ_２ＣＦ_２−又は−Ｃ≡Ｃ−を表し、uは１〜２０を表し、ここでアルキル基の非隣接ＣＨ_２基の内の１つ以上が独立してＱによって置換されることができ、ここでＱは、−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−、−Ｏ−ＣＯ−Ｏ−を表し、Ｒは独立して水素又は炭素原子数１から５のアルキル基を表し；
A³、A⁴、A⁵及びA⁶は、それぞれ独立的にトランス−１，４−シクロヘキシレン基、トランス−１，３−ジオキサン−２，５−イル基、１，４−ナフチレン基、２，６−ナフチレン基、２，５−ピリジル基、２，５−ピリミジル基、２，５−チオフェニレン基、２，５−フラニレン基又は１，４−フェニレン基を表し、これらは無置換であるか１個以上水素原子がフッ素原子、塩素原子、メチル基又はメトキシ基によって置換されていてもよく；
ｒ、s、ｔ及びwは、０又は１を表し；
R²は、水素、フッ素、塩素、シアノ基又は炭素数１〜２０のアルキル基（適宜フッ素置換されていてもよく、また適宜1つのCH₂基又は２以上の非隣接CH2基は-O-、-CO-O-、-O-CO-及び／又は-CH=CH-で置換されていても良い）を表す。）
で表される構造を必須成分として有する化合物であることが好ましい。

(Where the dashed line represents a bond to S _c , S _aa , S _bb or S _aaa ;
Z ⁴ , Z ⁵ , Z ⁶ and Z ⁷ are each independently a single bond, — (CH ₂ ) _u —, —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CH═ CH—, —CF═CF—, —CF ₂ O—, —OCF ₂ —, —CF ₂ CF ₂ — or —C≡C—, where u represents 1 to 20, where non-adjacent of an alkyl group One or more of the CH ₂ groups can be independently replaced by Q, where Q is —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—, —O—CO—O—, wherein R independently represents hydrogen or an alkyl group having 1 to 5 carbon atoms;
A ³ , A ⁴ , A ⁵ and A ⁶ are each independently trans-1,4-cyclohexylene group, trans-1,3-dioxane-2,5-yl group, 1,4-naphthylene group, 2 , 6-naphthylene group, 2,5-pyridyl group, 2,5-pyrimidyl group, 2,5-thiophenylene group, 2,5-furylene group or 1,4-phenylene group, which are unsubstituted Or one or more hydrogen atoms may be substituted by fluorine atom, chlorine atom, methyl group or methoxy group;
r, s, t and w represent 0 or 1;
R ² represents hydrogen, fluorine, chlorine, a cyano group or an alkyl group having 1 to 20 carbon atoms (which may be appropriately substituted with fluorine, and one CH ₂ group or two or more non-adjacent CH 2 groups may be —O— , -CO-O-, -O-CO- and / or -CH = CH-). )
It is preferable that it is a compound which has the structure represented by these as an essential component.

Z ⁴ , Z ⁵ , Z ⁶ and Z ⁷ in the general formula (V) are each independently a single bond, — (CH ₂ ) _u — (wherein _u represents 1 to 12, and non-adjacent CH ₂ groups One or more of -O-, -CO-, -CO-O-, -O-CO-, -NR-CO-, -CO-NR-, -NR-CO-NR-,- CH = CH—, —C≡C— or —O—CO—O—, wherein R independently represents hydrogen, a methyl group or an ethyl group), —OCH ₂ —, —CH ₂ O—, — COO—, —OCO—, —CH═CH—, —CF ₂ O—, —OCF ₂ — or —C≡C— are preferred,
A ³ , A ⁴ , A ⁵ and A ⁶ are each independently trans-1,4-cyclohexylene group, 2,6-naphthylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group. Or a 1,4-phenylene group, which is unsubstituted or preferably one or more hydrogen atoms are substituted by a fluorine atom, a chlorine atom, a methyl group or a methoxy group,
r, s, t and u are preferably such that r + s + t + u is from 0 to 3,
R ² is hydrogen, fluorine, chlorine, a cyano group or an alkyl group having 1 to 18 carbon atoms (one CH ₂ group or two or more non-adjacent CH ₂ groups in the alkyl group are —O—, —CO—O— , —O—CO— and / or —CH═CH— may be substituted.

In order to improve the liquid crystal orientation, Z ⁴ , Z ⁵ , Z ⁶ and Z ⁷ are each independently a single bond, — (CH ₂ ) _u — (wherein u represents 1 to 8, One or two of the CH ₂ groups are independently —O—, —CO—O—, —O—CO—, —Si (CH ₃ ) ₂ —O—Si (CH ₃ ) ₂ —, —CH. ═CH—, —C≡C—), —COO—, —OCO—, —CH═CH—, —CF═CF— or —C≡C— are preferred, and A ³ , A ⁴ , A ⁵ And A ⁶ are each independently a trans-1,4-cyclohexylene group, a trans-1,3-dioxane-2,5-diyl group, a pyridine-2,5-diyl group, or a pyrimidine-2,5-diyl group. 2,5-thiophenylene group or 1,4-phenylene group is preferred.

In order to improve the thermal stability of the orientation, Z ⁴ , Z ⁵ , Z ⁶ and Z ⁷ are each independently —NR—CO—, —CO—NR—, —NR—CO—O—, — O-CO-NR-, -NR-CO-NR-, or -O-CO-O- is preferred, and A ³ , A ⁴ , A ⁵ and A ⁶ are each independently a 1,4-naphthylene group, 2 , 6-naphthylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, 2,5-thiophenylene group, 2,5-furylene group or 1,4-phenylene group is preferable. In order to improve the solubility of the polymer, Z ⁴ , Z ⁵ , Z ⁶ and Z ⁷ are each independently —OCH ₂ —, —CH ₂ O—, —CF ₂ O—, —OCF ₂ —, —CF ₂ CF ₂ —, —NR— or —CO— is preferable, and A ³ , A ⁴ , A ⁵ and A ⁶ are each independently a trans-1,4-cyclohexylene group, 1,4-naphthylene group, A 2,6-naphthylene group or a 2,5-furylene group is preferred.

In order to give a pretilt angle of 80 degrees or more, Z ⁴ , Z ⁵ , Z ⁶ and Z ⁷ are each independently a single bond, —OCH ₂ —, —CH ₂ O—, —COO—, —OCO. -And -C≡C- are preferred, and A ³ , A ⁴ , A ⁵ and A ⁶ are each independently a trans-1,4-cyclohexylene group, trans-1,3-dioxane-2,5-diyl group. And 1,4-phenylene group is preferable, and R ² is preferably an alkyl group having 1 to 10 carbon atoms, an alkoxy group, fluorine, a trifluoromethyl group or a trifluoromethoxy group.

  The general formula (V) includes many compounds, specifically, the following formulas (V-a-1) to (V-q-10)

で表される化合物が特に好ましい。
中でも式(V-a-1)〜(V-a-15)、式(V-b-11)〜(V-b-15)、式(V-c-1)〜(V-c-11)、式(V-d-10)〜(V-d-15)、式(V-f-1)〜(V-f-10)、式(V-g-1)〜(V-g-10)、式(V-h-1)〜(V-h-10)、式(V-j-1)〜(V-j-9)、式(V-l-1)〜(V-l-11)又は式(V-m-1)〜(V-m-11)がさらに好ましい。

Is particularly preferred.
Above all, formula (Va-1) to (Va-15), formula (Vb-11) to (Vb-15), formula (Vc-1) to (Vc-11), formula (Vd-10) to (Vd- 15), formula (Vf-1) to (Vf-10), formula (Vg-1) to (Vg-10), formula (Vh-1) to (Vh-10), formula (Vj-1) to (V Vj-9), formulas (Vl-1) to (Vl-11) or formulas (Vm-1) to (Vm-11) are more preferred.

[Preparation of polymer for alignment layer]
The mixing ratio of the polymers in the liquid crystal alignment layer composition of the present invention was such that the photochemically isomerizable site in the polymer was 0.1 times the photochemically crosslinkable site 100 times mole in the polymer. It is preferable that it is -30 times mole. Further, it is more preferable that the number of photochemically isomerizable sites in the polymer is 2 to 10 times mol with respect to 100 times mol of the photochemically crosslinkable sites in the polymer. These compounds are preferably liquid crystalline compounds.

  In preparing the polymer contained in the composition for liquid crystal alignment layer in the present invention, a polymerization initiator can be arbitrarily used according to the polymerization mode of the polymerization functional group. Examples of the polymerization initiator are high It is known for the synthesis and reaction of molecules (edited by the Society of Polymer Science, Kyoritsu Shuppan). Examples of the thermal polymerization initiator in radical polymerization include azo compounds such as azobisisobutyronitrile and peroxides such as benzoyl peroxide. As photopolymerization initiators, aromatic ketone compounds such as benzophenone, Michler's ketone, xanthone, and thioxanthone, quinone compounds such as 2-ethylanthraquinone, acetophenone, trichloroacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl Acetophenone compounds such as phenyl ketone, benzoin ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, diketone compounds such as benzyl and methylbenzoylformate, 1-phenyl-1,2-propanedione-2 -Acyl oxime ester compounds such as (o-benzoyl) oxime, acyl phosphine oxide compounds such as 2,4,6-trimethylbenzoyl diphenylphosphine oxide Tetramethylthiuram, sulfur compounds such as dithiocarbamate, organic peroxides such as benzoyl peroxide, azo compounds such as azobisisobutyronitrile may be mentioned as examples. Moreover, an aromatic sulfonium salt compound etc. are mentioned as a thermal-polymerization initiator in cationic polymerization. Examples of the photopolymerization initiator include organic sulfonium salt compounds, iodonium salt compounds, and phosphonium compounds. The addition amount of the polymerization initiator is preferably 0.1 to 10% by mass in the composition, more preferably 0.1 to 6% by mass, and 0.1 to 3% by mass. More preferably. Moreover, the target polymer can also be synthesized by an addition reaction to the polymer main chain, such as a polysiloxane compound.

  The polymer in the present invention can be obtained by purifying the produced polymer after conducting a polymerization reaction in a reaction vessel made of glass or stainless steel in advance. The polymerization reaction can also be performed by dissolving the raw material monomer in a solvent. Examples of preferred solvents include benzene, toluene, xylene, ethylbenzene, pentane, hexane, heptane, octane, cyclohexane, cycloheptane, methanol, Ethanol, 1-propanol, 2-propanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, 2-butanone, acetone, tetrahydrofuran, γ-butyrolactone, N-methyl-pyrrolidone, dimethyl sulfoxide, dimethylformamide and the like. Two or more kinds of organic solvents may be used in combination. The polymer in the present invention can also be obtained by dissolving a monomer composition in a solvent, applying the solution on a substrate and drying and removing the solvent, and then performing a polymerization reaction by heating or light irradiation.

[Method for forming alignment layer]
By irradiating the polymer in the present invention with light, it is possible to impart alignment control ability to liquid crystal molecules and to provide stability to alignment heat and light. Examples of the method for producing a photo-alignment film of the present invention include a method in which the polymer is dissolved in a solvent and coated on a substrate, and then the coating film is irradiated with light to develop an alignment control ability to form an alignment film. It is done. The solvent used to dissolve the polymer is preferably one that dissolves the polymer of the present invention and other optional components and does not react with them, such as 1,1,2-trichloroethane, N-methyl. Examples include pyrrolidone, butoxyethanol, γ-butyrolactone, ethylene glycol, polyethylene glycol monomethyl ether, propylene glycol, 2-pyrrolidone, N, N-dimethylformamide, phenoxyethanol, tetrahydrofuran, dimethyl sulfoxide, methyl isobutyl ketone, and cyclohexanone. You may use the above organic solvent together.

  In addition, as a method for producing a photo-alignment film of the present invention, a polymer composition is prepared by dissolving a monomer composition in a solvent, coating the substrate, and then heating or irradiating the coating film to polymerize each polymer. And a method of forming an alignment film by irradiating the polymer composition with light to develop the alignment control ability. Moreover, after preparing a polymer on a board | substrate, you may prepare a polymer composition by adding a polymer further. As the solvent used for dissolving the monomer composition, a solvent similar to the solvent used for dissolving the polymer can be used. In addition, polymer preparation and orientation control ability may be performed simultaneously by light irradiation, and polymer preparation and orientation control by methods such as combined use of heating and light irradiation, or combination of two or more types of light having different wavelengths. The expression of ability may be performed separately. Furthermore, in any case of the method for producing the photo-alignment film, the photo-alignment film is further produced on the substrate on which the alignment film has been formed in advance, thereby controlling the orientation direction and the orientation angle by the polymer composition of the present invention. Capability can also be imparted to the substrate.

Examples of the material for the substrate include glass, silicon, polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, and triacetyl cellulose. When used in a liquid crystal display element, these substrates may be provided with electrode layers such as an ITO film made of Cr, Al, In ₂ O ₃ —SnO _2, an NESA film made of SnO ₂ , etc. For patterning the layer, a photo-etching method or a method using a mask when forming an electrode layer is used. Further, a color filter layer or the like may be formed. Examples of the method for applying the solution of the polymer composition on the substrate in the present invention include spin coating, die coating, gravure coating, flexographic printing, and inkjet printing. The solid content concentration of the solution at the time of coating is preferably 0.5 to 10% by weight, and more preferably selected from this range in consideration of the method of coating the solution on the substrate, viscosity, volatility and the like. Moreover, it is preferable to remove the solvent by heating the coated surface after coating, and the drying conditions are preferably 50 to 300 ° C., more preferably 80 to 200 ° C., preferably 5 to 200 minutes, more preferably. Is 10 to 100 minutes.

Further, when the monomer composition in the present invention is used, it is possible to prepare a polymer on a substrate by performing thermal polymerization in the heating step, and in this case, a polymerization initiator is contained in the composition. Is preferred. Or after removing a solvent by the said heating process, a non-polarized light can be irradiated and a polymer can also be prepared by photopolymerization, and thermal polymerization and photopolymerization can also be used together.
When preparing the polymer by thermal polymerization on a substrate, the heating temperature is not particularly limited as long as it is sufficient for the polymerization to proceed, but is generally about 50 to 250 ° C, and 70 to 200 ° C. More preferably, it is about. Moreover, it is not necessary to add a polymerization initiator in the composition.

When preparing the polymer by photopolymerization on a substrate, it is preferable to use non-polarized ultraviolet rays for light irradiation. The composition preferably contains a polymerization initiator. The irradiation energy is preferably ^{20mJ / cm 2 ~8J / cm 2} , further preferably ^{40mJ / cm 2 ~5J / cm 2} . Illuminance is preferably 10 to 1,000 / cm ^2, and more preferably 20 to 500 mW / cm ^2. The irradiation wavelength preferably has a peak at 250 to 450 nm.

  Next, the coating film formed by the above method is subjected to photoisomerization reaction and photocrosslinking reaction by linearly polarized light irradiation from the normal direction of the coating film surface, non-polarized light from the oblique direction, or linearly polarized light irradiation. Ability may be expressed, and these irradiation methods may be combined. In order to provide a desired pretilt angle, linearly polarized light irradiation from an oblique direction is preferable. In the present invention, the irradiation from the oblique direction is a case where the angle formed by the light irradiation direction and the substrate surface is 1 degree or more and 89 degrees or less. When used as an alignment film for vertical alignment, generally, the pretilt angle is preferably 70 to 89.8 °. Further, when used as an alignment film for horizontal alignment, generally, the pretilt angle is preferably 0 to 20 °.

For the irradiation light, for example, ultraviolet rays including visible light having a wavelength of 150 nm to 800 nm and visible rays can be used, and ultraviolet rays of 270 nm to 450 nm are particularly preferable. Examples of the light source include a xenon lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, and a metal halide lamp. Linearly polarized light can be obtained by using a polarizing filter or a polarizing prism for the light from these light sources. Further, the wavelength range of the ultraviolet light and visible light obtained from such a light source may be limited using an interference filter or a color filter. Further, the irradiation energy is preferably ^{15mJ / cm 2 ~500mJ / cm 2} , further preferably ^{20mJ / cm 2 ~300mJ / cm 2} . More preferably illuminance is 15~500mW / cm ^2, further preferably ^{20mJ / cm 2 ~300mW / cm 2} .

  The thickness of the formed photoalignment film is preferably about 10 to 250 nm, more preferably about 10 to 100 nm.

In the present invention, the optical axis means that the refractive index is constant in a liquid crystal display element or an optical anisotropic body, and birefringence does not occur even when unpolarized light is incident, and normal light and extraordinary light coincide with each other. Or, it is assumed that the direction is the direction in which the deviation is minimized. In the present invention, the orientation is the direction when the liquid crystal molecules in the liquid crystal cell of the liquid crystal display element or the polymerizable liquid crystal molecules forming the optical anisotropic body are oriented in a certain direction, and are rod-like. In the case of liquid crystal molecules, the direction taken by the major axis of the molecule is assumed, and in the case of disc-like liquid crystal molecules, the direction is a direction perpendicular to the disc surface. In the present invention, the pretilt angle is an angle formed by the alignment direction of liquid crystal molecules or polymerizable liquid crystal molecules and the substrate surface. In the present invention, the polymerizable liquid crystal is a compound that exhibits a liquid crystal phase and includes a polymerizable chemical structure. In the present invention, the homogeneous alignment is an alignment having a pretilt angle of 0 ° or more and 20 ° or less. In the present invention, homeotropic alignment is an alignment having a pretilt angle of 70 degrees or more and 90 degrees or less. The angle formed by the optical axis with respect to the substrate surface and the pretilt angle may or may not match.
[Method of manufacturing liquid crystal display element]
Using the alignment film formed by the above method, for example, a liquid crystal cell in which a liquid crystal composition is sandwiched between a pair of substrates and a liquid crystal display element using the same can be manufactured as follows.

  A liquid crystal cell can be manufactured by preparing two substrates on which the alignment film according to the present invention is formed and disposing a liquid crystal between the two substrates. The alignment film may be formed on only one of the two substrates.

  As a manufacturing method of a liquid crystal cell, the following method is mentioned, for example. First, two substrates are arranged so that the respective alignment films face each other, and a peripheral portion is bonded using a sealant in a state where a certain gap (cell gap) is maintained between the two substrates. A liquid crystal cell can be manufactured by injecting and filling liquid crystal into the cell gap defined by the surface and the sealing agent, and then sealing the injection hole.

The liquid crystal cell can also be manufactured by a technique called an ODF (One Drop Fill) method. As a procedure, for example, an ultraviolet light curable sealant is applied to a predetermined place on the substrate on which the alignment film is formed, and a liquid crystal is dropped on the alignment film surface, and then the alignment film faces. A liquid crystal cell can be manufactured by bonding another substrate and then irradiating the entire surface of the substrate with ultraviolet light to cure the sealant.
In any case of producing a liquid crystal cell, it is desirable to remove the flow alignment at the time of injection by heating to a temperature at which the liquid crystal used has an isotropic phase and then slowly cooling to room temperature.

  As said sealing agent, an epoxy resin etc. can be used, for example. Further, in order to keep the cell gap constant, beads such as silica gel, alumina, and acrylic resin can be used as spacers before the two substrates are bonded to each other. The two substrates may be bonded together after being mixed with a sealing agent.

  As the liquid crystal, for example, a nematic liquid crystal can be used. In the case of a vertical alignment type liquid crystal cell, those having negative dielectric anisotropy are preferable, and in the case of a horizontal alignment type liquid crystal cell, those having positive dielectric anisotropy are preferable. Examples of the liquid crystal used include dicyanobenzene liquid crystal, pyridazine liquid crystal, Schiff base liquid crystal, azoxy liquid crystal, naphthalene liquid crystal, biphenyl liquid crystal, and phenylcyclohexane liquid crystal.

  A liquid crystal display element can be obtained by attaching a polarizing plate to the outer surface of the liquid crystal cell thus manufactured. Examples of the polarizing plate include a polarizing plate made of “H film” in which iodine is absorbed while polyvinyl alcohol is stretched and oriented, or a polarizing plate in which the H film is sandwiched between cellulose acetate protective films.

[Method of manufacturing optical anisotropic body]
Using the alignment film formed by the above method, for example, an optical anisotropic body useful for an optical anisotropic film used for optical compensation of a liquid crystal display element can be produced as follows.

  When the polymerizable liquid crystal composition is applied on the photo-alignment film, a known and commonly used coating method such as bar coating, spin coating, roll coating, gravure coating, spray coating, die coating, cap coating, dipping method may be used. Good. At this time, in order to improve coatability, a known and commonly used organic solvent may be added to the polymerizable liquid crystal composition. In this case, after the polymerizable liquid crystal composition is applied on the photo-alignment film, the organic solvent is removed by natural drying, heat drying, reduced pressure drying, reduced pressure heat drying, or the like.

In order to obtain an optical anisotropic body using the photo-alignment film of the present invention, a polymerizable liquid crystal composition is applied on the photo-alignment film described above and polymerized in an aligned state. Examples of the method for polymerizing the polymerizable liquid crystal composition of the present invention include a method of irradiating active energy rays and a thermal polymerization method. In the case of the method of irradiating active energy rays, the polymerization operation of the polymerizable liquid crystal composition is preferably performed by irradiating light such as ultraviolet rays and performing photopolymerization because the operation is simple. In the case of photopolymerization, the photo-alignment film may be formed in the same manner as the photopolymerization. Ultraviolet irradiation intensity is ^preferably in the range of ^{1W / m 2 ~10kW / m 2} , the range of 5W / ^{m 2} ~2kW / m 2 is particularly preferred. 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 temperature. It is preferable to use those within the region. Moreover, this thermal polymerization initiator and a photoinitiator can also be used together. Although the heating temperature depends on the transition temperature from the liquid crystal phase to the isotropic phase of the polymerizable liquid crystal composition, it is preferably performed at a temperature lower than the temperature at which inhomogeneous polymerization is induced by heat. 300 degreeC is preferable, 30 to 200 degreeC is more preferable, and 30 to 120 degreeC is especially preferable. For example, when the polymerizable group is a (meth) acryloyloxy group, it is preferably performed at a temperature lower than 90 ° C.

  In the present invention, the optical axis of the optical anisotropic body can be adjusted by controlling the pretilt angle by the photo-alignment layer, but the angle formed by the optical axis with respect to the substrate surface is changed from 0 degrees to 45 degrees. Therefore, the pretilt angle is preferably 0 to 45 degrees, and in order to make the angle formed by the optical axis with respect to the substrate surface 45 to 90 degrees, the pretilt angle is 45 to 90 degrees. It is preferable that

  As a manufacturing process of a photo-alignment film and an optical anisotropic body, the following method is mentioned, for example. As a 1st process, the film | membrane of the said composition for photo-alignment films is created on a board | substrate. As a second step, an anisotropic light is irradiated to impart alignment control capability to the film of the composition for photo-alignment film, thereby forming a photo-alignment film. As a third step, a polymerizable liquid crystal composition film is formed on the photo-alignment film. As a fourth step, the polymerizable liquid crystal composition film is polymerized to form an optical anisotropic body. At this time, in the fourth step, a polymerization reaction or a crosslinking reaction may proceed simultaneously in the photo-alignment film. In the production process, the film of the composition for photo-alignment film is directly irradiated with light, so that a photo-alignment film having higher liquid crystal alignment ability can be obtained.

  Further, as another production method, the following method may be mentioned. As a first step, a film of the composition for photo-alignment film is formed on a substrate. As a second step, a polymerizable liquid crystal composition film is formed on the film of the photoalignment film composition. As a third step, an anisotropic light is irradiated to impart alignment control ability to the composition for photo-alignment film to form a photo-alignment film. As a fourth step, the polymerizable liquid crystal composition film is polymerized to form an optical anisotropic body. At this time, the third process and the fourth process may proceed simultaneously by light irradiation or the like, and the number of processes can be reduced in the manufacturing process.

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. After forming the optical anisotropic body on the photo-alignment film, a photo-alignment film and an optical anisotropic body may be further laminated on the optical anisotropic body, and the optical anisotropic body is formed on the photo-alignment film. After forming, an optical anisotropic body may be further laminated. The thus obtained optical anisotropic body having a plurality of optical isomer layers simultaneously performs optical compensation of the liquid crystal layer and the polarizing plate of the liquid crystal display element, or simultaneously performs optical compensation and brightness improvement of the liquid crystal layer of the liquid crystal display element. It can be used for applications such as performing optical compensation of a polarizing plate of a liquid crystal display element and improving luminance at the same time.

After only a specific part is polymerized by UV irradiation using a mask, the orientation state of the unpolymerized part is changed by applying an electric field, a magnetic field or temperature, and then the unpolymerized part is polymerized. An optical anisotropic body having a plurality of regions having orientation directions can also be obtained.
Further, when only a specific portion was polymerized by ultraviolet irradiation using a mask, the alignment was regulated in advance by applying an electric field, magnetic field or temperature to the unpolymerized polymerizable liquid crystal composition, and the state was maintained. An optical anisotropic body having a plurality of regions having different orientation directions can also be obtained by irradiating light from above the mask and polymerizing it.

  In order to stabilize the solvent resistance and heat resistance of the obtained optical anisotropic body, the optical anisotropic body can be subjected to a heat aging treatment. In this case, it is preferable to heat above the glass transition point of the prepolymerizable liquid crystal film. Usually, 50 to 300 ° C is preferable, 80 to 240 ° C is more preferable, and 100 to 220 ° C is particularly preferable.

  The optical anisotropic body obtained by the above steps can be used as an optical anisotropic body by separating the optical anisotropic layer from the substrate alone or as an optical anisotropic body without peeling from the substrate. You can also. 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.

[Preparation of polymerizable liquid crystal composition]
The polymerizable liquid crystal composition used for producing the optical anisotropic body in the present invention is a liquid crystal composition containing a polymerizable liquid crystal that exhibits liquid crystallinity alone or in a composition with another liquid crystal compound. For example, Handbook of Liquid Crystals (edited by D. Demus, JW Goodby, GW Gray, HW Spies, V. Vill, published by Wiley-VCH, 1998), Quarterly Chemical Review No. 22, Liquid Crystal Chemistry (Edited by Chemical Society of Japan, 1994), or JP-A-7-294735, JP-A-8-3111, JP-A-8-29618, JP-A-11-80090, 1,4-phenylene group, 1,4-cyclohexene, as described in Kaihei 11-148079, JP-A 2000-178233, JP-A 2002-308831, and JP-A 2002-145830. A rod-like polymerizable liquid crystal compound having a rigid site called a mesogen in which a plurality of structures such as a silene group are connected, and a polymerizable functional group such as a (meth) acryloyloxy group, a vinyloxy group, and an epoxy group, or JP-A-2004-2373 And a rod-like polymerizable liquid crystal compound having a maleimide group as described in JP-A-2004-99446 Alternatively, a rod-like polycyclic liquid crystal compound having an allyl ether group as described in JP-A No. 2004-149522, or, for example, Handbook of Liquid Crystals (D. Demus, JW Goodbye, GW Gray, H. W. Spiess, V. Vill, published by Wiley-VCH, 1998), Quarterly Chemical Review No. 22. Liquid crystal chemistry (edited by Chemical Society of Japan, 1994) and discotic polymerizable compounds described in JP-A-07-146409. Among these, a rod-like liquid crystal compound having a polymerizable group is preferable because it can easily produce a liquid crystal having a temperature range around room temperature.

  Although there is no limitation in particular as a solvent used for the said polymeric liquid crystal composition, the solvent in which the said compound shows favorable solubility can be used. For example, aromatic hydrocarbons such as toluene, xylene and mesitylene, ester solvents such as methyl acetate, ethyl acetate and propyl acetate, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, tetrahydrofuran, 1,2-dimethoxyethane And ether solvents such as anisole, amide solvents such as N, N-dimethylformamide and N-methyl-2-pyrrolidone, γ-butyrolactone, and chlorobenzene. These can be used alone or in combination of two or more. Moreover, an additive can also be added.

  The polymerizable liquid crystal composition may be added with a liquid crystal compound having no polymerizable group, if 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 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 5 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 may contain 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 cholesteryl group as cholesterol group, cholesterol stearate, and 2-methylbutyl group 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, “CM-21”, “CM-22” and the like manufactured by the company can be mentioned.

  When adding a chiral compound, depending on the use of the polymer of the polymerizable liquid crystal composition, a 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 ranging from 0.1 to 100, and more preferably in an amount ranging from 0.1 to 20.

  A stabilizer may be added to the polymerizable liquid crystal composition in order to improve storage stability. Examples of the stabilizer include hydroquinone, hydroquinone monoalkyl ethers, tert-butylcatechols, pyrogallols, thiophenols, nitro compounds, β-naphthylamines, β-naphthols and the like. When adding, it is preferable that it is 1 mass% or less with respect to the polymeric liquid crystal composition of this invention, and 0.5 mass% or less is especially preferable.

  The optically anisotropic body obtained from the composition for photo-alignment film and the polymerizable liquid crystal composition of the present invention is used for, for example, a polarizing film, a raw material for the alignment film, or printing ink, paint, protective film and the like. In some cases, the polymerizable liquid crystal composition used in the present invention has a metal, a metal complex, a dye, a pigment, a fluorescent material, a phosphorescent material, a surfactant, a leveling agent, a thixotropic agent, a gelling agent, depending on the purpose. Polysaccharides, ultraviolet absorbers, infrared absorbers, antioxidants, ion exchange resins, metal oxides such as titanium oxide, and the like may be added.

Hereinafter, although an example is given and this invention is further explained in full detail, this invention is not limited by these. The structure of the compound was confirmed by nuclear magnetic resonance spectrum (NMR), mass spectrum (MS) and the like. Unless otherwise specified, “part” and “%” are based on mass.
(Synthesis of monomers used as raw materials for polymers in liquid crystal alignment layer compositions)

4-ヒドロキシアゾベンゼン8.44g及び炭酸セシウム27.9gをジメチルスルホキシド110mLに溶解させ、室温で1時間撹拌した。この反応溶液に6-クロロヘキシルアクリレート9.94gを滴下し、85℃で4時間撹拌した。この反応溶液を室温まで冷却し、水150mLを加えて5℃で30分撹拌した。析出した固体をろ過し、メタノールで洗浄した。集めた固体をジクロロメタン150mlに溶かし、硫酸ナトリウムを加えて乾燥させた。硫酸ナトリウムを除去し、溶媒を減圧留去して体積を40ml程度に減らし、ヘキサン80mlを加えた。カラムクロマトグラフィー(アルミナ/シリカゲル、ヘキサン/ジクロロメタン=2:1)を用いて精製し、溶媒を減圧留去し、再結晶することにより白色結晶として(P-1)を得た（9.67g）。
¹H-NMR (400MHz, CDCl₃)δ: 1.47-1.54 (m, 4H), 1.71-1.74 (m, 2H), 1.82-1.86 (m, 2H), 4.04 (t, J=6.4Hz, 2H), 4.18 (t, J=6.6Hz, 2H), 5.82 (dd, J=1.6Hz, 10.4Hz, 1H), 6.13 (dd, J= 10.4Hz, 17.4Hz, 1H), 6.41 (dd, J=1.2Hz, 17.2Hz, 1H), 7.00 (d, J=9.2Hz, 2H), 7.43-7.52 (m, 3H), 7.87-7.93 (d+d, J=7.2Hz, 9.2Hz, 2H)
EI-MS:352[M⁺]

8.44 g of 4-hydroxyazobenzene and 27.9 g of cesium carbonate were dissolved in 110 mL of dimethyl sulfoxide and stirred at room temperature for 1 hour. To this reaction solution, 9.94 g of 6-chlorohexyl acrylate was added dropwise and stirred at 85 ° C. for 4 hours. The reaction solution was cooled to room temperature, 150 mL of water was added, and the mixture was stirred at 5 ° C. for 30 minutes. The precipitated solid was filtered and washed with methanol. The collected solid was dissolved in 150 ml of dichloromethane and dried by adding sodium sulfate. Sodium sulfate was removed, the solvent was distilled off under reduced pressure to reduce the volume to about 40 ml, and 80 ml of hexane was added. Purification using column chromatography (alumina / silica gel, hexane / dichloromethane = 2: 1), the solvent was distilled off under reduced pressure, and recrystallization gave (P-1) as white crystals (9.67 g).
¹ H-NMR (400MHz, CDCl ₃ ) δ: 1.47-1.54 (m, 4H), 1.71-1.74 (m, 2H), 1.82-1.86 (m, 2H), 4.04 (t, J = 6.4Hz, 2H) , 4.18 (t, J = 6.6Hz, 2H), 5.82 (dd, J = 1.6Hz, 10.4Hz, 1H), 6.13 (dd, J = 10.4Hz, 17.4Hz, 1H), 6.41 (dd, J = 1.2 Hz, 17.2Hz, 1H), 7.00 (d, J = 9.2Hz, 2H), 7.43-7.52 (m, 3H), 7.87-7.93 (d + d, J = 7.2Hz, 9.2Hz, 2H)
EI-MS: 352 [M ⁺ ]

公知文献（Journal of Materials Chemistry, Vol.19 (2009),60-62）に記載されている手順に従い、化合物(Ｐ−２)を合成した。

The compound (P-2) was synthesized according to the procedure described in a known document (Journal of Materials Chemistry, Vol. 19 (2009), 60-62).

特表平６−５０９８８９号公報の実施例に記載されている手順と同様の方法で、化合物(Ｐ−３)〜（Ｐ−６）を合成した。

Compounds (P-3) to (P-6) were synthesized by a method similar to the procedure described in the examples of JP-T-6-509889.

特開平９−１１８７１７号公報の実施例５に記載されている手順と同様の方法で、化合物(Ｐ−７)を合成した。

Compound (P-7) was synthesized by a method similar to the procedure described in Example 5 of JP-A-9-118717.

公知文献（Journal of Polymer Science: Part A: Polymer Chemistry(2009) 5426-5436）に記載されている手順に従い、化合物(Ｐ−８)を合成した。

Compound (P-8) was synthesized according to the procedure described in a publicly known document (Journal of Polymer Science: Part A: Polymer Chemistry (2009) 5426-5436).

特開平９−１１８７１７号公報の実施例４に記載されている手順に従って（Ｄ−１）を合成した。

(D-1) was synthesized according to the procedure described in Example 4 of JP-A-9-118717.

4-ブロモフェノール30.0g、アクリル酸t-ブチル33.5g、酢酸パラジウム50mg及び炭酸カリウム27.9gをN-メチルピロリドン300mLに溶解させ、120℃で3時間撹拌した。この反応溶液を室温まで冷却し、水900mL及びジクロロメタン300mlを加えた。有機層を分離し、さらに水層をジクロロメタン100mlで2回抽出した。有機層を集め、10％塩酸、飽和重曹水、飽和食塩水で洗浄した後、硫酸ナトリウムを加えて乾燥させた。硫酸ナトリウムを除去し、カラムクロマトグラフィー(アルミナ/シリカゲル、ジクロロメタン)を用いて精製し、溶媒を減圧留去することにより白色固体として4-ヒドロキシ桂皮酸t-ブチル（51g）を得た。

4-Bromophenol (30.0 g), t-butyl acrylate (33.5 g), palladium acetate (50 mg) and potassium carbonate (27.9 g) were dissolved in N-methylpyrrolidone (300 mL), and the mixture was stirred at 120 ° C. for 3 hours. The reaction solution was cooled to room temperature and 900 mL of water and 300 mL of dichloromethane were added. The organic layer was separated and the aqueous layer was extracted twice with 100 ml of dichloromethane. The organic layer was collected, washed with 10% hydrochloric acid, saturated aqueous sodium hydrogen carbonate and saturated brine, and dried by adding sodium sulfate. Sodium sulfate was removed, the residue was purified using column chromatography (alumina / silica gel, dichloromethane), and the solvent was distilled off under reduced pressure to obtain t-butyl 4-hydroxycinnamate (51 g) as a white solid.

  Next, 20.0 g of t-butyl 4-hydroxycinnamate, 20.0 g of 6-chlorohexyl acrylate and 59 g of cesium carbonate were dissolved in 150 ml of dimethyl sulfoxide and stirred at 60 ° C. for 3 hours. The reaction solution was cooled to room temperature, and 600 ml of water and 300 ml of dichloromethane were added. The organic layer was separated and the aqueous layer was extracted twice with 150 ml of dichloromethane. The organic layer was collected, washed with 10% hydrochloric acid, saturated aqueous sodium hydrogen carbonate and saturated brine, and dried by adding sodium sulfate. Sodium sulfate was removed, purification was performed using column chromatography (alumina / silica gel, dichloromethane), and the solvent was distilled off under reduced pressure to obtain 4- (6-acryloyloxy) cinnamate t-butyl (23 g) as a white solid. Obtained.

  Next, 23 g of t-butyl 4- (6-acryloyloxy) cinnamate obtained was dissolved in 70 ml of formic acid and stirred at 50 ° C. for 2 hours. 200 ml of water was added to the reaction solution, and the precipitated solid was collected by filtration. The solid was air-dried overnight, 150 ml of ethyl acetate and 200 ml of hexane were added, and the mixture was suspended and stirred. The solid was filtered to obtain 4- (6-acryloyloxy) cinnamic acid (10.75 g).

Next, 10.0 g of the obtained 4- (6-acryloyloxy) cinnamic acid, 3.0 g of phenol and 0.19 g of N, N-dimethylaminopyridine were dissolved in 70 ml of dichloromethane. The mixture was stirred at 0 ° C., and 5.15 g of N, N-diisopropylcarbodiimide was added dropwise. After stirring at room temperature for 2 hours, purification was performed using column chromatography (alumina / silica gel, dichloromethane (ethyl acetate 3%)), the solvent was distilled off under reduced pressure, and reprecipitation with methanol was performed as a white solid (D- 2) was obtained (9.89 g).
¹ H-NMR (400MHz, CDCl ₃ ) δ: 1.46-1.53 (m, 4H), 1.70-1.74 (m, 2H), 1.80-1.84 (m, 2H), 4.01 (t, J = 6.2Hz, 2H) , 4.19 (t, J = 6.6Hz, 2H), 5.82 (dd, J = 1.6Hz, 10.4Hz, 1H), 6.14 (dd, J = 10.4Hz, 17.4Hz, 1H), 6.41 (dd, J = 1.2 Hz, 17.2Hz, 1H), 6.49 (d, J = 16Hz, 1H), 6.92 (d, J = 8.4Hz, 2H), 7.16 (d, J = 8.4Hz, 2H), 7.25 (dd, J = 6.8 Hz, 1.0Hz, 1H) 7.40 (dd, J = 7.8 Hz, 7.8Hz, 2H), 7.53 (d, J = 8.4Hz, 2H) 7.82 (d, J = 16Hz, 1H)
EI-MS: 394 [M ⁺ ]

欧州特許出願ＥＰ−Ａ−０７６３５５２の例６に記載されている手順に従って（Ｄ−３）を合成した。

(D-3) was synthesized according to the procedure described in Example 6 of European Patent Application EP-A-0763552.

公知文献（Journal of Medicinal Chemistry, Vol.23(1980)、50-59）に記載されている手順に従い、（Ｄ−４）を合成した。

(D-4) was synthesized according to the procedure described in a known literature (Journal of Medicinal Chemistry, Vol. 23 (1980), 50-59).

特開平９−１１８７１７公報の実施例４に記載されている手順に従って（Ｄ−５）を合成した。

(D-5) was synthesized according to the procedure described in Example 4 of JP-A-9-118717.

公知文献（Molecules vol.11 (2007) 11, 2533-2545）に記載されている手順に従い、化合物(Ｄ−６)を合成した。

Compound (D-6) was synthesized according to a procedure described in a known document (Molecules vol.11 (2007) 11, 2533-2545).

マレイミド酢酸ブチル9.01g、酸化ジブチルスズ（IV）0.33g及びテトラデカノール9.14gをトルエン40mLに溶解させ、加熱還流しながら15時間撹拌した。この反応溶液を室温まで冷却し、トルエン100mlを加え、飽和重曹水、飽和食塩水の順で分液洗浄した。この溶液に硫酸ナトリウムを加えて乾燥させた。硫酸ナトリウムを除去し、溶媒を減圧留去して体積を50ml程度に減らし、ヘキサン40ml及びジクロロメタン20mlを加えた。カラムクロマトグラフィー(アルミナ/シリカゲル、ヘキサン/ジクロロメタン=2:1)を用いて精製し、溶媒を減圧留去し、メタノールで再沈殿することで白色結晶として(V-1)を得た（7.95g）。
¹H-NMR (400MHz, CDCl₃)δ: 0.88 (t, J=6.8Hz, 3H), 1.15-1.40 (m, 22H), 1.61-1.66 (tt, 2H), 4.14 (t, J=6.6Hz, 2H), 4.15 (s, 2H), 6.79 (s, 2H)
EI-MS:351[M⁺]

9.01 g of maleimidobutyl acetate, 0.33 g of dibutyltin (IV) oxide and 9.14 g of tetradecanol were dissolved in 40 mL of toluene and stirred for 15 hours while heating under reflux. The reaction solution was cooled to room temperature, 100 ml of toluene was added, and the mixture was separated and washed in the order of saturated aqueous sodium hydrogen carbonate and saturated brine. Sodium sulfate was added to this solution and dried. Sodium sulfate was removed, the solvent was distilled off under reduced pressure to reduce the volume to about 50 ml, and 40 ml of hexane and 20 ml of dichloromethane were added. Purification using column chromatography (alumina / silica gel, hexane / dichloromethane = 2: 1), the solvent was distilled off under reduced pressure, and reprecipitation with methanol gave (V-1) as white crystals (7.95 g ).
¹ H-NMR (400MHz, CDCl ₃ ) δ: 0.88 (t, J = 6.8Hz, 3H), 1.15-1.40 (m, 22H), 1.61-1.66 (tt, 2H), 4.14 (t, J = 6.6Hz , 2H), 4.15 (s, 2H), 6.79 (s, 2H)
EI-MS: 351 [M ⁺ ]

アクリル酸ステアリル（V-2）（東京化成工業製）を購入し用いた。

Stearyl acrylate (V-2) (manufactured by Tokyo Chemical Industry Co., Ltd.) was purchased and used.

N-(ブトキシメチル)アクリルアミド（V-3）（東京化成工業製）を購入し用いた。

N- (butoxymethyl) acrylamide (V-3) (manufactured by Tokyo Chemical Industry) was purchased and used.

公知文献（Farmaco. Edizione Scientifica Vol.22 (1967) 190, 590-598）に記載されている手順に従い、化合物(V-4)を合成した。

Compound (V-4) was synthesized according to a procedure described in a known literature (Farmaco. Edizione Scientifica Vol. 22 (1967) 190, 590-598).

公知文献（Journal of the American Chemical Society Vol.119 (1997) 13, 3027-3037）に記載されている手順と同様の手順で、化合物(V-5)を合成した。

Compound (V-5) was synthesized by a procedure similar to that described in known literature (Journal of the American Chemical Society Vol. 119 (1997) 13, 3027-3037).

エポキシデカン（V-6）(東京化成工業製)を購入し用いた。

Epoxy decane (V-6) (manufactured by Tokyo Chemical Industry Co., Ltd.) was purchased and used.

(Preparation of polymer (A-1) having photochemically isomerizable moiety)
1 part (10.0 mmol) of the compound represented by the formula (P-1) was dissolved in 10 parts of ethyl methyl ketone to obtain a solution 1. Next, 0.01 part of azobisisobutyronitrile (AIBN) was added to Solution 1 and heated under reflux for 2 days under a nitrogen atmosphere to obtain Solution 2. Next, the solution 2 was dropped and stirred in 60 parts of methanol, and the precipitated solid was filtered. The obtained solid was dissolved in 5 parts of tetrahydrofuran (THF), dropped into 120 parts of ice-cooled hexane and stirred, and the precipitated solid was filtered. The obtained solid was dissolved in 5 parts of THF, stirred dropwise in 120 parts of ice-cooled methanol, and the precipitated solid was filtered. The obtained solid was dissolved in THF and then vacuum-dried to obtain a polymer (A-1) having a photochemically isomerizable moiety.

(Preparation of polymers (A-2) to (A-6) having photochemically isomerizable moieties)
In the same manner as (A-1), polymers (A-2) to (A-6) having photochemically isomerizable sites were obtained. The composition of each substance is as shown in Table 1.

(Preparation of polymer (A-8) having photochemically isomerizable moiety)
A compound (10.0 mmol) represented by the formula (P-8) and 3,5-di-t-butylphenol are added to a Schlenk flask whose glass surface has been silylated in advance, and 10 ml of dry tetrahydrofuran is added and dissolved. The reaction system was purged with nitrogen. Next, 0.2 ml of a 1M hexane solution of phosphazene (t-butyl-4-phosphorus) was added and heated at 60 ° C. for 2 days to obtain Solution 5. Next, the solution 5 was dropped and stirred in 600 ml of a mixed solvent (methanol: concentrated hydrochloric acid: water = 97: 1: 2 (V: V: V)), and the precipitated solid was separated. Next, the obtained solid was dissolved in 15 ml of tetrahydrofuran, dropped into and stirred in 400 ml of methanol, and the obtained solid was dried in a high vacuum to obtain a photoalignment film substance (A-8). .

(Preparation of polymers (AV-1) to (AV-4) having photochemically isomerizable sites)
In the same manner as (A-1), polymers (AV-1) to (AV-4) having photochemically isomerizable sites were obtained. The composition of each substance is as shown in Table 2.

(Preparation of polymer (AV-7) having photochemically isomerizable moiety)
A compound represented by the formula (P-7) (0.7 mmol), a compound represented by the formula (V-5) (0.7 mmol) and 0.04 g of poly (methylhydrogensiloxane) were dissolved in 3 ml of toluene, Solution 3 was obtained. The reaction system containing the solution 1 was degassed under vacuum and purged with nitrogen. Next, 8 μl of a platinum-divinyltetramethyldisiloxane complex solution was sprayed onto the reaction mixture at room temperature while stirring, and the solution was stirred at 55 ° C. for 24 hours to obtain a solution 4. Next, the solution 4 was dropped and stirred in 400 ml of hexane, and the precipitated solid was separated and dried. The resulting solid was then dissolved in about 5 ml of toluene and precipitated in 400 ml of methanol. After repeating this operation twice, the polymer (AV-7) having a site capable of photochemical isomerization was obtained by drying in a high vacuum.

(Preparation of polymer having photochemically isomerizable moiety (AV-8))
In a Schlenk flask in which the glass surface was previously silylated, the compound (5.0 mmol) represented by the formula (P-8), the compound (5.0 mmol) represented by the formula (V-6), and 3, 5 -Di-t-butylphenol was added, 10 ml of dry tetrahydrofuran was added and dissolved, and the reaction system was purged with nitrogen. Next, 0.2 ml of a 1M hexane solution of phosphazene (t-butyl-4-phosphorus) was added and heated at 60 ° C. for 2 days to obtain Solution 5. Next, the solution 5 was dropped and stirred in 600 ml of a mixed solvent (methanol: concentrated hydrochloric acid: water = 97: 1: 2 (V: V: V)), and the precipitated solid was separated. Next, the obtained solid was dissolved in 15 ml of tetrahydrofuran, dropped and stirred in 400 ml of methanol, and the obtained solid was dried in a high vacuum, whereby a polymer having a photochemically isomerizable moiety (AV -8) was obtained.

(Preparation of polymer (AC-1) having photochemically isomerizable moiety and photochemically crosslinkable moiety)
Dissolve 0.5 part (5,0 mmol) of the compound represented by the formula (P-1) and 0.63 part (5.0 mmol) of the compound represented by the formula (D-1) in 10 parts of ethyl methyl ketone. Solution 1 was obtained. Next, 0.01 part of azobisisobutyronitrile (AIBN) was added to Solution 1 and heated under reflux for 2 days under a nitrogen atmosphere to obtain Solution 2. Next, the solution 2 was dropped and stirred in 60 parts of methanol, and the precipitated solid was filtered. The obtained solid was dissolved in 5 parts of tetrahydrofuran (THF), dropped into 120 parts of ice-cooled hexane and stirred, and the precipitated solid was filtered. The obtained solid was dissolved in 5 parts of THF, stirred dropwise in 120 parts of ice-cooled methanol, and the precipitated solid was filtered. The obtained solid was dissolved in THF and then vacuum dried to obtain a polymer (AC-1) having a photochemically isomerizable site and a photochemically crosslinkable site.

(Preparation of polymers (AC-2) to (AC-8) having photochemically isomerizable sites and photochemically crosslinkable sites)
(AC-2) to (AC-8) were obtained in the same manner as (AC-1). The composition of each substance is as shown in Table 3.

(Preparation of polymer (AC-9) having photochemically isomerizable moiety and photochemically crosslinkable moiety)
A compound represented by the formula (P-7) (0.7 mmol), a compound represented by the formula (D-5) (0.7 mmol) and 0.04 g of poly (methylhydrogensiloxane) were dissolved in 3 ml of toluene, Solution 3 was obtained. The reaction system containing the solution 1 was degassed under vacuum and purged with nitrogen. Next, 8 μl of a platinum-divinyltetramethyldisiloxane complex solution was sprayed onto the reaction mixture at room temperature while stirring, and the solution was stirred at 55 ° C. for 24 hours to obtain a solution 4. Next, the solution 4 was dropped and stirred in 400 ml of hexane, and the precipitated solid was separated and dried. The resulting solid was then dissolved in about 5 ml of toluene and precipitated in 400 ml of methanol. This operation was repeated twice, followed by drying in a high vacuum to obtain a polymer (AC-9) having a photochemically isomerizable site and a photochemically crosslinkable site.

(Preparation of polymer (AC-10) having photochemically isomerizable moiety and photochemically crosslinkable moiety)
In a Schlenk flask in which the glass surface was previously silylated, the compound represented by the formula (P-8) (5.0 mmol), the compound represented by the formula (D-6) (5.0 mmol), and 3, 5 -Di-t-butylphenol was added, 10 ml of dry tetrahydrofuran was added and dissolved, and the reaction system was purged with nitrogen. Next, 0.2 ml of a 1M hexane solution of phosphazene (t-butyl-4-phosphorus) was added and heated at 60 ° C. for 2 days to obtain Solution 5. Next, the solution 5 was dropped and stirred in 600 ml of a mixed solvent (methanol: concentrated hydrochloric acid: water = 97: 1: 2 (V: V: V)), and the precipitated solid was separated. Next, the obtained solid is dissolved in 15 ml of tetrahydrofuran, stirred dropwise in 400 ml of methanol, and the obtained solid is dried in a high vacuum, so that photochemically isomerizable sites and photochemical crosslinking are performed. A polymer (AC-10) with possible sites was obtained.

(Preparation of polymer (C-1) having photochemically crosslinkable sites)
1 part (10.0 mmol) of the compound represented by the formula (D-1) was dissolved in 10 parts of ethyl methyl ketone to obtain Solution 1. Next, 0.01 part of azobisisobutyronitrile (AIBN) was added to Solution 1 and heated under reflux for 2 days under a nitrogen atmosphere to obtain Solution 2. Next, the solution 2 was dropped and stirred in 60 parts of methanol, and the precipitated solid was filtered. The obtained solid was dissolved in 5 parts of tetrahydrofuran (THF), dropped into 120 parts of ice-cooled hexane and stirred, and the precipitated solid was filtered. The obtained solid was dissolved in 5 parts of THF, stirred dropwise in 120 parts of ice-cooled methanol, and the precipitated solid was filtered. The obtained solid was dissolved in THF and then vacuum-dried to obtain a polymer (C-1) having a photochemically crosslinkable moiety.

(Preparation of polymers (C-2) to (C-4) having photochemically crosslinkable sites)
In the same manner as (C-1), polymers (C-2) to (C-4) having photochemically isomerizable sites were obtained. The composition of each substance is as shown in Table 4.

(Preparation of polymers (CV-1) to (CV-4) having photochemically crosslinkable sites)
In the same manner as (C-1), polymers (CV-1) to (CV-4) having photochemically isomerizable sites were obtained. The composition of each substance is as shown in Table 5.

(Preparation of photoalignable liquid crystal alignment layer composition (LPM-1))
(A-1) 0.05 g and (C-1) 0.95 g were dissolved in 10 ml of tetrahydrofuran in an eggplant flask, and then the tetrahydrofuran was distilled off under reduced pressure. A composition (LPM-1) was obtained.

(Preparation of composition (LPM-2) to (LPM-9) for liquid crystal alignment layer capable of photo-alignment)
In the same manner as (LPM-1), photoalignable compositions for liquid crystal alignment layers (LPM-2) to (LPM-9) were obtained. The composition of each substance is as shown in Table 6 and Table 7.

(Preparation of composition (LPM-10) to (LPM-21) for liquid crystal alignment layer capable of photo-alignment)
In the same manner as (LPM-1), photoalignable compositions for liquid crystal alignment layers (LPM-10) to (LPM-21) were obtained. The composition of each substance is as shown in Table 8 and Table 9.

(Preparation of composition (LPM-10) to (LPM-21) for liquid crystal alignment layer capable of photo-alignment)
In the same manner as (LPM-1), photoalignable compositions for liquid crystal alignment layers (LPM-10) to (LPM-21) were obtained. The composition of each substance is as shown in Table 10, Table 11, Table 12, and Table 13.

(Evaluation as photo-alignment film)
Example 1
A liquid crystal alignment layer composition (LPM-1) capable of photo-alignment was dissolved in N-methylpyrrolidone (NMP) by 0.5% and stirred at room temperature for 10 minutes. Next, the solution was applied onto a glass plate as a substrate using a spin coater and dried at 100 ° C. for 30 minutes.
Next, the ultra high pressure mercury lamp was coated with linearly polarized light of visible ultraviolet light (wavelength 365 nm, irradiation intensity: 20 mW / cm ² ) and parallel light through a wavelength cut filter, a band pass filter, and a polarizing filter. The glass plate substrate was irradiated from an oblique direction of 45 degrees. The irradiation amount was 90 mJ / cm ² .

  A liquid crystal cell was manufactured using the coated glass plate prepared by the above method. The distance between the plates was set to 10 μm, and two glass plates were bonded together. Next, the nematic liquid crystal mixture (RDP-V0037 manufactured by DIC) was filled in the cell at a temperature just exceeding the clearing point (Tc = 84.4 ° C.), and then cooled to room temperature. When the tilt angle of the liquid crystal in the cell was measured optically by the crystal rotation method, the tilt angle was 1 degree.

Hereinafter, in the same manner as in (LPM-1), liquid crystal cells were prepared for (LPM-2) to (LPM-41), and the results of measurement of the tilt angle are also shown in Table 14, Table 15, Table 16, and Table. 17 shows. Regarding the liquid crystal alignment, the presence of abnormal domains and alignment unevenness of the liquid crystal cell was observed, and the case of 0 places was evaluated as ○, the case of 2 or less places as Δ, and the case of 3 or more places as x. The pretilt angle is optically measured by the crystal rotation method.For the vertical alignment cell, the case of 88 degrees or more and less than 89 degrees is ○, the case of 80 degrees or more and less than 88 degrees and the case of 89 degrees or more and 90 degrees or less is Δ, The case of less than 80 degrees was set as x. For the horizontally oriented cells, the case of 1 degree or more and less than 2 degrees was indicated by ◯, the case of 2 degree or more and less than 10 degrees and 0 degree or more and less than 1 degree were indicated by Δ, and the case of 10 degrees or more was indicated by ×. For light stability, the liquid crystal cell is irradiated with non-polarized ultraviolet rays at 30 J / cm ² , and the change in the pretilt angle before and after irradiation is less than 0.3 degrees, the case where it is 0.3 degrees or more and less than 1 degree is Δ, The case of 1 degree or more was set as x.

以上の結果から、本発明の光配向膜用物質によって、極めて少ない紫外線照射量で、液晶配向性に優れ、プレチルト角が大きく、光安定性の高い光配向膜が得られることが判る。

From the above results, it can be seen that the photo-alignment film material of the present invention can provide a photo-alignment film having excellent liquid crystal orientation, a large pretilt angle, and high light stability with an extremely small amount of ultraviolet irradiation.

(Comparative Example 1)
For comparison, the liquid crystal alignment layer compositions (LPM-A1), (LPM-C1), (LPM-AV1) and (LPM-CV1) that can be aligned in the same manner as in Example 1 are used. Prepared.

又、実施例１と同様の方法で各種測定を行った結果を表１９に示す。

Table 19 shows the results of various measurements performed in the same manner as in Example 1.

以上の結果から、光化学的に異性化可能であり、かつ光化学的に架橋されない部位を持たないサンプルでは、多くの紫外線照射を必要とし、配向安定性に劣ることが分かる。又、光化学的に架橋可能な部位を持たないサンプルでは、光安定性に劣ることが分かる。
したがって、本発明によって、少ない紫外線照射量で配向およびプレチルト角の制御が可能であり、配向安定性および光安定性に優れるといった効果を有する垂直配向用組成物及び当該組成物を用いた垂直配向層を得られることが分かる。
（重合性液晶組成物（ＬＣ−１）の調製）

From the above results, it can be seen that a sample that can be photochemically isomerized and does not have a site that is not photochemically cross-linked requires a lot of ultraviolet irradiation and is inferior in alignment stability. In addition, it can be seen that the sample having no photochemically crosslinkable portion is inferior in light stability.
Therefore, according to the present invention, it is possible to control the orientation and the pretilt angle with a small amount of ultraviolet irradiation, and the composition for vertical alignment having the effects of excellent alignment stability and light stability, and a vertical alignment layer using the composition It can be seen that
(Preparation of polymerizable liquid crystal composition (LC-1))

式（ｍ）で示される化合物１５部、式（ｎ）で示される化合物１５部をキシレン７０部に溶解させた後、イルガキュア９０７（チバスペシャリティケミカルズ（株）社製）１．２部、式（ｐ）で示されるアクリル共重合体０．３部を加え、溶液を得た。得られた溶液を０．４５μｍのメンブランフィルターでろ過し、重合性液晶組成物（ＬＣ−１）を得た。
（重合性液晶組成物（ＬＣ−２）の調製）

After dissolving 15 parts of the compound represented by formula (m) and 15 parts of the compound represented by formula (n) in 70 parts of xylene, 1.2 parts of Irgacure 907 (manufactured by Ciba Specialty Chemicals Co., Ltd.), 0.3 parts of the acrylic copolymer represented by p) was added to obtain a solution. The obtained solution was filtered with a 0.45 μm membrane filter to obtain a polymerizable liquid crystal composition (LC-1).
(Preparation of polymerizable liquid crystal composition (LC-2))

式（ｍ）で示される化合物４３部、式（ｎ）で示される化合物４３部および式（ｑ）で示される化合物１４部をプロピレングリコールモノメチルエーテルアセテート７０部に溶解させた後、イルガキュア６５１（チバスペシャリティケミカルズ（株）社製）２部を加え、溶液を得た。得られた溶液を０．４５μｍのメンブランフィルターでろ過し、重合性液晶組成物（ＬＣ−２）を得た。

43 parts of the compound represented by the formula (m), 43 parts of the compound represented by the formula (n) and 14 parts of the compound represented by the formula (q) were dissolved in 70 parts of propylene glycol monomethyl ether acetate, and then Irgacure 651 (Ciba 2 parts of Specialty Chemicals Co., Ltd. were added to obtain a solution. The obtained solution was filtered with a 0.45 μm membrane filter to obtain a polymerizable liquid crystal composition (LC-2).

(Evaluation method of orientation)
The orientation of the optical anisotropic body was evaluated in five stages by visual observation and observation with a polarizing microscope.
A: Uniform orientation is obtained visually, and there are no defects even when observed with a polarizing microscope. B: Uniform orientation is obtained visually, but the orientation area is 90 to 100% when observed with a polarizing microscope.
C: Although alignment as much as A and B is not obtained visually, the alignment area in observation with a polarizing microscope is 60 to 90%.
D: Nearly non-oriented by visual observation, but the orientation area by polarizing microscope observation is 40 to 60%.
E: No orientation by visual observation, and orientation area by polarization microscope observation is 40% or less

(Solvent / chemical resistance evaluation method)
The solvent and chemical resistance of the optical anisotropic body is determined by applying NMP / 2-butoxyethanol (BC) as a test solvent on the optical anisotropic body obtained with a spin coater and drying at 80 ° C. for 1 minute. The results of observing the film state were evaluated in five stages by visual observation and observation with a polarizing microscope. The test solvent used here is a combination of solvents generally used for the purpose of diluting the alignment film composition.
A: No change in film visually, no defects even with polarization microscope observation B: No change in film visually, but cracks observed in polarization microscope observation C: Partial film peeling off with visual observation However, the occurrence of cracks in the polarizing microscope is the same level as B. D: Most of the film is peeled off visually. E: The whole film is peeled off visually.

(Preparation of photo-alignment film and preparation of optical anisotropic body)
(Example 42)
The material for photo-alignment film (LPM-1) was dissolved in N-methylpyrrolidone (NMP) by 0.5% and stirred at room temperature for 10 minutes. Next, the solution was applied onto a glass plate as a substrate using a spin coater and dried at 100 ° C. for 30 minutes.
Next, the ultra high pressure mercury lamp was coated with linearly polarized light of visible ultraviolet light (wavelength 365 nm, irradiation intensity: 20 mW / cm ² ) and parallel light through a wavelength cut filter, a band pass filter, and a polarizing filter. The glass plate substrate was irradiated from an oblique direction of 45 degrees. The irradiation amount was 90 mJ / cm ² .
The polymerizable liquid crystal composition (LC-1) was applied onto the obtained photo-alignment film with a spin coater, dried at 80 ° C. for 1 minute, and then irradiated with 1 J / cm ² of ultraviolet light in a nitrogen atmosphere, and (LC- 1) was polymerized to obtain an optical anisotropic body. As a result, the orientation was A, and good orientation could be obtained with a small dose of 90 mJ / cm ² . The evaluation result of solvent resistance and chemical resistance of the optical anisotropic body was B. When the orientation direction was observed, the orientation was homogeneous.

  The optical anisotropic body of the present invention has high solvent resistance and chemical resistance, and the optical anisotropic body of the present invention can impart orientation and control the orientation direction with an extremely small amount of UV irradiation during production. It turns out that it is.

(Examples 43 to 88)
The optical anisotropic films of Examples 43 to 88 were used in the same manner as in Example 1 except that the materials for optical alignment film (LPM-2) to (LPM-41) were used instead of the optical alignment film material (LPM-1). Table 20, Table 21, Table 22, and Table 23 collectively show the results of preparing the body and examining the orientation, solvent resistance / chemical resistance, and orientation direction.

以上の結果から、実施例２から４７の光学異方体もまた耐溶剤・耐薬品性が高く光学異方体は製造に際して極めて少ない紫外線照射量で、配向性を付与すること及び、配向方向のコントロールが可能であることが判る。

From the above results, the optical anisotropic bodies of Examples 2 to 47 also have high solvent resistance and chemical resistance, and the optical anisotropic bodies can impart orientation with an extremely small amount of UV irradiation during production, and It can be seen that control is possible.

(Comparative Examples 5 to 8)
For comparison, compositions for liquid crystal alignment layers (LPM-A1), (LPM-C1), (LPM-AV1) and (LPM-CV1) capable of photo-alignment were prepared at the ratios shown in Table 18, respectively.
(LPM-A1) and (LPM-AV1) do not contain compounds with photochemically crosslinkable sites, and (LPM-C1) and (LPM-CV1) have photochemically isomerizable sites It does not contain a compound. Using these photoalignable liquid crystal alignment layer compositions, the optical anisotropic bodies of Comparative Examples 5 to 8 were prepared in the same manner as in Example 1, and the orientation, solvent resistance / chemical resistance, and orientation direction were adjusted. The examination results are shown together in Table 24.

以上の結果から、光化学的に架橋可能な部位を持たない、光配向可能な液晶配向層用組成物（LPM-A1）又は（LPM-AV1）を用いた光学異方体は、耐溶剤・耐薬品性に問題があることが分かる。又、光化学的に異性化可能な部位を持たない、光配向可能な液晶配向層用組成物（LPM-C1）又は（LPM-CV1）を用いた光学異方体は、液晶配向性が劣り、その製造に際して、多くの紫外線照射を必要とすることが分かる。

From the above results, optically anisotropic bodies using the photoalignable liquid crystal alignment layer composition (LPM-A1) or (LPM-AV1) that do not have photochemically crosslinkable sites are It can be seen that there is a problem with chemical properties. In addition, the optically anisotropic body using the photoalignable liquid crystal alignment layer composition (LPM-C1) or (LPM-CV1) having no photochemically isomerizable site has poor liquid crystal alignment, It can be seen that the production requires a lot of ultraviolet irradiation.

  The liquid crystal alignment layer composition of the present invention can produce a photo-alignment film with a small amount of optically anisotropic light, and can be used for optical anisotropic bodies such as liquid crystal display elements and optical compensation films. It can use suitably for manufacture of. Furthermore, the present invention has a liquid crystal orientation capable of controlling the orientation with a small UV irradiation amount, can obtain an arbitrary pretilt angle, is excellent in light stability, and is not eroded by a solvent or the like. Has characteristics.

Claims (26)

(a) a polymer having a photochemically isomerizable site and (b) a polymer having a photochemically crosslinkable site, wherein (a) and (b) have different structures. A composition for an alignment layer of a liquid crystal. The composition according to claim 1, wherein (a) does not undergo a photochemical crosslinking reaction at the isomerizable site. A composition according to claim 1 or 2 comprising at least one further monomer or polymer. The composition according to any one of claims 1 to 3, comprising two or more polymers having photochemically isomerizable sites. The composition as described in any one of Claims 1-4 containing 2 or more types of polymers which have a site | part which can be photochemically crosslinked. As polymers having photochemically isomerizable moieties, the following general formulas (Ia-1) to (Id-1), (If-1) to (Ii-1), (Im-1) to (Ip-1) )

(In the formula, Ma represents a monomer unit of the polymer, S _a and S _aa each represents a spacer unit which may be the same or different, P is photochemically isomerizable, and photochemically Represents a site not cross-linked, V represents a side chain end)

(In the formula, S _a , S _{aa and} S _aaa are the same or different spacer units, D represents a photochemically crosslinkable site, and Ma, P and V represent general formulas (Ia -1) means the same)),

(In the formula, S _a , S _aa, S _aaa , D, Ma, P and V represent the same meaning as in the general formula (Ib-1)).

(In the formula, Ma and Mb each represent a monomer unit of a polymer which may be the same or different, and S _a , S _aa, S _b and S _bb may be the same or different spacers, respectively. Unit represents, Va and Vb represent side chain ends, and D and P represent the same meaning as in the general formula (Ib-1)).

(In the formula, M _a and M _c each represent a monomer unit of a polymer that may be the same or different, and S _a and S _c each represent a spacer unit that may be the same or different. , V _c represents a side chain end, and P represents the same meaning as in the general formula (Ia-1)).

(In the formula, M _a and M _c each represents a monomer unit of a polymer which may be the same or different, and S _a , S _aa and S _c may be the same or different, respectively. Represents a unit, V _c represents a side chain end, and P and D represent the same meaning as in the general formula (Ib-1)).

(In the formula, M _a and M _c each represents a monomer unit of a polymer which may be the same or different, and S _a , S _aa and S _c may be the same or different, respectively. Represents a unit, V _c represents a side chain end, and P and D represent the same meaning as in the general formula (Ib-1)).

(In the formula, M _a , M _b and M _c each represent a monomer unit of a polymer which may be the same or different, and S _a , S _b and S _c may be the same or different, respectively. Represents a good spacer unit, V _c represents a side chain end, and P and D represent the same meaning as in the general formula (Ib-1)).

(Wherein, S _a spacer unit, Ma and P have the same meanings as those in formula (Ia-1).),

( _Wherein , S _a , S _aa, D, Ma and P represent the same meaning as in general formula (Ib-1)).

( _Wherein , S _a , S _aa, D, Ma and P represent the same meaning as in general formula (Ib-1)).

(In the formula, M _a and M _b each represent a monomer unit of a polymer that may be the same or different, and S _a and S _b each represent a spacer unit that may be the same or different. , P and D represent the same meaning as in formula (Ib-1).) The composition according to any one of claims 1 to 5, comprising a cured product of a monomer selected from the group consisting of: As polymers having photochemically isomerizable moieties, the following general formulas (Ia) to (Id), (If) to (Ii), (Im) to (Ip)

(In the formula, Ma and Md each represent a monomer unit of a polymer which may be the same or different, and the monomer unit of Md may be composed of one type or two or more different units, and S _a and S _aa each represents a different spacer unit, P represents a photochemically isomerizable and non-photochemically cross-linked site, V represents a side chain end, x and w are the moles of the copolymer. In any case, 0 <x ≦ 1 and 0 ≦ w <1, and n represents 4 to 1000000).

(In the formula, S _a , S _{aa and} S _aaa are the same or different spacer units, D represents a photochemically crosslinkable site, and Ma, Md, P, V, x, w And n represent the same meaning as in the general formula (Ia).

( _Wherein , S _a , S _aa, S _aaa , D, Ma, Md, P, V, x, w and n represent the same meaning as in general formula (Ib)).

(In the formula, Ma, Mb and Md each represent a monomer unit of a polymer which may be the same or different, and the arrangement of Ma, Mb and Md may be the same as or different from the formula. The monomer unit may be composed of one type or two or more different units, and S _a , S _aa, S _b and S _bb each represents a spacer unit which may be the same or different, and Va and Vb represents the end of the side chain, x, y and w represent the mole fraction of the copolymer, and in each case 0 <x <1, 0 <y <1, and 0 ≦ w <1 , D, P and n represent the same meaning as in general formula (Ib)).

(In the formula, M _a , M _c and M _d each represent a monomer unit of a polymer which may be the same or different, and the arrangement of M _a , M _c and M _d may be the same as the formula The monomer units of M _d may be different from one another or may be composed of two or more different units, and x, z and w represent the mole fraction of the copolymer, and 0 <x <1 and 0 <z <1 and satisfies 0 ≦ w <1, represents the S _a and S _c good spacer unit are each independently selected from a same, V _c represents the side chain end, P and n represent the same meaning as in the general formula (Ia)).

(In the formula, M _a , M _c and M _d each represent a monomer unit of a polymer which may be the same or different, and the arrangement of M _a , M _c and M _d may be the same as the formula The monomer units of M _d may be different from one another or may be composed of two or more different units, and x, z and w represent the mole fraction of the copolymer, and 0 <x <1 and 0 <z <1 and 0 ≦ w <1 are satisfied, S _a , S _aa and S _c each represents a spacer unit which may be the same or different, and V _c represents a side chain terminal P, D and n represent the same meaning as in general formula (Ib)).

(In the formula, M _a , M _c and M _d each represent a monomer unit of a polymer which may be the same or different, and the arrangement of M _a , M _c and M _d may be the same as the formula The monomer units of M _d may be different from one another or may be composed of two or more different units, and x, z and w represent the mole fraction of the copolymer, and 0 <x <1 and 0 <z <1 and 0 ≦ w <1 are satisfied, S _a , S _aa and S _c each represents a spacer unit which may be the same or different, and V _c represents a side chain terminal P, D and n represent the same meaning as in general formula (Ib)).

(In the formula, M _a , M _b , M _c and M _d each represent a monomer unit of a polymer which may be the same or different, and the arrangement of M _a , M _b , M _c and M _d is the formula May be the same as or different from each other, the monomer unit of M _d may be composed of one kind or two or more kinds of different units, and x, y, z and w represent the molar fraction of the copolymer. 0 <x <1, 0 <y <1, 0 <z <1, and 0 ≦ w <1, and S _a , S _b and S _c are the same or different represents an spacer unit even though, V _c represents the side chain terminal, P, D and n are. represents the same meaning as in formula (Ib)),

(Wherein, S _a spacer unit, Ma, Md, P, x , w and n have the same meanings as those in formula (Ia).),

(In the formula, S _a , S _aa, D, Ma, Md, P, x, w and n represent the same meaning as in the general formula (Ib)).

(In the formula, S _a , S _aa, D, Ma, Md, P, x, w and n represent the same meaning as in the general formula (Ib)).

(In the formula, M _a , M _b and M _d each represent a monomer unit of a polymer which may be the same or different, and the arrangement of M _a , M _b and M _d may be the same as the formula The monomer units of M _d may be different from one another or may be composed of two or more different units, and x, y and w represent the mole fraction of the copolymer, and 0 <x <1 and 0 <y <1 and satisfies 0 ≦ w <1, represents the S _a and S _b good spacer unit are each independently selected from a same, P, D and n have the general formula (It has the same meaning as (Ib).)
The composition as described in any one of Claims 1-6 containing the polymer chosen from the group which consists of. As a polymer having a photochemically crosslinkable moiety, a general formula (Ie-1)

(In the formula, Ma represents a monomer unit of the polymer, S _a and S _aa each represents a spacer unit which may be the same or different, D represents a photochemically crosslinkable site, and V represents a side. Cured product of monomer represented by general formula (Ij-1) and general formula (Ij-2)

(Wherein, M _a and M _c each represent a monomer unit of a polymer that may be the same or different, and S _a and S _c each represent a spacer unit that may be the same or different, D represents a photochemically crosslinkable site, and V _c represents a side chain end.) Or a cured product of the monomer represented by the general formula (Iq-1)

(In the formula, it represents a monomer unit of a Ma polymer, S _a represents _a spacer unit, and D represents a photochemically crosslinkable site). The composition according to any one of the above. As a polymer having a photochemically crosslinkable moiety, a polymer represented by the general formula (Ie)

(Wherein, Ma and Md each represents a monomer unit may be different even in the same polymer, monomer units M _d may be composed of two or more different units in one, S _a And S _aa each represents a spacer unit, which may be the same or different, D represents a photochemically crosslinkable site, V represents a side chain end, x and w represent the mole fraction of the copolymer. A polymer represented by the general formula (Ij): 0 <x ≦ 1 and 0 ≦ w <1, and n represents 4 to 1000000.

(In the formula, M _a , M _c, and M _d each represent a monomer unit of a polymer that may be the same or different, and the arrangement of M _a , M _c, and M _d is the same as or different from the formula The monomer unit of M _d may be composed of one kind or two or more kinds of different units, and x, z and w represent the mole fraction of the copolymer, and 0 <x < 1 and 0 <z <1 and satisfies 0 ≦ w <1, represents the S _a and S _c good spacer unit are each independently selected from a same, D is a photochemically crosslinkable site represents, V _c represents the side chain end, n represents a polymer represented by the representative.) the 4-1,000,000, or the general formula (Iq)

(Wherein, Ma and Md each represents a monomer unit may be different even in the same polymer, monomer units M _d may be composed of two or more different units in one, S _a Represents a spacer unit, D represents a photochemically crosslinkable site, x and w represent the molar fraction of the copolymer, and in each case 0 <x ≦ 1 and 0 ≦ w <1 And n represents 4 to 1000000.) The composition according to any one of claims 1 to 6, comprising a polymer represented by: Formula (Ik-1)

(Wherein, M _c represents a monomer unit of the polymer, S _c represents a spacer unit, and V _c represents a side chain end), and includes a cured product of the monomer represented by any one of claims 1 to 9. A composition according to claim 1. General formula (Ik)

(In the formula, M _c and M _d each represent a monomer unit of a polymer which may be the same or different, and the monomer unit of M _d may consist of one type or two or more different units, S _c represents a spacer unit, V _c represents a side chain end, z and w represent the molar fraction of the copolymer, and in each case 0 <z ≦ 1 and 0 ≦ w <1 The composition according to any one of claims 1 to 10, comprising a polymer represented by: n represents 4 to 1,000,000. Polymers having photochemically crosslinkable moieties are represented by formulas (II-1) to (II-8)

(In the formula, a broken line represents a bond to Sa, Saa, Saaa, Sb, or Sbb, and any hydrogen atom in each structure may be substituted with a fluorine atom, a chlorine atom, a methyl group, or a methoxy group. The composition according to any one of claims 1 to 11, which is a polymer having a group selected from: Ma, Mb and Mc are each independently represented by formulas (III-1) to (III-17)

(In the formula, a broken line represents a bond to Sa, Sb or Sc, R independently represents hydrogen or an alkyl group having 1 to 5 carbon atoms, and an arbitrary hydrogen atom in each structure represents a fluorine atom, chlorine The composition according to claim 1, which represents an atom, a methyl group or a methoxy group. The composition according to any one of claims 1 to 13, wherein the polymer having a photochemically isomerizable moiety is a homopolymer having an azo group. The composition according to any one of claims 1 to 14, wherein the polymer having a photochemically crosslinkable moiety is a polymer having a group selected from formulas (II-6) to (II-8). S _a , S _aa , S _aaa , S _b, S _bb and S _c are each represented by the following general formula (IV)

(Where the dashed line represents binding to Ma, Mb, M _c , P, V, Va, Vb, V _c or D;
Z ¹ , Z ² and Z ³ are each independently a single bond, — (CH ₂ ) _u —, —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CH═CH—, _{-CF = CF -, - CF 2} O -, - OCF 2 -, - CF 2 CF 2 - or an -C≡C-, u represents 1 to 20, wherein non-adjacent CH ₂ groups of an alkyl group Can be independently substituted by Q, where Q is —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—, —O—CO—O—, wherein R independently represents hydrogen or an alkyl group having 1 to 5 carbon atoms;
A ¹ and A ² are each independently a trans-1,4-cyclohexylene group, a trans-1,3-dioxane-2,5-yl group, a 1,4-naphthylene group, a 2,6-naphthylene group, 2,5-pyridyl group, 2,5-pyrimidyl group, 2,5-thiophenylene group, 2,5-furanylene group or 1,4-phenylene group, which are unsubstituted or one or more hydrogen atoms May be substituted by a fluorine atom, a chlorine atom, a methyl group or a methoxy group;
p and q represent 0 or 1. )
The composition as described in any one of Claims 1-15 represented by these. V, Va, Vb and Vc are represented by the following general formula (V),

(Where the dashed line represents a bond to S _c , S _aa , S _bb or S _aaa ;
Z ⁴ , Z ⁵ , Z ⁶ and Z ⁷ are each independently a single bond, — (CH ₂ ) _u —, —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CH═ CH—, —CF═CF—, —CF ₂ O—, —OCF ₂ —, —CF ₂ CF ₂ — or —C≡C—, where u represents 1 to 20, where non-adjacent of an alkyl group One or more of the CH ₂ groups can be independently replaced by Q, where Q is —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—, —O—CO—O—, wherein R independently represents hydrogen or an alkyl group having 1 to 5 carbon atoms;
A ³ , A ⁴ , A ⁵ and A ⁶ are each independently trans-1,4-cyclohexylene group, trans-1,3-dioxane-2,5-yl group, 1,4-naphthylene group, 2 , 6-naphthylene group, 2,5-pyridyl group, 2,5-pyrimidyl group, 2,5-thiophenylene group, 2,5-furylene group or 1,4-phenylene group, which are unsubstituted Or one or more hydrogen atoms may be substituted by fluorine atom, chlorine atom, methyl group or methoxy group;
r, s, t and w represent 0 or 1;
R ² represents hydrogen, fluorine, chlorine, a cyano group or an alkyl group having 1 to 20 carbon atoms (which may be appropriately substituted with fluorine, and one CH ₂ group or two or more non-adjacent CH 2 groups may be —O— , -CO-O-, -O-CO- and / or -CH = CH-). )
The composition in any one of Claims 1-16 represented by these. P is the following general formula (VI)

(In the formula, a broken line represents a bond to S _a , S _b , S _aa , and S _aaa , but when only one broken line is bonded, the other broken line is bonded to a hydrogen atom;
A ¹ , A ² , A ³ , A ⁴ and A ⁵ are each independently 1,4-naphthylene group, 2,6-naphthylene group, 2,5-pyridyl group, 2,5-pyrimidyl group, 2, Represents a 5-thiophenylene group, a 2,5-furylene group or a 1,4-phenylene group, which are unsubstituted, fluorine atom, chlorine atom, bromine atom, methyl group, methoxy group, nitro group, -NR Monosubstituted or polysubstituted by ¹ R ² or by linear or branched alkyl residues having 1 to 10 carbon atoms, the alkyl residues being unsubstituted or monosubstituted or polysubstituted by fluorine Wherein one or more of the non-adjacent CH ₂ groups can be independently replaced by Q, where Q is —O—, —CO—, —CO—O—, —O—CO _{-, - Si (CH 3)} 2 -O-Si (CH 3) 2 -, - R—, —NR—CO—, —CO—NR—, —NR—CO—O—, —O—CO—NR—, —NR—CO—NR—, —CH═CH—, —C≡C— , -O-CO-O-, wherein R, R ¹ and R ² independently represent hydrogen or an alkyl group having 1 to 5 carbon atoms;
p, q, r, s and t each independently represent 0 or 1, but 0 <q + r + s + t. )
The composition as described in any one of Claims 1-17 represented by these. D represents the following general formula (VII)

(In the formula, the broken line represents the bond to S _a , S _aa , S _aaa , S _b and S _bb , but when only one broken line is bonded, the other broken line is bonded to a hydrogen atom. ;
A ⁷ is independently 1,4-naphthylene group, 2,6-naphthylene group, 2,5-pyridyl group, 2,5-pyrimidyl group, 2,5-thiophenylene group, 2,5-furylene group. Or a 1,4-phenylene group, which is unsubstituted or one or more hydrogen atoms may be substituted by a fluorine atom, a chlorine atom, a methyl group or a methoxy group;
X and Y are each independently hydrogen, fluorine, chlorine, a cyano group or an alkyl group having 1 to 20 carbon atoms (which may be appropriately substituted with fluorine, and optionally one CH ₂ group or two or more non-adjacent CH ₂ groups represent -O-, -CO-O-, -O-CO- and / or -CH = CH-);
Z is a single bond, —O— or —NR ¹ — (wherein R ¹ is hydrogen, a linear or branched alkyl group having 1 to 20 carbon atoms optionally substituted with fluorine or chlorine, or optionally fluorine , A cycloalkyl group having 3 to 8 ring members which may be substituted with chlorine, an alkyl group or an alkoxy group);
r represents 0, 1 or 2. )
The composition as described in any one of Claims 1-18 represented by these. 20. The composition according to any one of claims 1 to 19, wherein Ma, Mb and Mc each independently represents an acrylate, methacrylate, acrylamide, methacrylamide, maleic acid derivative, siloxane or epoxide. 21. Composition according to any one of the preceding claims, characterized in that it comprises (c) a compound that stabilizes vertical alignment as at least one further substance. The liquid crystal aligning layer for vertical alignment mode liquid crystal display elements using the composition as described in any one of Claims 1-21. A vertical alignment mode liquid crystal display device using the liquid crystal alignment film according to claim 22. The liquid crystal aligning layer for horizontal alignment mode liquid crystal display elements using the composition as described in any one of Claims 1-20. A horizontal alignment mode liquid crystal display element using the liquid crystal alignment layer according to claim 24. In the optical anisotropic body comprised by the polymer of a polymeric liquid crystal composition, the polymeric liquid crystal molecule in this polymeric liquid crystal composition is used using the composition as described in any one of Claims 1-21. An optically anisotropic body characterized by being oriented.

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