JP4957976B2 - Composition for vertical alignment layer - Google Patents

Description

  The present invention relates to a material for aligning liquid crystal in a liquid crystal display element, and relates to a material for manufacturing a vertical alignment layer of liquid crystal.

  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, various methods have been studied since the alignment of liquid crystal greatly affects the display characteristics. Among them, a liquid crystal display device using a vertical alignment type liquid crystal layer (sometimes referred to as a VA mode liquid crystal display device) replaces a liquid crystal display device using a horizontal alignment type liquid crystal layer because of excellent display characteristics. Widely used for display. However, even in the VA mode liquid crystal display device, the viewing angle characteristic is not necessarily sufficient when compared with a self-luminous display element, and various methods have been studied to improve the viewing angle characteristic. It was.

  In order to improve viewing angle characteristics in a VA mode liquid crystal display device, a multi-domain vertical alignment method (MVA method) in which an alignment division structure in which a plurality of liquid crystal domains are formed in one pixel is introduced. 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. For example, there is a problem that a distribution occurs in the response speed. 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 voltage is applied to polymerize the monomer in a tilted state by applying a voltage to change the tilt direction of the liquid crystal molecules. A memorized polymer orientation support (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 for applying a force for controlling the tilt alignment to the vertical alignment film, but it is difficult to form a precise alignment division structure, and there is a problem of generation of static electricity and impurity components due to friction.

  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 control of horizontal alignment by the conventional photo-alignment method is widely known, but in order to control the vertical alignment in which the alignment direction is completely different, the structure is completely different from the conventional photo-alignment film for horizontal alignment. It is necessary to use a material for a vertical alignment layer having This material is required to exhibit 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 even in active matrix driving. The material for forming the material has not been known so far.

  On the other hand, a composition for a photoalignment layer having an azo group as a skeleton having a photochemically isomerizable site and a cinnamate skeleton as a skeleton having a photochemically crosslinkable site has already been disclosed. (See Patent Documents 3, 4 and 5). In the side chain polymer, a skeleton having an azo group as a skeleton having a photochemically isomerizable site and a cinnamic acid skeleton as a skeleton having a photochemically crosslinkable site in the same side chain. The polymer which has and the example which used this for the material for photo-alignment layers have already been disclosed (refer patent document 6 and 7). However, Patent Document 6 only discloses use as an optical nonlinear polymer, and does not disclose use as a photo-alignment film. In Patent Documents 1, 2, 3, 4, 5 and 7, the composition is used for the purpose of horizontally aligning liquid crystal molecules on a substrate, and a skeleton is formed on a vertical alignment layer having a completely different alignment. It is impossible to use a material for a photo-alignment layer having Furthermore, since there is no disclosure of specific means used for vertical alignment, development of a material for a photo-alignment film has been required for vertical alignment applications.

JP 2003-149647 A Japanese Patent No. 2682771 JP-A-6-287453 Japanese Patent Laid-Open No. 10-310613 Special table 2002-517605 gazette Japanese Patent Publication No. 6-509889 JP 2002-90750 A

  An object of the present invention is to provide a vertical alignment material having a liquid crystal alignment property capable of controlling alignment with a small amount of ultraviolet irradiation, a large pretilt angle, and excellent light stability, and a vertical alignment layer using the material. There is.

  As a result of intensive investigations on various materials to solve the above-mentioned problems, the present inventors have solved the above-mentioned problems by using them as compounds having three characteristic structures or as materials for vertical alignment containing the compounds. As a result, the present invention was completed.

  The present invention stabilizes (a) a site that is photochemically isomerizable and not photochemically crosslinked, (b) a site that can be photochemically crosslinked, and (c) a vertical orientation in one molecule. A liquid crystal vertical alignment layer material comprising a monomer having a moiety or an oligomer, prepolymer or polymer of the monomer, and a vertical alignment layer polymer and vertical alignment layer using the vertical alignment layer material composition provide.

  By using the material for a vertical alignment layer of the present invention, a vertical alignment layer whose alignment is controlled with a small amount of ultraviolet irradiation can be produced. Since the vertical alignment layer has a large pretilt angle and excellent light stability, a VA mode liquid crystal display device having an alignment division structure and excellent viewing angle characteristics can be efficiently manufactured.

The material for the vertical alignment layer of the liquid crystal used in the present invention comprises, in one molecule, (a) a site that can be photochemically isomerized and not photochemically crosslinked, (b) a site that can be photochemically crosslinked, And (c) a monomer having a portion that stabilizes vertical alignment or an oligomer, prepolymer or polymer of the monomer.
In the material for the vertical alignment layer of the present invention, the photochemically crosslinkable site is from general formula (VIII-1) to general formula (VIII-8).

(式中、破線はS_a、S_aa又はS_aaa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) で表される構造であることが好ましく、一般式(VIII-6)、(VIII-7)又は(VIII-8)がより好ましく、(VIII-7)がさらに好ましい。

(Wherein the broken line represents a bond to S _a , S _aa or S _aaa, and any hydrogen atom in each structure may be substituted by a fluorine atom, a chlorine atom, a methyl group or a methoxy group) A structure represented by formula (VIII-6), (VIII-7) or (VIII-8) is more preferred, and (VIII-7) is more preferred.

In order to improve the thermal stability of the polymer, the general formula (VIII-3), (VIII-4) or (VIII-5) is preferred. In order to improve the solubility of the polymer, the general formula (VIII-1), (VIII-2), (VIII-6), (VIII-7) or (VIII-8) is preferred, and the general formula (VIII -6), (VIII-7) or (VIII-8) is more preferred. In order to improve the speed of the photocrosslinking reaction, the general formula (VIII-2), (VIII-6), (VIII-7) or (VIII-8) is preferable, and the general formula (VIII-7) is more preferable. preferable.
More specifically, (a) a site that can be photochemically isomerized and not photochemically crosslinked, (b) a site that can be photochemically crosslinked, and (c) a site that stabilizes vertical alignment, It is preferable that it is the aspect described below.
(Monomer embodiment)
A monomer having a site that can be photochemically isomerized and not photochemically crosslinked, a site that can be photochemically crosslinked, and a site that stabilizes vertical alignment is represented by the general formula (Ia) or (Ib). If it is a compound.

( _{Wherein La} represents _a polymerizable group, S _a , S _aa and S _aaa each represent a spacer unit which may be different, P is photochemically isomerizable and not photochemically crosslinked) represents sites, D is represents a photochemically crosslinkable site, V _a represents a site to stabilize the vertical alignment.)
Although the vertical alignment layer for liquid crystals is comprised by the polymer of the said monomer or the composition containing the said monomer, what is described below is preferable as these specific aspects.
(Mode of polymer for vertical alignment layer)
An embodiment comprising a cured product of the monomer described in the embodiment of the monomer or a composition containing the monomer, wherein the cured product has a structural unit represented by the general formula (IIa) or (IIb).

(In the formula, M _a and M _d each independently represent a monomer unit of an oligomer, a prepolymer or a polymer, and x and w are the mole fraction of each monomer unit in the general formula (IIa) and the general formula (IIb)). Represents a ratio, satisfies 0 <x ≦ 1 and 0 ≦ w <1, S _a , S _aa and S _aaa each represent a different spacer unit, P is photochemically isomerizable, and represents a site that is not photochemically crosslinked, D is represents a photochemically crosslinkable site, V _a represents a site to stabilize the vertical orientation, n is representative of 4～100,000.)
The liquid crystal vertical alignment layer is obtained by forming a polymer layer for a liquid crystal vertical alignment layer on the surface of a substrate used for aligning liquid crystals, and then irradiating with light to perform crosslinking and / or isomerization.
Since the compounds represented by the general formula (Ia) and the general formula (Ib) have polymerizability, the compound has a polymerizable substituent. Specifically polymerizable substituents, the substituents in L _a are each independently formula (III-1) ~ (III -17)

(In the formula, a broken line represents a bond to S _a , R independently represents hydrogen or an alkyl group having 1 to 5 carbon atoms, and any hydrogen atom in each structure may be substituted) It is preferably any substituent selected from the group consisting of general formulas (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, Formula (III-1), (III-2), (III-3), (III-6), (III-7), (III-8), (III-13), (III-16) or ( III-17) is more preferred, and general formula (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 general 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, among which general formulas (III-1), (III-2), (III-10) , (III-12) or (III-17) is particularly preferred. In order to improve the polymerization rate, the general formulas (III-3), (III-8), (III-10), (III-12), (III-13), (III-14), (III -15), (III-16) or (III-17) are preferred, among which general formula (III-3), (III-8), (III-10), (III-12) or (III-17) Is more preferable. In order to narrow the molecular weight distribution of the polymer, the general formula (III-2), (III-10), (III-11) or (III-12) is preferable. In order to improve the stability of the orientation, the general 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 general formulas (III-1), (III-6), (III-7), (III-8), (III-9), (III-10) , (III-12), (III-13) or (III-17) are preferred, and among them, general 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 unit (M _a ), and _a known monomer unit can be used without particular limitation. Moreover, there is no restriction | limiting in particular in the order and randomness of the arrangement | sequence of the monomer unit (Ma and _Md ) in _a polymer. Further, as the monomer unit (M _d ), 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 not photochemically crosslinked. It is desirable to use them to such an extent that they do not interfere with the effects of (b) photochemically crosslinkable sites and (c) sites that stabilize vertical alignment. The monomer unit (M _d ) is preferably acrylate, methacrylate, acrylamide, methacrylamide, maleic acid derivatives, siloxanes or epoxides, or acryloyloxy group, methacryloyloxy group, 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, Mention may be made of maleic esters, fumaric esters, siloxanes, vinyl groups and epoxy groups. Specifically, the formulas (QIII-1) to (QIII-17) can be used.

(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, (Optionally 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 addition, as the monovalent organic group, the general formula (QIV)

（式中、破線はモノマー単位（M_d）への結合を表わし、S_aaaはスペーサー単位を表し、Ｖ_aは垂直配向を安定化する部位を表す。）
を例示することができる。
一般式（Ia）、（Ib）、（IIa）、（IIb）、及び（QIV）において、S_a、S_aa及びS_aaaがそれぞれ独立して、一般式（IV）

(In the formula, a broken line represents a bond to the monomer unit (M _d ), S _aaa represents a spacer unit, and V _a represents a site that stabilizes vertical alignment.)
Can be illustrated.
In the general formulas (Ia), (Ib), (IIa), (IIb), and (QIV), S _a , S _aa, and S _aaa are each independently represented by the general formula (IV)

(Wherein the dashed line represents a bond to _{L a, M a, P,} D or V _a,
Z ¹ , Z ² and Z ³ are each independently a single bond, — (CH ₂ ) _u — (wherein _u represents 1 to 20), —OCH ₂ —, —CH ₂ O—, — COO—, —OCO—, —CH═CH—, —CF═CF—, —CF ₂ O—, —OCF ₂ —, —CF ₂ CF ₂ — or —C≡C—, but these substituents In the formula, one or more of non-adjacent CH ₂ groups are independently —O—, —CO—, —CO—O—, —O—CO—, —Si (CH ₃ ) ₂ —O—Si (CH _3). ) ₂ —, —NR—, —NR—CO—, —CO—NR—, —NR—CO—O—, —O—CO—NR—, —NR—CO—NR—, —CH═CH—, -C≡C- or -O-CO-O- (wherein R independently represents hydrogen or an alkyl group having 1 to 5 carbon atoms),
A ¹ and A ² are each independently a trans-1,4-cyclohexylene group, a trans-1,3-dioxane-2,5-diyl group, a 1,4-naphthylene group, a 2,6-naphthylene group, Represents a pyridine-2,5-diyl group, a pyrimidine-2,5-diyl group, a 2,5-thiophenylene group, a 2,5-furylene group or a 1,4-phenylene group, which are unsubstituted or One or more hydrogen atoms may be substituted by fluorine atoms, chlorine atoms, methyl groups or methoxy groups,
p and q each independently represent 0 or 1. )
Is preferably a structure represented by

Z ¹ , Z ² and Z ³ 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 independently , -O-, -CO-, -CO-O-, -O-CO-, -NR-, -NR-CO-, -CO-NR-, -NR-CO-NR-, -CH = CH- represents -C≡C- or -O-CO-O-a, 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— is preferred, and A ¹ and A ² are each independently a trans-1,4-cyclohexylene group, trans-1, 3-dioxane-2,5-diyl group, 1,4-naphthylene group, 2,6-naphthylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group It is 1,4-phenylene group represents, they preferably substituted by unsubstituted or substituted with or one or more hydrogen atoms are fluorine atom, a chlorine atom, a methyl group or a methoxy group, Z ^1, Z ² and Z ³ is each independently a single bond, — (CH ₂ ) _u — (wherein _u represents 1 to 10, and one or more of non-adjacent CH ₂ groups are independently —O—, — CO—, —CO—O—, —O—CO—, —NR—, —NR—CO—, —CO—NR—, —CH═CH— or —C≡C—, where R is hydrogen, methyl A group or an ethyl group), —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CH═CH—, or —C≡C— is more preferred, and A ¹ and A ² are Each independently represents a trans-1,4-cyclohexylene group, a 2,6-naphthylene group, or a 1,4-phenylene group, It is more preferable that these are unsubstituted or one or more hydrogen atoms are substituted with a fluorine atom, a chlorine atom, a methyl group or a methoxy group, and Z ¹ , Z ² and Z ³ are each independently a single atom. A bond, — (CH ₂ ) _u — (wherein _u represents 1 to 6 and one or more of the non-adjacent CH ₂ groups are independently —O—, —CO—O—, —O—CO; —, —CH═CH— or —C≡C—), —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CH═CH—, or —C≡C—. Particularly preferably, A ¹ and A ² each independently represent a trans-1,4-cyclohexylene group, a 2,6-naphthylene group, or a 1,4-phenylene group, which are unsubstituted or one It is particularly preferred that the above hydrogen atoms are substituted by fluorine atoms, methyl groups or methoxy groups. .

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 general formula (Sa-1) to general formula (S-ad-9)

Is particularly preferred.
Among these, general formulas (Sa-6) to (Sa-16), general formulas (Sb-3) to (Sb-10), general formulas (Sc-3) to (Sc-10), and general formulas (Sd -3) to (Sd-12), general formulas (Sk-4) to (Sk-7), general formulas (Sl-13) to (Sl-17), general formulas (So-3) to (So-14) ), General formula (Sp-2) to (Sp-13), general formula (Ss-1) to (Ss-8), general formula (St-1) to (St-8), general formula (Sy-1 ) To (Sy-9) and compounds represented by the general formulas (S-aa-1) to (S-aa-9) are more preferable.
Formula (Ia), formula (Ib), formula (IIa), formula (IIb), and in the general formula (QIV), V _a is represented by the following general formula (V)

(In the formula, the broken line represents the bond to S _aaa ,
Z ⁴ , Z ⁵ , Z ⁶ and Z ⁷ are each independently a single bond, — (CH ₂ ) _u — (wherein _u represents 1 to 20), —OCH ₂ —, —CH ₂ O. —, —COO—, —OCO—, —CH═CH—, —CF═CF—, —CF ₂ O—, —OCF ₂ —, —CF ₂ CF ₂ — or —C≡C— One or more of the non-adjacent CH ₂ groups in the substituents are independently —O—, —CO—, —CO—O—, —O—CO—, —Si (CH ₃ ) ₂ —O—Si. (CH ₃ ) ₂ —, —NR—, —NR—CO—, —CO—NR—, —NR—CO—O—, —O—CO—NR—, —NR—CO—NR—, —CH═ CH—, —C≡C— or —O—CO—O— (wherein R independently represents hydrogen or an alkyl group having 1 to 5 carbon atoms),
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 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, May be unsubstituted or one or more hydrogen atoms may be replaced by fluorine, chlorine, methyl or methoxy groups;
r, s, t and u each independently represents 0 or 1,
R ² represents hydrogen, fluorine, chlorine, a cyano group or an alkyl group having 1 to 20 carbon atoms, and the hydrogen atom in the alkyl group may be substituted with a fluorine atom, and one CH ₂ group or two or more These non-adjacent CH ₂ groups may be substituted with —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 general formula (Va-1) to general formula (Vq-10)

Is particularly preferred.
Among them, general formulas (Va-1) to (Va-15), general formulas (Vb-11) to (Vb-15), general formulas (Vc-1) to (Vc-11), general formulas (Vd-10) ~ (Vd-15), general formula (Vf-1) ~ (Vf-10), general formula (Vg-1) ~ (Vg-10), general formula (Vh-1) ~ (Vh-10), general Formulas (Vj-1) to (Vj-9), general formulas (Vl-1) to (Vl-11), or general formulas (Vm-1) to (Vm-11) are more preferable.
In general formula (Ia), general formula (Ib), general formula (IIa) and general formula (IIb), P represents the following general formula (VI)

(In the formula, a broken line represents a bond to S _a , S _aa or S _aaa ,
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-diyl group, pyrimidine-2,5-diyl. Group, 2,5-thiophenylene group, 2,5-furylene group, 1,3-phenylene group or 1,4-phenylene group, which are unsubstituted or one or more hydrogen atoms are fluorine atoms , Chlorine atom, bromine atom, methyl group, methoxy group, nitro group, —NR ¹ R ² (wherein R ¹ and R ² each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms) Or a linear or branched alkyl group having 1 to 10 carbon atoms, the alkyl group may be unsubstituted or substituted with a fluorine atom,
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, a 1,3-phenylene group or a 1,4-phenylene group, which are unsubstituted, or one or more hydrogen atoms are fluorine atoms, chlorine atoms, It is preferably substituted with a bromine atom, a methyl group, a methoxy group or a nitro group, and 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 1,4-phenylene group, which are unsubstituted, or one or more hydrogen atoms are fluorine atom, chlorine atom, methyl group, methoxy group And more preferably q + r + s + t More preferably 1 to ^{2, A 1, A 2, A} 3, A 4 and A ⁵ are each independently a 2,6-naphthylene group, or 1,4-phenylene group, they are unsubstituted It is particularly preferred that one or more hydrogen atoms are substituted by fluorine atoms, chlorine atoms, methyl groups, methoxy groups, and it is particularly preferred that p and q + r + s + t are 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, a 1,3-phenylene 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 general formula (Pa-1) to general formula (Pe-7)

Is particularly preferred.
Among them, compounds represented by general formulas (Pa-1) to (Pa-9), general formulas (Pb-1) to (Pb-8), general formulas (Pc-1) or general formulas (Pe-5) Further preferred.
In general formula (Ia), general formula (Ib), general formula (IIa) and general formula (IIb), D represents the following general formula (VII),

(In the formula, a broken line represents a bond to S _a , S _aa or S _aaa ,
A ⁷ is 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, Represents a 5-furylene group, a 1,3-phenylene 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. It ’s okay,
X and Y each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group or an alkyl group having 1 to 20 carbon atoms, and the hydrogen atom in the alkyl group may be substituted with a fluorine atom. , One CH ₂ group or two or more non-adjacent CH ₂ groups may be substituted with —O—, —CO—O—, —O—CO— and / or —CH═CH—,
Z is a single bond, —O— or —NR ¹ — (wherein R ¹ is a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, or a cycloalkyl group having 3 to 8 ring members. Wherein the alkyl group is unsubstituted or optionally substituted with a fluorine atom or a chlorine atom, the cycloalkyl group is unsubstituted or an alkyl group having 1 to 10 carbon atoms, Which may be substituted with an alkoxy group having 1 to 10 carbon atoms, a fluorine atom or a chlorine atom),
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 1,4-naphthylene group, 2,6-naphthylene group, 2,5-thiophenylene group, 1,3-phenylene group or 2,5-furylene group. Is preferred. 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 general formula (Da-1) to general formula (Dd-7)

Is particularly preferred.
Among these, compounds represented by general formulas (Da-1) to (Da-10) or general formulas (Db-1) to (Db-10) are more preferable.
[Preparation of polymer for alignment layer]
The monomers in the present invention can be used alone or mixed with other monomers and used as a composition. This composition can be prepared in any mixing ratio, but in one molecule, (a) a site that can be photochemically isomerized and not photochemically crosslinked, (b) a photochemically. It is preferable that the amount of the monomer having a crosslinkable portion and (c) a portion for stabilizing the vertical alignment is 0.1 to 50% by weight of the composition. Moreover, it is preferable that the other monomer which comprises the said composition has a site | part which can be bridge | crosslinked photochemically, and a site | part which stabilizes vertical alignment. These compounds are preferably liquid crystalline compounds.

  In the present invention, the monomer and the composition are used for polymerizing to prepare a polymer. In the polymerization, a polymerization initiator can be arbitrarily used in accordance with the polymerization mode of the polymerization functional group, and examples of the polymerization initiator include polymer synthesis and reaction (edited by the Polymer Society, Kyoritsu Shuppan). It is known. Examples of the thermal polymerization initiator in radical polymerization include azo compounds such as azobisisobutyronitrile and peroxides such as benzoyl peroxide. Photopolymerization initiators include 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-hydroxycyclohexylphenyl Ketone, benzoin ether, 2,2-diethoxyacetophenone, acetophenone compounds such as 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 and 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 carried out by dissolving the composition 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, etc. Two or more organic solvents may be used in combination. The polymer in the present invention can also be obtained by dissolving the 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. The liquid crystal alignment layer thus obtained can be referred to as a photo-alignment film. 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 the photo-alignment film of the present invention, the composition in the present invention is dissolved in a solvent and applied onto a substrate, and then the coating film is heated or irradiated with light to prepare a polymer, and further irradiated with light. Further, a method for producing an alignment film by exhibiting the alignment control ability can also be mentioned. As the solvent used for dissolving the composition, a solvent similar to the solvent used for dissolving the polymer in the previous period 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, by further producing a photo-alignment film on the substrate on which the alignment film has been formed in advance, the orientation direction and orientation angle by the composition or the polymer of the present invention. The control ability 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. 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. An 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 composition or the polymer solution in the present invention on a substrate 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 composition in the present invention is used, it is possible to prepare a polymer on the substrate by performing thermal polymerization in the heating step, and in this case, a polymerization initiator may be contained in the composition. preferable. 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. The oblique direction refers to an inclination with respect to a direction parallel to the substrate surface, and the inclination angle is referred to as a pretilt angle. When used as an alignment film for vertical alignment, generally, the pretilt angle is preferably 70 to 89.8 °.

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. For the light from these light sources, linearly polarized light can be obtained by using a polarizing filter or a polarizing prism. 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 ^{20mW / 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.
[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 liquid crystal is dropped on the alignment film surface so that the alignment films face each other. 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, for example, dicyanobenzene liquid crystal, pyridazine liquid crystal, Schiff base liquid crystal, azoxy liquid crystal, naphthalene liquid crystal, biphenyl liquid crystal, phenylcyclohexane. System liquid crystal or the like is used.

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.
The liquid crystal display element of the present invention thus produced is excellent in various properties such as display characteristics and reliability.

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.
Examples 1 to 8 Synthesis of liquid crystal vertical alignment layer materials

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、液晶の垂直配向層用材料である化合物(Ｐ−１)〜（Ｐ−６）を合成した。

Compounds (P-1) to (P-6), which are materials for vertical alignment layers of liquid crystals, were synthesized by the same method as described in the examples of JP-T-6-509889.

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-7) 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−８)を合成した。

Compound (P-8) was synthesized according to the procedure described in known literature (Journal of Materials Chemistry, Vol. 19 (2009), 60-62).

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-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).

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 ⁺ ]

N-(ブトキシメチル)アクリルアミド（V-2）（東京化成工業製）を購入し用いた。

N- (butoxymethyl) acrylamide (V-2) (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-3)を合成した。

Compound (V-3) was synthesized according to a procedure described in a known literature (Farmaco. Edizione Scientifica Vol. 22 (1967) 190, 590-598).

(Example 9) Preparation of alignment layer polymer (ACV-1) 1 part (10 mmol) of a compound represented by the formula (P-1), which is a material for liquid crystal vertical alignment layer, is 10 parts of ethyl methyl ketone (MEK). 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 an alignment layer polymer (ACV-1).
(Examples 10 to 14) Preparation of alignment layer polymers (ACV-2) to (ACV-6) In the same manner as the alignment layer polymer (ACV-1), the alignment layer polymers (ACV-2) to (ACV-) 6) was obtained. The composition of each polymer is as shown in Table 1.

Examples 15 to 32 Preparation of Alignment Layer Polymers (ACVC-1) to (ACVC-10) and (ACVV-1) to (ACVV-8) Alignment in the same manner as the alignment layer polymer (ACV-1). Polymers for layers (ACVC-1) to (ACVC-10) and (ACVV-1) to (ACVV-8) were obtained. The composition of each polymer is as shown in Tables 2 and 3.

(Example 33) Preparation of alignment layer and electro-optical element 0.5% of alignment layer polymer (ACV-1) was dissolved in N-methylpyrrolidone (NMP) 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 70 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, a nematic liquid crystal mixture having the following composition having a negative dielectric anisotropy

Was filled into the cell at a temperature just above 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 89 degrees.
Examples 34 to 49 Preparation of Alignment Layer and Electro-Optic Element Hereinafter, the alignment layer polymers (ACV-2) to (ACV-6) and (ACVC-), similarly to the alignment layer polymer (ACV-1). 1) to (ACVC-10) and (ACVV-1) to (ACVV-8) were also prepared for alignment layers, liquid crystal cells, and measured tilt angles. It is shown in FIG. 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, ○ when it is 88 degrees or more and less than 89 degrees, △ when it is 80 degrees or more and less than 88 degrees and 89 degrees or more and 90 degrees or less, and when it is less than 80 degrees X. 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.

From the above results, it can be seen that the alignment layer polymer of the present invention can provide a vertical alignment layer having excellent liquid crystal alignment, a large pretilt angle, and high light stability with a very small amount of ultraviolet irradiation. In addition, when the liquid crystal cell thus obtained was sandwiched between two orthogonal polarizing plates and the voltage was turned on and off between the electrodes, a clear change in brightness was observed, and an electro-optic element could be obtained.
(Comparative Example 1)
For comparison, the alignment layer polymers (A-1), (C-1), (AV-1) and (AC-1) shown in Table 7 were prepared in the same manner as in Example 1.

又、実施例１と同様の方法で配向層を作製し、各種測定を行った結果を表８に示す。

In addition, Table 8 shows the results of producing an alignment layer by the same method as in Example 1 and performing various measurements.

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. Further, it can be seen that a sample having no site for stabilizing the vertical alignment cannot give a desired pretilt angle.

  Therefore, according to the present invention, the composition can be controlled with a small amount of UV irradiation, the pretilt angle is large, the composition for vertical alignment having the effects of excellent alignment stability and light stability, and the vertical alignment using the composition. It can be seen that an alignment layer polymer, a vertical alignment layer, and an electro-optic element can be obtained.

Claims (17)

Monomer having (a) a site that is photochemically isomerizable and not photochemically cross-linked, (b) a site that can be photochemically cross-linked, and (c) a site that stabilizes vertical alignment in one molecule. Alternatively, a material for a vertical alignment layer of liquid crystal containing an oligomer, prepolymer or polymer of the monomer. Monomers having photochemically isomerizable and non-photochemically cross-linked sites, photochemically cross-linkable sites, and sites that stabilize vertical alignment are represented by the general formula (Ia) or (Ib)

( _{Wherein La} represents _a polymerizable group, S _a , S _aa and S _aaa each represent a spacer unit which may be different, P is photochemically isomerizable and not photochemically crosslinked) The material according to claim 1, wherein D represents a site capable of photochemical crosslinking, and V _a represents a site that stabilizes vertical alignment. Monomers or oligomers, prepolymers or monomers having photochemically isomerizable and photochemically non-crosslinkable sites, photochemically crosslinkable sites, and sites that stabilize vertical alignment in one molecule The material according to claim 1, wherein the site that is photochemically isomerizable and not photochemically crosslinked in the polymer is an azo group. Monomers or oligomers, prepolymers or monomers having photochemically isomerizable and photochemically non-crosslinkable sites, photochemically crosslinkable sites, and sites that stabilize vertical alignment in one molecule In the polymer, the photochemically crosslinkable site is changed from the general formula (VIII-1) to the general formula (VIII-8).

(In the formula, a broken line represents a bond to S _a , S _aa or S _aaa, and any hydrogen atom in each structure may be substituted by a fluorine atom, a chlorine atom, a methyl group or a methoxy group) The material of claim 1 represented. Formula (Ia) and the general formula (Ib), L _a is the formula from the formula (III-1) (III- 17)

(In the formula, a broken line represents a bond to S _a , R independently represents hydrogen or an alkyl group having 1 to 5 carbon atoms, and any hydrogen atom in each structure may be substituted) The material according to claim 2, which represents any substituent selected from the group consisting of: In general formula (Ia) and general formula (Ib), S _a , S _aa and S _aaa are each independently represented by general formula (IV),

(Wherein the dashed line represents a bond to _{L a, M a, P,} D or V _a,
Z ¹ , Z ² and Z ³ are each independently a single bond, — (CH ₂ ) _u — (wherein _u represents 1 to 20), —OCH ₂ —, —CH ₂ O—, — COO—, —OCO—, —CH═CH—, —CF═CF—, —CF ₂ O—, —OCF ₂ —, —CF ₂ CF ₂ — or —C≡C—, but these substituents In the formula, one or more of non-adjacent CH ₂ groups are independently —O—, —CO—, —CO—O—, —O—CO—, —Si (CH ₃ ) ₂ —O—Si (CH _3). ) ₂ —, —NR—, —NR—CO—, —CO—NR—, —NR—CO—O—, —O—CO—NR—, —NR—CO—NR—, —CH═CH—, -C≡C- or -O-CO-O- (wherein R independently represents hydrogen or an alkyl group having 1 to 5 carbon atoms),
A ¹ and A ² are each independently a trans-1,4-cyclohexylene group, a trans-1,3-dioxane-2,5-diyl group, a 1,4-naphthylene group, a 2,6-naphthylene group, Represents a pyridine-2,5-diyl group, a pyrimidine-2,5-diyl group, a 2,5-thiophenylene group, a 2,5-furylene group or a 1,4-phenylene group, which are unsubstituted or One or more hydrogen atoms may be substituted by fluorine atoms, chlorine atoms, methyl groups or methoxy groups,
p and q each independently represent 0 or 1. )
The material according to claim 2 represented by: In the general formula (Ia) and formula (Ib), V _a is the general formula (V)

(In the formula, the broken line represents the bond to S _aaa ,
Z ⁴ , Z ⁵ , Z ⁶ and Z ⁷ are each independently a single bond, — (CH ₂ ) _u — (wherein _u represents 1 to 20), —OCH ₂ —, —CH ₂ O. —, —COO—, —OCO—, —CH═CH—, —CF═CF—, —CF ₂ O—, —OCF ₂ —, —CF ₂ CF ₂ — or —C≡C— One or more of the non-adjacent CH ₂ groups in the substituents are independently —O—, —CO—, —CO—O—, —O—CO—, —Si (CH ₃ ) ₂ —O—Si. (CH ₃ ) ₂ —, —NR—, —NR—CO—, —CO—NR—, —NR—CO—O—, —O—CO—NR—, —NR—CO—NR—, —CH═ CH—, —C≡C— or —O—CO—O— (wherein R independently represents hydrogen or an alkyl group having 1 to 5 carbon atoms),
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 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, May be unsubstituted or one or more hydrogen atoms may be replaced by fluorine, chlorine, methyl or methoxy groups;
r, s, t and u each independently represents 0 or 1,
R ² represents hydrogen, fluorine, chlorine, a cyano group or an alkyl group having 1 to 20 carbon atoms, and the hydrogen atom in the alkyl group may be substituted with a fluorine atom, and one CH ₂ group or 2 These non-adjacent CH ₂ groups may be substituted with —O—, —CO—O—, —O—CO— and / or —CH═CH—. )
The material of Claim 2 or 6 represented by these. In general formula (Ia) and general formula (Ib), P represents general formula (VI).

(In the formula, a broken line represents a bond to S _a , S _aa or S _aaa ,
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-diyl group, pyrimidine-2,5-diyl. Group, 2,5-thiophenylene group, 2,5-furylene group, 1,3-phenylene group or 1,4-phenylene group, which are unsubstituted or one or more hydrogen atoms are fluorine atoms , Chlorine atom, bromine atom, methyl group, methoxy group, nitro group, —NR ¹ R ² (wherein R ¹ and R ² each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms) Or a linear or branched alkyl group having 1 to 10 carbon atoms, the alkyl group may be unsubstituted or substituted with a fluorine atom,
p, q, r, s and t each independently represent 0 or 1, but 0 <q + r + s + t. )
The material of Claim 2 or 6 represented by these. In general formula (Ia) and general formula (Ib), D represents general formula (VII)

(In the formula, a broken line represents a bond to S _a , S _aa or S _aaa , but when only one broken line is bonded, the other broken line is bonded to a hydrogen atom;
A ⁷ is 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, Represents a 5-furylene group, a 1,3-phenylene 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. It ’s okay,
X and Y each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group or an alkyl group having 1 to 20 carbon atoms, and the hydrogen atom in the alkyl group may be substituted with a fluorine atom. , One CH ₂ group or two or more non-adjacent CH ₂ groups may be substituted with —O—, —CO—O—, —O—CO— and / or —CH═CH—,
Z is a single bond, —O— or —NR ¹ — (wherein R ¹ is a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, or a cycloalkyl group having 3 to 8 ring members. Wherein the alkyl group is unsubstituted or optionally substituted with a fluorine atom or a chlorine atom, the cycloalkyl group is unsubstituted or an alkyl group having 1 to 10 carbon atoms, Which may be substituted with an alkoxy group having 1 to 10 carbon atoms, a fluorine atom or a chlorine atom),
r represents 0, 1 or 2. )
The material of Claim 2 or 6 represented by these. It is comprised by the hardened | cured material of the composition containing the composition of Claim 2, and this hardened | cured material is general formula (IIa) or general formula (IIb)

(In the formula, M _a and M _d each independently represent a monomer unit of an oligomer, a prepolymer or a polymer, and x and w are the mole fraction of each monomer unit in the general formula (IIa) and the general formula (IIb)). Represents a ratio, satisfies 0 <x ≦ 1 and 0 ≦ w <1, S _a , S _aa and S _aaa each represent a different spacer unit, P is photochemically isomerizable, And D represents a photochemically crosslinkable site, V _a represents a site that stabilizes vertical alignment, and n represents 4 to 100,000. A polymer for a vertical alignment layer for liquid crystals having a structural unit. In the general formula (IIa) and the general formula (IIb), S _a , S _aa and S _aaa are each independently represented by the general formula (IV),

(Wherein the dashed line represents a bond to _{L a, M a, P,} D or V _a,
Z ¹ , Z ² and Z ³ are each independently a single bond, — (CH ₂ ) _u — (wherein _u represents 1 to 20), —OCH ₂ —, —CH ₂ O—, — COO—, —OCO—, —CH═CH—, —CF═CF—, —CF ₂ O—, —OCF ₂ —, —CF ₂ CF ₂ — or —C≡C—, but these substituents In the formula, one or more of non-adjacent CH ₂ groups are independently —O—, —CO—, —CO—O—, —O—CO—, —Si (CH ₃ ) ₂ —O—Si (CH _3). ) ₂ —, —NR—, —NR—CO—, —CO—NR—, —NR—CO—O—, —O—CO—NR—, —NR—CO—NR—, —CH═CH—, -C≡C- or -O-CO-O- (wherein R independently represents hydrogen or an alkyl group having 1 to 5 carbon atoms),
A ¹ and A ² are each independently a trans-1,4-cyclohexylene group, a trans-1,3-dioxane-2,5-diyl group, a 1,4-naphthylene group, a 2,6-naphthylene group, Represents a pyridine-2,5-diyl group, a pyrimidine-2,5-diyl group, a 2,5-thiophenylene group, a 2,5-furylene group or a 1,4-phenylene group, which are unsubstituted or One or more hydrogen atoms may be substituted by fluorine atoms, chlorine atoms, methyl groups or methoxy groups,
p and q each independently represent 0 or 1. )
The vertical alignment layer polymer for liquid crystal of Claim 10 represented by these. In the general formula (IIa) and the general formula (IIb), V _a is the general formula (V)

(In the formula, the broken line represents the bond to S _aaa ,
Z ⁴ , Z ⁵ , Z ⁶ and Z ⁷ are each independently a single bond, — (CH ₂ ) _u — (wherein _u represents 1 to 20), —OCH ₂ —, —CH ₂ O. —, —COO—, —OCO—, —CH═CH—, —CF═CF—, —CF ₂ O—, —OCF ₂ —, —CF ₂ CF ₂ — or —C≡C— One or more of the non-adjacent CH ₂ groups in the substituents are independently —O—, —CO—, —CO—O—, —O—CO—, —Si (CH ₃ ) ₂ —O—Si. (CH ₃ ) ₂ —, —NR—, —NR—CO—, —CO—NR—, —NR—CO—O—, —O—CO—NR—, —NR—CO—NR—, —CH═ CH—, —C≡C— or —O—CO—O— (wherein R independently represents hydrogen or an alkyl group having 1 to 5 carbon atoms),
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 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, May be unsubstituted or one or more hydrogen atoms may be replaced by fluorine, chlorine, methyl or methoxy groups;
r, s, t and u each independently represents 0 or 1,
R ² represents hydrogen, fluorine, chlorine, a cyano group or an alkyl group having 1 to 20 carbon atoms, and the hydrogen atom in the alkyl group may be substituted with a fluorine atom, and one CH ₂ group or 2 These non-adjacent CH ₂ groups may be substituted with —O—, —CO—O—, —O—CO— and / or —CH═CH—. )
The vertical alignment layer polymer for liquid crystal of Claim 10 or 11 represented by these. In general formula (IIa) and general formula (IIb), P represents general formula (VI)

(In the formula, a broken line represents a bond to S _a , S _aa or S _aaa ,
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-diyl group, pyrimidine-2,5-diyl. Group, 2,5-thiophenylene group, 2,5-furylene group, 1,3-phenylene group or 1,4-phenylene group, which are unsubstituted or one or more hydrogen atoms are fluorine atoms , Chlorine atom, bromine atom, methyl group, methoxy group, nitro group, —NR ¹ R ² (wherein R ¹ and R ² each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms) Or a linear or branched alkyl group having 1 to 10 carbon atoms, the alkyl group may be unsubstituted or substituted with a fluorine atom,
p, q, r, s and t each independently represent 0 or 1, but 0 <q + r + s + t. )
The vertical alignment layer polymer for liquid crystal according to any one of claims 10 to 12, represented by: In general formula (IIa) and general formula (IIb), D represents general formula (VII)

(In the formula, a broken line represents a bond to S _a , S _aa or S _aaa , but when only one broken line is bonded, the other broken line is bonded to a hydrogen atom;
A ⁷ is 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, Represents a 5-furylene group, a 1,3-phenylene 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. It ’s okay,
X and Y each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group or an alkyl group having 1 to 20 carbon atoms, and the hydrogen atom in the alkyl group may be substituted with a fluorine atom. , One CH ₂ group or two or more non-adjacent CH ₂ groups may be substituted with —O—, —CO—O—, —O—CO— and / or —CH═CH—,
Z is a single bond, —O— or —NR ¹ — (wherein R ¹ is a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, or a cycloalkyl group having 3 to 8 ring members. Wherein the alkyl group is unsubstituted or optionally substituted with a fluorine atom or a chlorine atom, the cycloalkyl group is unsubstituted or an alkyl group having 1 to 10 carbon atoms, Which may be substituted with an alkoxy group having 1 to 10 carbon atoms, a fluorine atom or a chlorine atom),
r represents 0, 1 or 2. )
The vertical alignment layer polymer for liquid crystal according to any one of claims 10 to 13, represented by: The composition as described in any one of Claim 1 to 9 used in order to manufacture the liquid crystal aligning film for liquid crystal display devices of a vertical alignment mode. The vertical alignment layer for liquid crystals using the polymer for vertical alignment layers for liquid crystals as described in any one of Claims 10-14. An electro-optic element using the vertical alignment layer according to claim 16.