TW201731891A - Photo-alignment film polymer, polymer solution, photo-alignment film, optically anisotropic body and liquid crystal display element - Google Patents

Abstract

The purpose of the present invention is to provide a photo-alignment film polymer which can form a photo-alignment film which can obtain a high VHR, a photo-alignment film formed from the photo-alignment film polymer, and an optically anisotropic body and a liquid crystal display element having the photo-alignment film. A first form of the present invention is a photo-alignment film polymer represented by general formula (X). A second form of the present invention is a photo-alignment film formed from the photo-alignment film polymer of the first form. A third form of the present invention is an optically anisotropic body having the photo-alignment film of the second form. A fourth form of the present invention is a liquid crystal display element having the photo-alignment film of the second form.

Description

Polymer for light alignment film, polymer solution, optical alignment film, optical anisotropic body, and liquid crystal display element

The present invention relates to a polymer for a photo-alignment film, a polymer solution, a photo-alignment film, an optically-isotropic body, and a liquid crystal display element.

The photo-alignment film is characterized in that it does not have minute damage caused by mechanical friction, and there is no risk of dust generation due to friction and destruction of the TFT element accompanying it, and high-definition patterning can be realized. Therefore, the industry is vigorously promoting its application in various liquid crystal displays. In particular, there is a greater demand for optical alignment films for horizontal alignment (planar alignment) of IPS/FFS displays.

The method for producing a photo-alignment film which is not subjected to rubbing treatment is generally a method in which a solution containing a photo-alignment polymer is first applied onto a substrate and dried to form a film, and then the film is irradiated with polarized light to thereby illuminate the film. The surface of the alignment film imparts an alignment regulating force to the liquid crystal (for example, refer to Patent Document 1).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] International Publication No. 2013/002260

In order to obtain an excellent liquid crystal driving force in a liquid crystal display element (liquid crystal panel), a high voltage holding ratio (VHR) is required for a liquid crystal. Since the alignment limiting force of the photoalignment film has a large influence on the performance of the VHR, the industry is strongly expected to obtain an excellent photoalignment film having a high VHR.

The present invention has been made in view of the above circumstances, and an object of the invention is to provide a photo-alignment film polymer capable of forming a photo-alignment film having a high VHR and a photo-alignment film formed of the photo-alignment film polymer. An optical anisotropic body and a liquid crystal display element of the above photoalignment film.

The first aspect of the present invention is a polymer for a photo-alignment film which is represented by the following general formula (X):

(In the above formula (X), Sp ¹ and Sp ² each independently represent a spacer, and R ¹¹ represents a monovalent substituent or a halogen atom composed of two or more atoms, and the above monovalent substituents are bonded to each other. The absolute value of the difference between the electronegativity of the atoms in any combination of two atoms is 0.45 or more and 1.70 or less, and m is an integer of 1 to 5. When m is 2 or more, a plurality of R ^{11 are} mutually The same or different, A ²¹ , A ²² and A ²³ are each independently selected from (a) trans-1,4-cyclohexylene (one methylene group present in the group or not adjacent to 2) More than one methylene group may be substituted with -O-, -NH- or -S-), (b) 1,4-phenylene group (one or two or more present in the group -CH= Can be substituted with -N=), and (c) 1,4-cyclohexenylene, 2,5-thienthiophenyl, 2,5-extended furanyl, 1,4-bicyclo[2.2.2] Octyl, naphthalene-1,4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl and 1,2,3,4-tetrahydronaphthalene-2,6-diyl In the group formed, the above-mentioned group (a), group (b) or group (c) may be unsubstituted, respectively, or one or more hydrogen atoms may be substituted with a fluorine atom, a chlorine atom, a cyano group or an alkane. Base or alkane When group, p, q and r each independently represent an integer of 0 to 4, in the p, q and r are 2 or more of the case, a plurality of ^{A 21, A 22, A 23} , Z 22 and Z ²⁴ may be identical to each other also Alternatively, Z ²¹ , Z ²² , Z ²³ and Z ²⁴ are each independently selected from a single bond, -O-, -(CH ₂ ) _u - (wherein, u represents 1 to 20), -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -CH=CH-, -CF=CF-, -CF ₂ O-, -OCF ₂ -, -CF ₂ CF ₂ -, and -C≡C- At least one divalent linking group in the group satisfying the condition that D ¹ is -(L ¹ -A ¹ ) _k -C(=O)- and D ² is a single bond, or D ² is -C(=O - (A ^{1 -} L ¹ ) _f - and D ¹ is a single bond condition, L ¹ represents 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-contiguous -CH ₂ - groups constituting L ¹ may be independently substituted with -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 alkane having 1 to 5 carbon atoms ), K, and f is an integer of 0 to 3, A ¹ represents selected from the group consisting of (a) trans-1,4-cyclohexylene group (the presence of the above or adjacent to the group of one of the two methylene The methylene group may be substituted with -O-, -NH- or -S-), (b) 1,4-phenylene group (one or two or more present in the group -CH= may be substituted Is -N=), and (c) 1,4-cyclohexene, 2,5-thienyl, 2,5-extended furyl, 1,4-bicyclo[2.2.2] octyl, Naphthalene-1,4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl and 1,2,3,4-tetrahydronaphthalene-2,6-diyl The group in the group, the above group (a), the group (b) or the group (c) may be unsubstituted, respectively, or one or more hydrogen atoms may be substituted with a fluorine atom, a chlorine atom, a cyano group, a methyl group or a group. Oxygen, X and Y each independently represent a hydrogen atom or a halogen atom, and Z represents a formula (IIa) or (IIb) ----OR ¹ (IIa)

(wherein, the dotted line indicates a bond with D ² , and R ¹ and R ² each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 50 carbon atoms, and R ¹ and R ² One of the -CH ₂ - groups or two or more non-contiguous -CH ₂ - groups may be substituted from -O-, -CO-, -CO-O-, -O-CO-, -CO-NH One of or a group consisting of -, -NH-CO-, -NCH ₃ -, -CH=CH-, -CF=CF-, and -C≡C-, one of R ¹ and R ² or Two or more -CH ₂ - groups may be independently substituted with a cycloalkyl group having a ring number of 3 to 8, and a hydrogen atom of R ¹ and R ² may be substituted with an alkyl group having 1 to 20 carbon atoms. a cyano group or a halogen atom), a, b and c represent the molar fraction of the copolymer, in any case 0 < a ≦ 1 and 0 < b ≦ 1 and 0 ≦ c < 1, Ma, Mb and Md The arrangement of the monomer units may be the same as or different from the formula, and the monomer units of Ma, Mb and Md may be independently one type, or may be two or more different units, and each monomer unit of Ma, Mb and Md. Expressing the general formula (U-1)~(U-13) independently

(In the above general formulae (U-1) to (U-13), when the expression represents Ma or Mb, the broken line indicates the bond with Sp ¹ and Sp ² , and when the expression indicates Md, The broken line indicates a bond with a hydrogen atom or a monovalent organic group, and R ^a independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, a halogen atom, and the above formula (U-1) to (U- Any hydrogen atom in 13) may be substituted with a fluorine atom, a chlorine atom, a methyl group, a phenyl group, or a methoxy group; R ^1a represents a tetravalent ring structure, R ^2a represents a trivalent organic group, and R ^3a represents a hydrogen atom, Any one of a repeating unit of a hydroxyl group, an alkyl group having 1 to 15 carbon atoms, or an alkoxy group having 1 to 15 carbon atoms).

The second aspect of the present invention is a polymer solution which is a photo-alignment film polymer and an organic solvent as a necessary component in the first aspect.

A third aspect of the present invention is a photo-alignment film formed of a polymer of a photoalignment film of a first aspect.

A fourth aspect of the invention is an optically anisotropic body having a photoalignment film of a third aspect.

A fifth aspect of the invention is a liquid crystal display element having a photoalignment film of a third aspect.

According to the polymer for photo-alignment film of the present invention, a photo-alignment film which can induce alignment of liquid crystals with less amount of polarized light irradiation and which can obtain a higher VHR can be formed. Since the photo-alignment film of the present invention has excellent liquid crystal alignment, an excellent optical anisotropic body and a liquid crystal alignment layer can be formed. According to the liquid crystal display element of the present invention, a higher VHR can be obtained.

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

"Polymer for film for optical alignment"

The polymer for a photo-alignment film according to the first embodiment of the present invention is a polymer represented by the following formula (X).

(In the above formula (X), Sp ¹ and Sp ² each independently represent a spacer, and R ¹¹ represents a one-valent substituent or a halogen atom composed of two or more atoms, and the above monovalent substituents are bonded to each other. The absolute value of the difference between the electronegativity of the atoms in any combination of two atoms is 0.45 or more and 1.70 or less, and m is an integer of 1 to 5. When m is 2 or more, a plurality of R ^{11 are} mutually The same or different, A ²¹ , A ²² and A ²³ are each independently selected from (a) trans-1,4-cyclohexylene (one methylene group present in the group or not adjacent to 2) More than one methylene group may be substituted with -O-, -NH- or -S-), (b) 1,4-phenylene group (one or two or more present in the group -CH= Can be substituted with -N=), and (c) 1,4-cyclohexenylene, 2,5-thienthiophenyl, 2,5-extended furanyl, 1,4-bicyclo[2.2.2] Octyl, naphthalene-1,4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl and 1,2,3,4-tetrahydronaphthalene-2,6-diyl In the group formed, the above-mentioned group (a), group (b) or group (c) may be unsubstituted, respectively, or one or more hydrogen atoms may be substituted with a fluorine atom, a chlorine atom, a cyano group or an alkane. Base or alkane When group, p, q and r each independently represent an integer of 0 to 4, in the p, q and r are 2 or more of the case, a plurality of ^{A 21, A 22, A 23} , Z 22 and Z ²⁴ may be identical to each other also Alternatively, Z ²¹ , Z ²² , Z ²³ and Z ²⁴ are each independently selected from a single bond, -O-, -(CH ₂ ) _u - (wherein, u represents 1 to 20), -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -CH=CH-, -CF=CF-, -CF ₂ O-, -OCF ₂ -, -CF ₂ CF ₂ -, and -C≡C- At least one divalent linking group in the group satisfying the condition that D ¹ is -(L ¹ -A ¹ ) _k -C(=O)- and D ² is a single bond, or D ² is -C(=O - (A ^{1 -} L ¹ ) _f - and D ¹ is a single bond condition, L ¹ represents 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-contiguous -CH ₂ - groups constituting L ¹ may be independently substituted with -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 k, f is an integer of 0 to 3, and A ¹ is selected from (a) trans-1,4-cyclohexylene (one methylene group present in the group or two or more adjacent thereto) The methylene group may be substituted with -O-, -NH- or -S-), (b) 1,4-phenylene group (one or two or more present in the group -CH= may be substituted Is -N=), and (c) 1,4-cyclohexene, 2,5-thienyl, 2,5-extended furyl, 1,4-bicyclo[2.2.2] octyl, Naphthalene-1,4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl and 1,2,3,4-tetrahydronaphthalene-2,6-diyl The group in the group, the above group (a), the group (b) or the group (c) may be unsubstituted, respectively, or one or more hydrogen atoms may be substituted with a fluorine atom, a chlorine atom, a cyano group, a methyl group or a group. Oxy groups, X and Y each independently represent a hydrogen atom or a halogen atom, and Z represents a formula (IIa) or (IIb)----OR ¹ (IIa)

(wherein, the dotted line indicates a bond with D ² , and R ¹ and R ² each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 50 carbon atoms, and R ¹ and R ² One -CH ₂ - group or two or more non-contiguous -CH ₂ - groups may be substituted from -O-, -CO-, -CO-O-, -O-CO-, -CO-NH- One or more of R ¹ and R ² , one of or more of -NH-CO-, -NCH ₃ -, -CH=CH-, -CF=CF-, and -C≡C- More than one -CH ₂ - group may be independently substituted with a cycloalkyl group having a ring number of 3 to 8, and a hydrogen atom of R ¹ and R ² may be substituted with an alkyl group having 1 to 20 carbon atoms and cyanide. Base or halogen atom), a, b and c represent the molar fraction of the copolymer, in any case 0<a≦1 and 0<b≦1 and 0≦c<1, Ma, Mb and Md The arrangement of the monomer units may be the same as or different from the formula. The monomer units of Ma, Mb and Md may be independently one type, or may be two or more different units, and the individual units of Ma, Mb and Md are respectively Independently expresses the general formula (U-1)~(U-13)

(In the above general formulae (U-1) to (U-13), when the expression represents Ma or Mb, the broken line indicates the bond with Sp ¹ and Sp ² , and when the expression indicates Md, The broken line indicates a bond with a hydrogen atom or a monovalent organic group, and R ^a independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, a halogen atom, and the above formula (U-1) to (U- Any hydrogen atom in 13) may be substituted with a fluorine atom, a chlorine atom, a methyl group, a phenyl group, or a methoxy group; R ^1a represents a tetravalent ring structure, R ^2a represents a trivalent organic group, and R ^3a represents a hydrogen atom, Any one of a repeating unit of a hydroxyl group, an alkyl group having 1 to 15 carbon atoms, or an alkoxy group having 1 to 15 carbon atoms)

The polymer represented by the formula (X) has a copolymer of a side chain unit MA bonded to the monomer unit Ma and a side chain unit MB bonded to the monomer unit Mb.

Side Chain Unit MA <About Sp ¹ >

In the formula (X), the spacer represented by Sp ¹ represents a single bond, a linear or branched alkyl group having 1 to 40 carbon atoms, or the following formula (IVa), in the above alkyl group One or more of the non-contiguous -CH ₂ - may be independently substituted with -O-, -COO-, -OCO-, -CH=CH-, -CF=CF-, -CF ₂ O-, -OCF ₂ -, -CF ₂ CF ₂ -, -C≡C-, -CO-, -S-, -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 a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), and further, one or more hydrogen atoms of -CH ₂ - in the above alkyl group may be substituted It is a fluorine atom, a chlorine atom, a hydroxyl group, or a cyano group. Further, in the case where Sp ¹ and the group bonded to Sp ¹ have a hetero atom, the case where the hetero atom is bonded to each other is excluded.

In the case where Z ²¹ is a single bond, it is preferred that Sp ¹ is the above-described alkylene group or a structure represented by the following formula (IVa).

The alkyl group has preferably from 2 to 20, more preferably from 3 to 15, more preferably from 4 to 10. When it is such a preferable spacer, the VHR of the liquid crystal display element which uses the liquid crystal alignment layer of the polymer for optical alignment film of this embodiment can be improved.

Preferred examples of the spacer represented by Sp ¹ include a group represented by the formula (IVa) described below, and examples thereof include a chemical formula (Sp-a-1) to (Sp-a-20) and a chemical formula. (Sp-b-1)~(Sp-b-14), chemical formula (Sp-c-1)~(Sp-c-14) and chemical formula (Sp-d-1)~(Sp-d-16) The spacers indicated are preferred.

The spacer represented by Sp ¹ in the general formula (X) may be the same as or different from the spacer represented by Sp ² described below.

<About Z ²¹ and Z ²² >

In the general formula (X), Z ²¹ and Z ²² are each independently selected from a single bond, -O-, -(CH ₂ ) _u - (wherein, u represents 1 to 20), -OCH ₂ -, - Composition of CH ₂ O-, -COO-, -OCO-, -CH=CH-, -CF=CF-, -CF ₂ O-, -OCF ₂ -, -CF ₂ CF ₂ -, and -C≡C- At least one divalent linking group in the group.

In the general formula (X), when a plurality of Z ²² are present, the plurality of Z ²² may be the same or different from each other.

In the general formula (X), p and q each independently represent an integer of 0 to 4.

When p is 2 or more, the plurality of A ^21s may be the same or different from each other, and the plurality of Z ²² may be the same or different from each other.

When q is 2 or more, the plurality of A ^22s may be the same or different from each other.

p is preferably 0 or 1, and q is preferably 0 or 1.

<About A ²¹ and A ²² >

In the formula (X), A ²¹ and A ²² each independently represent a group selected from (a) trans-1,4-cyclohexylene (one methylene group present in the group or two adjacent groups) The above methylene group may be substituted with -O-, -NH- or -S-), (b) 1,4-phenylene group (one or two or more present in the group -CH= Substituted as -N=), and (c) 1,4-cyclohexenylene, 2,5-thienthiophenyl, 2,5-extended furyl, 1,4-bicyclo[2.2.2] Base, naphthalene-1,4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl and 1,2,3,4-tetrahydronaphthalene-2,6-diyl In the group of the composition, the above-mentioned group (a), group (b) or group (c) may be unsubstituted, respectively, or one or more hydrogen atoms may be substituted with a fluorine atom, a chlorine atom, a cyano group or an alkyl group. Or alkoxy.

In the general formula (X), when a plurality of A ²¹ and A ²² are present, respectively, the plurality of A ²¹ and A ²² may be the same or different from each other.

<About R ¹¹ >

R ¹¹ represents a one-valent substituent or a halogen atom composed of two or more atoms. The absolute value of the difference between the electronegativity of the atoms in any combination of the two atoms bonded to each other in the monovalent substituent includes a combination of 0.45 or more and 1.70 or less. m is an integer of 1 to 5, and when m is 2 or more, a plurality of R ^{11 's} may be the same or different from each other.

The above "electronegativity" refers to "Pauling's electricity" as described in Shriver and Atkins, Inorganic Chemistry, 5th ed., Freeman: New York, 2010 and Huheey, JE, Inorganic Chemistry, Harper & Row: New York, 1983. Negative χp". Based on the electronegativity, a combination of two atoms bonded to each other in a lateral arrangement and one atom in the longitudinal direction and another atom in the longitudinal direction are shown in Table 1.

In the combination table, the value described in the position of the vertical and horizontal intersection is the absolute value of the "difference in electronegativity". For example, the difference between the electronegativity of the carbon atoms-nitrogen atoms (CN) bonded to each other is 0.49, and the difference between the electronegativity of the carbon atoms-oxygen atoms (CO) bonded to each other is 0.89, and the carbon atoms bonded to each other. The difference in electronegativity of the fluorine atom (CF) is 1.43, and the difference in electronegativity between the oxygen atoms-hydrogen atoms (OH) bonded to each other is 1.24.

If R ¹¹ has the above monovalent substituent or a halogen atom, a photoalignment film having an excellent voltage holding ratio can be formed because it is considered that by having R ¹¹ , the side chain unit is moderately polarized, so that liquid crystal can be trapped. Impurities contained. Although the detailed mechanism is not known, it is considered that if the absolute value of the difference in the electronegativity is the above range, the degree of polarization of R ¹¹ tends to be moderate, and the effect of trapping impurities is likely to occur.

In the formula (X), R ^{11 is} preferably a cyano group, a hydroxyl group, a carboxyl group, a decylamino group, a fluorine atom, a chlorine atom, a thiol group, a sulfonic acid group, a nitro group, a linear or branched carbon atom number. An alkyl group of 1 to 20 or an alkoxy group having 1 to 20 carbon atoms, or the following formula (QX) -----S _aa -V _a (QX)

(wherein, a broken line indicates a bonding bond, _{Sa a} indicates a spacer, and Va indicates a terminal of a side chain).

One or more non-adjacent ones of the -CH ₂ - groups constituting the above alkyl group and alkoxy group may be independently substituted with -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- (wherein R independently represents hydrogen or an alkyl group having 1 to 5 carbon atoms), -CH=CH-, -C≡C-, -O-CO-O-, -CH=CH-CO-O-, and one or more substituents in the divalent ring structure.

One or more hydrogen atoms bonded to the above alkyl group, the above alkoxy group, and the group represented by the above formula (QX) may be substituted with a fluorine atom, a chlorine atom, a cyano group, a hydroxyl group, a carboxyl group, a decylamino group, Sulfonic acid group, nitro group.

The alkyl group and the alkyl group constituting the alkoxy group may be any of a linear chain, a branched chain or a cyclic group. A part of the methylene group of the above linear alkyl group may be substituted with a cyclic alkyl group.

The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, from the viewpoint of improving the solubility of the polymer.

Examples of the divalent ring structure include an aromatic cyclic group, a heterocyclic group, and a cyclic alkyl group.

In the case where the above divalent ring structure is substituted for the -CH ₂ - group of the above alkyl group, the ring structure is preferably a -CH ₂ - group which is substituted at the terminal of the alkyl group. That is, the above divalent ring structure is preferably a one-valent ring structure of a methyl group substituted for the terminal of the above alkyl group.

The divalent ring structure and the monovalent ring structure are preferably a divalent or monovalent ring structure having two or one hydrogen atoms constituting benzene, naphthalene and anthracene and having two or one bonding bonds. .

m is an integer of 1 to 5, and when m is 2 or more, a plurality of R ^{11 's} may be the same or different from each other. In the case where m is 1, the bonding position of R ¹¹ is preferably a meta or para position, more preferably a para position. By virtue of these preferred bonding positions, the VHR of the liquid crystal display element having the photoalignment film of the present invention can be further improved.

In the case where R ¹¹ is a group represented by the above formula (QX), a group represented by the following formula (VI) can be given as _Sa a in the same formula.

(wherein the left dotted line indicates the same meaning as the broken line of the general formula (QX), and the right broken line indicates the bond with V _a ; Z ¹¹ , Z ¹² and Z ¹³ each independently represent 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-contiguous -CH ₂ - groups of the substituents may be independently substituted with -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- (wherein R independently represents hydrogen or an alkyl group having 1 to 5 carbon atoms), -CH=CH-, -C≡C-, -O-CO-O-, or -CH=CH-CO-O-, A ¹¹ and A ¹² are each independently selected from (a) trans-1,4-cyclohexylene (present in the group) One methylene group or two or more methylene groups which are not adjacent may be substituted with -O-, -NH- or -S-), and (b) 1,4-phenylene group (present in the group) One or two or more -CH= may be substituted with -N=), and (c) 1,4-cyclohexenylene, 2,5-thienylene, 2,5-furanyl, 1 , 4-bicyclo[2.2.2] octyl, naphthalene-1,4-diyl, naphthalene-2,6-diyl, decahydro a group in the group consisting of -2,6-diyl and 1,2,3,4-tetrahydronaphthalene-2,6-diyl, the above-mentioned group (a), group (b) or group (c) Each of which may be unsubstituted, or one or more hydrogen atoms may be substituted with a fluorine atom, a chlorine atom, a cyano group, a methyl group or a methoxy group, and p and q each independently represent 0 or 1)

Z ¹¹ , Z ¹² and Z ^{13 of the} formula (VI) are preferably each independently a single bond or -(CH ₂ ) _u - (wherein, u represents 1 to 12, and 1 or more of the non-adjacent CH ₂ groups are present. Can be independently substituted with -O-, -CO-, -CO-O-, -O-CO-, -CH=CH-, -C≡C-, -O-CO-O-, or -CH= CH-CO-O-).

A ¹¹ and A ^{12 of the} formula (VI) each independently represent a trans-1,4-cyclohexylene group, a 1,4-phenylene group, and the like are preferably unsubstituted or one or more hydrogen atoms are Substituted as a fluorine atom, a chlorine atom, a methyl group or a methoxy group.

In the formula (QX), it is preferred that V _a is the following formula (VII)

(Wherein the broken line represents the S _aa ^{bond; Z 4, Z 5, Z} 6 and Z ⁷ each independently represent 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-contiguous -CH ₂ - groups of the substituents may be independently substituted with -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 And A ⁵ and A ⁶ each independently represent a methyl group selected from (a) trans-1,4-cyclohexylene (one methylene group present in the group or two or more methylene groups not adjacent thereto may be Substituted as -O-, -NH- or -S-), (b) 1,4-phenylene (one or two or more present in the group -CH= may be substituted with -N=) And (c) 1,4-cyclohexenylene, 2,5-thienthiophenyl, 2,5-extended furyl, 1,4-bicyclo[2.2.2]exenyl, naphthalene-1,4 a group consisting of di-, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl and 1,2,3,4-tetrahydronaphthalene-2,6-diyl Further, the above-mentioned group (a), group (b) or group (c) may be unsubstituted, respectively, or one or more hydrogen atoms may be substituted with a fluorine atom, a chlorine atom, a cyano group, a methyl group or a methoxy group. R1, s1, t1 and u1 each independently represent 0 or 1, and R ¹² represents a hydrogen atom, a halogen or a linear or branched alkyl group having 1 to 20 carbon atoms, and the hydrogen atom in the above alkyl group may be substituted with Halogen or cyano, 1 -CH ₂ - group or 2 or more non-contiguous CH ₂ groups may be substituted with -O-, -CO-O-, -O-CO- and/or -CH=CH- ) The structure represented.

In the formula (VII), r1, s1, t1 and u1 are preferably 0.

In the formula (VII), R ^{12 is} preferably a linear alkyl group having 1 to 20 carbon atoms, and a hydrogen atom in the above alkyl group is preferably substituted with a halogen or a cyano group.

Side Chain Unit MB <About Sp ² >

In the formula (X), the spacer represented by Sp ² is independently a Sp ¹ described above and represents a single bond, a linear or branched alkyl group having 1 to 40 carbon atoms, or the following Formula (IVa), one or more of the non-contiguous -CH ₂ - in the above alkylene group may be independently substituted with -O-, -COO-, -OCO-, -CH=CH-, -CF=CF- , -CF ₂ O-, -OCF ₂ -, -CF ₂ CF ₂ -, -C≡C-, -CO-, -S-, -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 a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), and further -CH ₂ in the above alkyl group One or more hydrogen atoms may be substituted with a fluorine atom, a chlorine atom, a hydroxyl group, or a cyano group. Further, in the case where the group bonded to Sp ² and Sp ² has a hetero atom, the case where the hetero atom is bonded to each other is excluded.

In the case where Z ²³ is a single bond, Sp ^{2 is} preferably an alkylene group or a structure represented by the following formula (IVa).

In the general formula (IVa), the dotted line on the left side indicates the bond with Mb, and the dotted line on the right side indicates the bond with Z ²³ , and Z ¹ , Z ² and Z ³ each independently represent a single bond, -(CH ₂ ) _u - (formula) Where u denotes 1~20), -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 none of the -CH ₂ - groups in Z ¹ , Z ² and Z ³ may be independently substituted with -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, and A ¹ and A ² are each independently selected from (a) trans-1,4-cyclohexylene (one methylene group present in the group or not) Two or more methylene groups adjacent to each other may be substituted with -O-, -NH- or -S-), and (b) 1,4-phenylene groups (one or more of the groups present in the group) -CH= can be substituted for -N=), and (c) 1,4-cyclohexenylene, 2,5-thienylene, 2,5-furanyl, 1,4-bicyclo[2.2. 2] octyl, naphthalene-1,4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl and 1,2,3,4-tetrahydro a group in the group consisting of -2,6-diyl, wherein the above-mentioned group (a), group (b) or group (c) may be unsubstituted, respectively, or one or more hydrogen atoms may be substituted with a fluorine atom, A chlorine atom, a cyano group, a methyl group or a methoxy group, and p1 and q1 each independently represent 0 or 1.

From the viewpoint of increasing the VHR of the liquid crystal display element of the present invention, each of the groups in the formula (IVa) is preferably the following group.

In the formula (IVa), Z ¹ , Z ² and Z ³ are each independently a single bond, -(CH ₂ ) _u - (wherein, u represents 1 to 20, and -CH ₂ - group is 1). Two or more of the non-contiguous -CH ₂ - groups may be independently substituted with -O-, -CO-O-, -O-CO-, -CH=CH- or -C≡C-), -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -CH=CH-, or -C≡C-.

In the formula (IVa), p1 is preferably 0.

In the formula (IVa), q1 is preferably 1.

In the formula (IVa), A ¹ and A ^{2 are} preferably each independently a trans-1,4-cyclohexylene group, a 2,6-anthranyl group, or a 1,4-phenylene group. . The hydrogen atom of the group may be unsubstituted, or one or more hydrogen atoms may be substituted with a fluorine atom, a methyl group or a methoxy group.

As Sp ² represented by the formula (IVa), for example, those represented by the following chemical formula (Sp-a-1) to chemical formula (Sp-ah1-8) are preferable. In the chemical formulas, the dotted line on the left side indicates the bond with the monomer unit Mb, and the dotted line on the right side indicates the bond with the Z ²³ line.

It can be selected as needed, but among these, it is more preferably a chemical formula (Sp-a-6)~(Sp-a-20), a chemical formula (Sp-b-3)~(Sp-b-10), a chemical formula (Sp -c-3)~(Sp-c-10), chemical formula (Sp-d-3)~(Sp-d-12), chemical formula (Sp-k-4)~(Sp-k-7), chemical formula ( Sp-1-13)~(Sp-1-17), chemical formula (Sp-o-3)~(Sp-o-14), chemical formula (Sp-p-2)~(Sp-p-13), chemical formula (Sp-s-1)~(Sp-s-8), chemical formula (Sp-t-1)~(Sp-t-8), chemical formula (Sp-y-1)~(Sp-y-9) and The chemical formula (Sp-aa-1)~(Sp-aa-9) is represented.

<About Z ²³ and Z ²⁴ >

In the general formula (X), Z ²³ and Z ²⁴ each independently represent a group selected from a single bond, -O-, -(CH ₂ ) _u - (wherein, u represents 1 to 20), -OCH ₂ -, - Composition of CH ₂ O-, -COO-, -OCO-, -CH=CH-, -CF=CF-, -CF ₂ O-, -OCF ₂ -, -CF ₂ CF ₂ -, and -C≡C- At least one divalent linking group in the group.

In the general formula (X), in the case where a plurality of Z ²⁴ are present, the plurality of Z ²³ may be the same or different from each other.

In the general formula (X), r represents an integer of 0 to 4. r is preferably 0 or 1. When r is 2 or more in the case, a plurality of A ²³ may be identical or different from each other, a plurality of Z ²⁴ may be the same or different from each other.

<About A ²³ >

In the formula (X), A ²³ represents a group selected from (a) trans-1,4-cyclohexylene (one methylene group present in the group or two or more methylene groups not adjacent thereto) Substituted as -O-, -NH- or -S-), (b) 1,4-phenylene (one or more than one in the group -CH= can be substituted for -N= And (c) 1,4-cyclohexene, 2,5-thienyl, 2,5-furanyl, 1,4-bicyclo[2.2.2]exenyl, naphthalene-1, a group consisting of 4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl and 1,2,3,4-tetrahydronaphthalene-2,6-diyl The above-mentioned group (a), group (b) or group (c) may be unsubstituted, respectively, or one or more hydrogen atoms may be substituted with a fluorine atom, a chlorine atom, a cyano group, an alkyl group or an alkoxy group.

A ^{23 is} preferably the above group (b).

It is preferred that one or more hydrogen atoms of A ²³ are substituted with an alkoxy group, preferably substituted with a methoxy group or an ethoxy group.

In the general formula (X), when a plurality of A ²³ are present, respectively, the plurality of A ²³ may be the same or different from each other.

<About D ¹ and D ² >

In the general formula (X), D ¹ and D ² satisfy the condition that D ¹ is -(L ¹ -A ¹ ) _k -C(=O)- and D ² is a single bond, or D ² is -C(= O)-(A ¹ -L ¹ ) _f - and D ¹ is any one of the conditions of a single bond.

L ¹ represents 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-contiguous CH ₂ groups constituting L ¹ may be independently substituted with -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 constituting D ¹ and D ² is preferably each independently a trans-1,4-cyclohexylene group, a 2,6-anthranyl group, or a 1,4-phenylene group. The hydrogen atom of the group may be unsubstituted, or one or more hydrogen atoms may be substituted with a fluorine atom, a methyl group or a methoxy group.

k and f are integers from 0 to 3, preferably 0 or 1.

When k or f is 2 or 3, the plurality of L1 constituting D ¹ and D ² may be the same or different, and a plurality of A ¹ constituting D ¹ and D ² may be the same or different.

<About X and Y>

In the formula (X), X and Y each independently represent a hydrogen atom or a halogen atom, preferably a hydrogen atom.

<About Z>

In the formula (X), Z represents the formula (IIa) or (IIb).

----OR ¹ (IIa)

(wherein, the dotted line indicates a bond with D ² , and R ¹ and R ² each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 50 carbon atoms, and R ¹ and R ² One of the -CH ₂ - groups or two or more non-contiguous -CH ₂ - groups may be substituted from -O-, -CO-, -CO-O-, -O-CO-, -CO-NH One of or a group consisting of -, -NH-CO-, -NCH ₃ -, -CH=CH-, -CF=CF-, and -C≡C-, one of R ¹ and R ² or Two or more -CH ₂ - groups may be independently substituted with a cycloalkyl group having a ring number of 3 to 8, and a hydrogen atom of R ¹ and R ² may be substituted with an alkyl group having 1 to 20 carbon atoms. Cyano or halogen atom)

In the formula (IIa) or (IIb), R ¹ preferably represents a linear or branched alkyl group having 1 to 30 carbon atoms (one of the above alkyl groups - CH ₂ - group or 2) More than one non-contiguous -CH ₂ - group may be substituted by -O-, -CO-, -CO-O-, -O-CO-, -CO-NH-, -NH-CO-, -NCH ₃ - One or two or more -CH ₂ - groups in the above alkyl group may be independently substituted with a cycloalkyl group having a ring number of 3 to 8, and a hydrogen atom in the above alkyl group may be substituted with a carbon number. 1 to 20 alkyl group, cyano group or halogen atom), and R ² represents a linear or branched alkyl group having 1 to 30 carbon atoms (one or more of the above alkyl groups - CH) _{The 2} -yl group may be independently substituted with a cycloalkyl group having 3 to 8 ring members, and the hydrogen atom in the above alkyl group may be unsubstituted or may be substituted with an alkyl group having 1 to 20 carbon atoms and a cyano group. Or a halogen atom).

<Monomer Unit>

In the general formula (X), the arrangement of the monomer units of Ma, Mb and Md may be the same as or different from the formula, and the monomer units of Ma, Mb and Md may be independently one type or two or more types. In the unit, each monomer unit of Ma, Mb, and Md independently represents any one of the repeating units of the general formulae (U-1) to (U-13).

(In the above general formulae (U-1) to (U-13), when the expression represents Ma or Mb, the broken line indicates the bond with Sp ¹ and Sp ² , and when the expression indicates Md, The broken line indicates a bond with a hydrogen atom or a monovalent organic group, and R ^a independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, a halogen atom, and the above formula (U-1) to (U- Any hydrogen atom in 13) may be substituted with a fluorine atom, a chlorine atom, a methyl group, a phenyl group, or a methoxy group; R ^1a represents a tetravalent ring structure, R ^2a represents a trivalent organic group, and R ^3a represents a hydrogen atom, Hydroxyl group, alkyl group having 1 to 15 carbon atoms, alkoxy group having 1 to 15 carbon atoms)

Preferred monomer units of Ma, Mb and Md are monomer units represented by the formula (U-1).

In the general formulae (U-1) to (U-13), R ^{a is} preferably independently a hydrogen atom or a methyl group, and one or more hydrogen atoms bonded to the methyl group may be substituted with a fluorine atom.

Examples of the tetravalent ring structure represented by R ^1a include a ring group having four hydrogen atoms bonded to an aromatic ring, a hetero ring or an aliphatic ring and having four bonding bonds. For example, it is preferably a cycloalkane such as cyclobutane, cyclopentane or cyclohexane.

Examples of the trivalent ring structure represented by R ^2a include a ring group having three hydrogen atoms bonded to an aromatic ring, a hetero ring or an aliphatic ring and having three bonding bonds. For example, it is preferably A base formed by removing three hydrogen atoms from the benzene ring.

When in the general formula (U-1) ~ (U -13) shows a case Ma of monomeric units, wherein the dashed line represents the bond with the Sp ^1.

In the case where the general formula (U-1) to (U-13) represents the monomer unit Mb, the broken line in the formula indicates the bond with Sp ² .

In the case where the general formula (U-1) to (U-13) represents the monomer unit Md, the broken line in the formula represents a bond with a hydrogen atom or a monovalent organic group.

The monovalent organic group may, for example, be a group represented by the above formula (QX).

<Composition of polymer>

The polymer for photo-alignment film represented by the formula (X) has a side chain unit MA bonded to the monomer unit Ma and a side chain unit MB bonded to the monomer unit Mb. The side chain unit MA is preferably photochemically isomerizable and does not photochemically crosslink. The side chain unit MB is preferably photochemically crosslinkable. The polymer for photo-alignment film may also contain a side chain unit MD bonded to the monomer unit Md.

In the formula (X), a, b and c represent the molar fraction of the copolymer, optionally In the case, both are 0 < a ≦ 1 and 0 < b ≦ 1 and 0 ≦ c < 1.

In the above molar fraction, the ratio represented by a/(a+b+c)×100% is preferably from 0.1 to 20%, more preferably from 1 to 15%, still more preferably from 2 to 10%.

If it is the above preferred range, the VHR can be further increased.

"Synthesis of Polymers for Photoalignment"

The method for synthesizing the photo-alignment polymer of the present invention is not particularly limited, and for example, the method described in Patent Document 1 can be applied. In the case of synthesizing a polymer for photoalignment, a known polymerization initiator can be used in combination with a polymerization method of a polymerizable functional group. As the polymerization initiator, for example, a known polymerization initiator described in the synthesis and reaction of a polymer (edited by Polymer Society, Kyoritsu Kogyo Co., Ltd.) can be applied.

The amount of the polymerization initiator to be added is, for example, 0.1 to 10% by mass based on the total mass of the mixture containing the monomer composition to be polymerized. Further, by using a polyoxyalkylene compound, an addition reaction to a polymer main chain is carried out, and a target polymer can also be synthesized.

The photoalignment polymer of the present invention can be polymerized in a reaction vessel and further purified. Examples of the solvent in the polymerization reaction include benzene, toluene, xylene, ethylbenzene, pentane, hexane, heptane, octane, cyclohexane, cycloheptane, methanol, ethanol, and 1-propanol. , 2-propanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, 2-butanone, acetone, tetrahydrofuran, γ-butyrolactone, N-methyl-pyrrolidone, dimethyl Kea, dimethylformamide, and the like. The solvent used for the polymerization reaction may be one type or a combination of two or more types.

Further, the photo-alignment polymer of the present invention can also be obtained by applying a composition containing each monomer onto a substrate, drying the solvent as necessary, and then performing polymerization by heating or light irradiation. .

Further, the photo-alignment polymer of the present invention can also be obtained by the following method: The photo-alignment polymer solution containing the polymer and the organic solvent as an essential component is applied onto the substrate, and after the organic solvent is dried and removed, the polymerization reaction is carried out by heating or light irradiation. The organic solvent to be used herein is not particularly limited, and examples thereof include N-methylpyrrolidone, butoxyethanol, 1,1,2-trichloroethane, and N-methylpyrrolidone. (pyrrolidone), γ-butyrolactone, ethylene glycol, polyethylene glycol monomethyl ether, propylene glycol, 2-pyrrolidone, N,N-dimethylformamide, phenoxyethanol, tetrahydrofuran, dimethyl Two or more organic solvents may be used in combination with sulfonium, methyl isobutyl ketone, and cyclohexanone. Examples of the mixed solvent of two or more kinds thereof include N-methylpyrrolidone: butoxyethanol = 1:1 (mass ratio). Further, in terms of coatability, the polymer solution preferably has a solid content of 1 to 20% by mass, particularly 0.5 to 10% by mass.

Formation of luminescent alignment film≫

By irradiating a polarizing ultraviolet ray to a film composed of the polymer of the present invention, a photo-alignment film having an alignment regulating force can be obtained. The method for obtaining a film composed of the above polymer can be obtained, for example, by applying a solution of the above polymer to a substrate and drying it.

The photoalignment film (liquid crystal alignment layer) of the present invention can be applied to a horizontal alignment or vertical alignment mode liquid crystal display element.

Examples of the material of the substrate include glass, ruthenium, polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polycarbonate, and triacetyl cellulose.

Electrode layers such as Cr, Al, an ITO film made of In ₂ O ₃ -SnO ₂ or a NESA film made of SnO ₂ may be provided on the substrates. The patterning of the electrode layers may be performed by photolithography or a method of using a mask when forming an electrode layer. Further, a color filter layer or the like may be formed on the substrate.

As a method of applying a solution containing a polymer onto a substrate, for example, Spin coating, die coating, gravure coating, flexographic printing, ink jet printing, and the like.

The solid content concentration of the solution at the time of coating is preferably from 0.5 to 10% by weight. Further, it is preferably selected from the range in consideration of a method of applying a solution onto a substrate, viscosity, volatility, and the like.

Preferably, after the polymer solution is applied onto the substrate, the coated surface is heated to remove the solvent. The heating temperature is, for example, preferably from 50 to 300 ° C, more preferably from 80 to 200 ° C. The heating time in the preferred temperature range is, for example, preferably from 2 to 200 minutes, more preferably from 2 to 100 minutes.

The isomerization reaction of the side chain unit MA is caused by irradiating the coating film formed on the substrate with linear polarized light from the normal direction of the coating film surface and/or irradiating non-polarized light or linearly polarized light from the oblique direction. The photocrosslinking reaction of the side chain unit MB can thereby obtain a photoalignment film to which an alignment control function is imparted. In order to impart the desired pretilt angle, it is preferred to illuminate from a linear oblique direction obliquely. Here, the irradiation from the oblique direction means that the angle between the irradiation direction of the light and the substrate surface is 1 degree or more and 89 degrees or less. In the case of use as a light alignment film for vertical alignment, the pretilt angle is usually preferably from 70 to 89.8°. Further, in the case of being used as a light alignment film for horizontal alignment, the pretilt angle is usually preferably 0 to 20°.

For the light to be applied to the coating film, for example, ultraviolet rays and visible rays containing light having a wavelength of 150 nm to 800 nm 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. Linear polarized light can be obtained by using a polarizing filter or a polarizing ray for light from the light sources. Further, the ultraviolet light and the visible light obtained by such a light source may be limited by the interference filter or the color filter.

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

制造Manufacturing method of liquid crystal display device≫

By using the photoalignment film of the present invention, 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.

Two sheets of the substrate on which the photoalignment film of the present invention is formed are prepared, and liquid crystal is disposed between the two substrates, whereby a liquid crystal cell can be manufactured. Further, the light alignment film may be formed on only one of the two substrates.

As a manufacturing method of a liquid crystal cell, the following methods are mentioned, for example. First, two substrates are disposed so that the respective light alignment films are opposed to each other, and the peripheral portion is bonded together with a sealant while maintaining a constant gap (cell gap) between the two substrates, on the surface of the substrate and the sealant. After the filled liquid crystal composition is injected into the divided cell gap, the injection hole is sealed, whereby the liquid crystal cell can be manufactured.

The liquid crystal cell can also be manufactured by a method called ODF (One Drop Fill). In the order, for example, a sealing agent such as an ultraviolet curable layer is applied to a specific portion on a substrate on which a photo-alignment film is formed, and after the liquid crystal composition is dropped onto the photo-alignment film, the photo-alignment film is attached to the film. Combine another substrate. Next, the entire surface of the substrate is irradiated with ultraviolet light to harden the sealant, whereby the liquid crystal cell can be manufactured.

It is preferred to take the temperature of the isotropic phase by heating to the liquid crystal light alignment film used here, and then slowly cool to room temperature to remove the flow alignment generated during the injection.

The liquid crystal composition is not particularly limited, and for example, a known nematic liquid crystal composition can be used. In the case of a vertical alignment type liquid crystal cell, it is preferred to have a negative dielectric anisotropy. In the case of a horizontal alignment type liquid crystal cell, it is preferred to have a positive dielectric anisotropy.

Liquid crystal display can be obtained by bonding a known polarizing plate to the outer surface of the liquid crystal cell Show components.

"Method of Manufacturing Optical Isotropic Body"

The optically oriented body of the present invention has the photoalignment film of the present invention. The optically oriented product of the present invention may further comprise a photoalignment film of the present invention and a film composed of a polymer of a polymerizable liquid crystal composition formed on the photoalignment film. The optically anisotropic body is useful for applications such as optical anisotropic films used for optical compensation of liquid crystal display elements. In the optically anisotropic body, when the light advances therein, the optical properties such as the propagation speed, the refractive index, and the absorption of the light differ depending on the direction of advancement.

As a method of producing the optically-oriented anisotropic body of the present invention, for example, a photo-alignment film is formed on a substrate, and a polymerizable liquid crystal composition is applied thereon to form a liquid crystal molecule containing the photo-alignment film. a film of a polymer.

When a polymerizable liquid crystal composition is applied onto a photo-alignment film to produce an optical anisotropic body, bar coating, spin coating, roll coating, gravure coating, spray coating, or die coating can be applied. A known coating method such as coating, dipping, or the like. In order to improve coatability, a known organic solvent may be added to the polymerizable liquid crystal composition. In the case where an organic solvent is added, the polymerizable liquid crystal composition is applied onto the photo-alignment film, and then the organic solvent is removed by a known drying method.

The method of polymerizing the polymerizable liquid crystal composition includes a method of irradiating the polymerizable liquid crystal composition with an active energy ray, a thermal polymerization method, or the like.

When the polymerizable liquid crystal composition is polymerized by irradiation with an active energy ray, it is preferred to apply a polymerizable liquid crystal composition to the photo-alignment film to align the polymerizable liquid crystal molecules. polymerization.

In the case where the polymerization of the polymerizable liquid crystal composition is carried out by irradiation with an active energy ray, for example, a method of irradiating ultraviolet rays at an irradiation intensity of 1 W/m ² to 10 kW/m ² is exemplified.

The temperature at which the polymerization of the polymerizable liquid crystal composition is carried out by heat is preferably carried out at a temperature at which the polymerizable liquid crystal composition exhibits a temperature of the liquid crystal phase or lower. The specific heating temperature is, for example, preferably 20 ° C to 300 ° C, more preferably 30 ° C to 200 ° C, still more preferably 30 ° C to 120 ° C. Further, when the polymerizable group is a (meth)acryloxy group, it is preferably carried out at a temperature lower than 90 °C. If it is the above preferred temperature, polymerization due to heat inequality can be prevented.

As the polymerization method of the polymerizable liquid crystal composition, either or both of photopolymerization and thermal polymerization can be employed.

The optical axis of the optically anisotropic body of the present invention can be adjusted by controlling the pretilt angle using a photo-alignment film. In order to adjust the angle formed by the optical axis with respect to the substrate surface to be 0 to 45 degrees, it is preferable that the pretilt angle is 0 to 45 degrees. Similarly, in order to set the angle formed by the optical axis with respect to the substrate surface to be 45 to 90 degrees, it is preferable that the pretilt angle is 45 to 90 degrees.

As a manufacturing process of the optical anisotropic body which has the optical alignment film of this invention, the following methods are mentioned, for example. As a first step, a coating film of the above polymer is formed on a substrate. In the second step, light having an anisotropy is irradiated, and an alignment control function is applied to the coating film to form a photo-alignment film. As a third step, a film of a polymerizable liquid crystal composition is formed on the above photo-alignment film. In the fourth step, a film of the polymerizable liquid crystal composition is polymerized to form an optical anisotropic body. In the fourth step, the isomerization reaction or the crosslinking reaction may be simultaneously carried out in the photo-alignment film.

In the manufacturing process exemplified above, the coating film of the polymer is directly irradiated with light, whereby a light alignment film having excellent alignment resistance of liquid crystal molecules can be obtained.

Moreover, as another manufacturing method, the following methods are mentioned. As a first step, a coating film of the above polymer is formed on a substrate. As a second step, polymerization is formed on the above coating film A film of a liquid crystal composition. In the third step, light having an anisotropy is irradiated, and an alignment control force of the liquid crystal is imparted to the coating film of the polymer to form a photo-alignment film. In the fourth step, a film of the polymerizable liquid crystal composition is polymerized to form an optical anisotropic body. Here, the third step and the fourth step may be simultaneously performed by light irradiation or the like. By performing simultaneously, the number of steps can be reduced.

It is possible to laminate a plurality of layers composed of optically anisotropic bodies as needed. As a method of forming the layered body of the optically anisotropic body, a method of repeating the method of forming a single layer may be mentioned. For example, there may be mentioned a method of forming a first layer of an optically oriented body on a photo-alignment film, newly forming a photo-alignment film on the first layer, and forming a second layer of the optically-isotropic body on the photo-alignment film; A second layer of optically anisotropic bodies is formed on the first layer of the optically oriented body formed on the photoalignment film.

The use of the laminated body of the optically anisotropic body having a layer of a plurality of optically anisotropic bodies is, for example, a method of simultaneously performing optical compensation of a liquid crystal layer of a liquid crystal display element and a polarizing plate, and simultaneously performing liquid crystal layer of the liquid crystal display element. The use of optical compensation and brightness enhancement, and the use of optical compensation and brightness enhancement of a polarizing plate of a liquid crystal display element.

The optical anisotropic body may be subjected to a heating and aging treatment for stabilizing the solvent resistance or heat resistance of the obtained optically opposed body.

The polymerizable liquid crystal composition used for the production of the optically anisotropic body is not particularly limited, and a known liquid crystal composition containing a polymerizable liquid crystal exhibiting liquid crystallinity with a composition of another liquid crystal compound can be used alone or in a single application.

The optically oriented body obtained by the above steps may be used as an optically anisotropic body by peeling off the optically anisotropic layer from the substrate, or may be used as an optically anisotropic body having a substrate without being peeled off from the substrate.

<About terms>

In the present specification, the optical axis system is set to be a liquid crystal display element or an optically anisotropic body, and has a constant refractive index. Even if light is not incident, birefringence does not occur, and ordinary light is consistent with or abnormal with ordinary light. Become the smallest direction.

In the present specification, the orientation of the liquid crystal molecules in the liquid crystal cell of the liquid crystal display element or the direction in which the polymerizable liquid crystal molecules forming the optically anisotropic body are oriented in a certain direction is set as a molecule in the case of a rod-shaped liquid crystal molecule. The orientation taken by the long axis is set to the normal direction with respect to the disk surface in the case of a disk-shaped liquid crystal molecule.

In the present specification, the pretilt angle is an angle formed by the alignment direction of the liquid crystal molecules or the polymerizable liquid crystal molecules and the substrate surface.

In the present specification, the polymerizable liquid crystal is a compound which exhibits a liquid crystal phase and contains a chemical structure capable of being polymerized.

In the present specification, the horizontal alignment system is an alignment in which the pretilt angle is 0 degrees or more and 20 degrees or less.

In the present specification, the vertical alignment system is an alignment in which the pretilt angle is 70 degrees or more and 90 degrees or less. The angle formed by the optical axis with respect to the substrate surface may be the same as the pretilt angle, or may be inconsistent.

[Examples]

The invention will be further illustrated by the examples, but the invention is not limited by the examples. Hereinafter, "parts" and "%" are quality standards unless otherwise specified.

<Synthesis Example 1>

The compound represented by the following formula (1) is added to a reaction vessel equipped with a thermometer and a stirring device, suspended in an aqueous hydrochloric acid solution, cooled in an ice bath, and reacted with sodium nitrite. After that, the mixture is reacted with phenol or sodium hydroxide to obtain a compound represented by the following formula (2).

The compound represented by the following formula (3) is reacted with methacrylic acid or p-toluenesulfonic acid monohydrate in a reaction vessel equipped with a thermometer, a stirring device, and a Dean-Stark apparatus to obtain the following formula (4). Expressed as a compound.

The compound represented by the following formula (2) and potassium carbonate are added to a reaction vessel equipped with a thermometer and a stirring device, and reacted with a compound represented by the following formula (4) to obtain the following formula (m1). Expressed as a compound.

<Synthesis Example 2>

The compound represented by the following formula (5) is added to a reaction vessel equipped with a thermometer and a stirring device, and reacted with a third butyl acrylate in the presence of a palladium catalyst to obtain a compound represented by the following formula (6). After the compound, it is reacted with hydrogen in the presence of zinc and ammonium chloride to obtain a compound represented by the following formula (7).

In a reaction vessel equipped with a thermometer and a stirring device, the combination represented by the following formula (7) is used. The product was suspended in an aqueous hydrochloric acid solution, cooled in an ice bath, and reacted with sodium nitrite, and then reacted with phenol or sodium hydroxide to obtain a compound represented by the following formula (8).

The compound represented by the following formula (3) is reacted with acrylic acid and p-toluenesulfonic acid monohydrate in a reaction vessel equipped with a thermometer, a stirring device, and a Dean-Stark apparatus to obtain a compound represented by the following formula (9). Compound.

The compound represented by the following formula (8) and potassium carbonate are added to a reaction vessel equipped with a thermometer and a stirring device, and reacted with a compound represented by the following formula (9) to obtain the following formula (10). After expressing the compound, it is allowed to react with trifluoroacetic acid to obtain a compound represented by the following formula (11).

The compound represented by the following formula (12) is added to a reaction vessel equipped with a thermometer and a stirring device, and reacted with a third butanol to obtain a compound represented by the following formula (13), and then The compound represented by the formula (14) is reacted to obtain a compound represented by the following formula (15).

The compound represented by the following formula (11) is reacted with a compound represented by the following formula (15) in a reaction vessel equipped with a thermometer and a stirring device in the presence of azodicarboxylic acid or triphenylphosphine. A compound represented by the following formula (16) is obtained.

The compound represented by the following formula (16) is added to a reaction vessel equipped with a thermometer and a stirring device, and reacted with trifluoroacetic acid, followed by 2-nitrile ethanol in the presence of azodicarboxylic acid and triphenylphosphine. The reaction is carried out to obtain a compound represented by the following formula (m2).

<Synthesis Example 3>

The compound represented by the following formula (5) is added to a reaction vessel equipped with a thermometer and a stirring device, and reacted with a third butyl acrylate in the presence of a palladium catalyst to obtain a compound represented by the following formula (6). It is reacted with hydrogen in the presence of zinc and ammonium chloride to obtain a compound represented by the following formula (17).

In a reaction vessel equipped with a thermometer and a stirring device, the compound represented by the following formula (17) is suspended in an aqueous hydrochloric acid solution, cooled in an ice bath, and reacted with sodium nitrite to cause phenol and hydration. Sodium is reacted, whereby a compound represented by the following formula (18) is obtained.

After obtaining a compound represented by the following formula (18) in the same manner as in the synthesis example 2, a compound represented by the following formula (9) and potassium carbonate are added to a reaction container equipped with a thermometer and a stirring device to obtain A compound represented by the following formula (19).

The following formula (19) was reacted with trifluoroacetic acid in the same manner as in Synthesis Example 2, and then reacted with 2-nitrileethanol in the presence of azodicarboxylic acid or triphenylphosphine to obtain the next The compound represented by the formula (m3).

<Synthesis Example 4>

The compound represented by the following formula (20) is added to a reaction vessel equipped with a thermometer and a stirring device, and reacted with ^t BuOK to obtain a compound represented by the following formula (21), which is then present in the presence of palladium/carbon. This is allowed to react with hydrogen to obtain a compound represented by the following formula (22).

The reaction container having a thermometer and a stirring device is a compound represented by the following formula (22) The mixture is suspended in an aqueous hydrochloric acid solution, cooled in an ice bath, and reacted with sodium nitrite, and then reacted with phenol or sodium hydroxide to obtain a compound represented by the following formula (23).

The compound represented by the following formula (23) and potassium carbonate are added to a reaction vessel equipped with a thermometer and a stirring device, and reacted with a compound represented by the following formula (9) to obtain the following formula (24). Expressed as a compound.

A compound represented by the following formula (24) was added to a reaction vessel equipped with a thermometer and a stirring apparatus, and reacted with trifluoroacetic acid in the same manner as in Synthesis Example 2, followed by azodicarboxylic acid and triphenylbenzene. The reaction with 2-nitrile ethanol is carried out in the presence of a phosphine to obtain a compound represented by the following formula (m4).

<Synthesis Example 5>

A compound represented by the following formula (18) and potassium carbonate obtained by the same method as in Synthesis Example 2 were added to a reaction vessel equipped with a thermometer and a stirring apparatus to obtain the following formula (4) obtained in Synthesis Example 1. The compound represented by the reaction is carried out to obtain the following formula (25), and The reaction is carried out with trifluoroacetic acid to obtain a compound represented by the following formula (m5).

<Synthesis Example 6>

The (m5) obtained in Synthesis Example 5 was reacted with 2-nitrile ethanol in the presence of azodicarboxylic acid and triphenylphosphine to obtain a compound represented by the following formula (m6).

<Synthesis Example 7>

The compound represented by the formula (23) was obtained by the same method as in the synthesis example 4, and the compound represented by the following formula (4) and potassium carbonate were added to a reaction container equipped with a thermometer and a stirring apparatus to obtain the following formula. (26) The compound represented.

The compound represented by the following formula (26) is added to a reaction vessel equipped with a thermometer and a stirring device, and reacted with trifluoroacetic acid, and then reacted with 2- in the presence of azodicarboxylic acid or triphenylphosphine. The nitrile ethanol is reacted to obtain a compound represented by the following formula (m7).

<Synthesis Example 8>

The compound represented by the formula (26) was obtained by the same method as in Synthesis Example 7, and then reacted with trifluoroacetic acid to obtain a compound represented by the following formula (m8).

<Synthesis Example 9>

The compound represented by the following formula (27) is reacted with methacrylic acid or p-toluenesulfonic acid monohydrate in a reaction vessel equipped with a thermometer, a stirring device, and a Dean-Stark apparatus to obtain the following formula (28). Expressed as a compound.

31.50 g of the compound represented by the following formula (29), 1.09 g of DMF, and 120 mL of CH ₂ Cl ₂ were mixed. After dropwise addition of 20.83 g of oxalic acid chloride, the mixture was heated under reflux for 2 hours. The obtained solution was concentrated, whereby 37.00 g of a compound represented by the following formula (30) was obtained.

37.00 g of the compound represented by the following formula (30) and 120 mL of THF were mixed. 23.44 g of potassium t-butoxide was dissolved in 176 mL of THF, and added thereto at 5 to 10 °C. After reacting at room temperature for 2 hours, 200 mL of water and 400 mL of toluene were added for liquid separation. The obtained solution was concentrated, and purified by column chromatography (solvent: hexane-ethyl acetate mixed solvent) to obtain 43.42 g of the compound represented by the following formula (31).

40.00 g of the compound represented by the following formula (31), 4.00 g of 5 wt% palladium carbon, and 160 mL of ethanol were mixed, and stirred at 40 ° C for 10 hours under a hydrogen pressure of 0.5 MPa. The obtained solution was concentrated by filtration to remove the catalyst, whereby 34.50 g of the compound represented by the following formula (32) was obtained.

15.00 g of the compound represented by the following formula (32) was suspended in 1.7 M hydrochloric acid. 3.53 g of sodium nitrite was dissolved in 35 mL of water, added at 2 to 3 ° C, and stirred at 2 to 3 ° C for a while. Next, it was diluted with 300 mL of MeOH. 4.81 g of phenol was dissolved in an aqueous potassium hydroxide solution, and the mixture was added dropwise at 0 to 2 ° C, and further stirred at 0 to 2 ° C for a while. After adding hydrochloric acid at 2 to 7 ° C, the precipitate extracted by filtration was purified by silica gel chromatography (solution: hexane-ethyl acetate mixed solvent), whereby 6.32 g of the following formula (33) was obtained. ) the compound represented.

3.00 g of the compound represented by the following formula (33), 1.77 g of potassium carbonate and 0.5 mg of methoxyphenol were mixed in 23 mL of DMF. 1.75 g of the compound represented by the following formula (28) was dissolved in 2 mL of DMF, and added dropwise thereto at 70 to 85 °C. Further, the mixture was stirred at 85 ° C for 7.5 hours. After cooling to room temperature and adding water, extraction was performed with ethyl acetate, and the organic layer was washed with water and dried over anhydrous sodium sulfate. After distilling off the solvent under reduced pressure, it was purified by silica gel chromatography (solution: hexane-ethyl acetate mixed solvent) to obtain 2.69 g. The compound represented by the formula (34).

1.5 g of 5-(4-((1-(methacryloxy)octyl)oxy)phenyl)diazenyl)isobutylene isophthalate, 9 mL of CH ₂ Cl _{2 was} mixed. 3 mL of trifluoroacetic acid was added dropwise thereto at 0 to 2 °C. After stirring at room temperature for 2 hours, the reaction solution was concentrated. Next, the obtained solid was dissolved in THF, and then hexane was added thereto to reprecipitate, thereby obtaining 0.75 g of a compound represented by the following formula (m9).

<Synthesis Example 10>

40 g of the compound represented by the following formula (35), 1.60 g of DMF, and 160 mL of CH ₂ Cl ₂ were mixed. After dropwise addition of 30.71 g of hydrazine chloride, the mixture was heated under reflux for 2 hours. The obtained solution was concentrated, whereby 43.90 g of the compound represented by the following formula (36) was obtained.

40.00 g of the compound represented by the following formula (26) and 200 mL of THF were mixed. 26.99 g of potassium t-butoxide was dissolved in 100 mL of THF, and added thereto at 5 to 10 °C. After reacting at room temperature for 2 hours, 200 mL of water and 600 mL of toluene were added to carry out liquid separation. The obtained solution was concentrated, and purified by column chromatography (solvent: hexane-ethyl acetate mixed solvent) to obtain 28.53 g of the compound represented by the following formula (37).

25.00 g of the compound represented by the following formula (37), 2.50 g of 5 wt% palladium carbon, and 150 mL of THF were mixed, and stirred at a hydrogen pressure of 0.3 MPa at 25 ° C for 6 hours. The obtained solution was concentrated by filtration to remove the catalyst, whereby 21.0 g of the compound represented by the following formula (38) was obtained.

20 g of the compound represented by the following formula (38) was suspended in 88 mL of 10% hydrochloric acid. 7.3 g of sodium nitrite was dissolved in 75 mL of water, added at 2 to 3 ° C, and stirred at 2 to 3 ° C for a while. Next, a solution obtained by mixing 9.08 g of phenol, 40.9 g of sodium carbonate, and 250 mL of water was added dropwise at 0 to 2 ° C, and further stirred at 0 to 2 ° C for a while. After adding 10% hydrochloric acid at 2 to 7 ° C, the precipitate extracted by filtration was purified by gelatin chromatography (solution: hexane-ethyl acetate mixed solvent), whereby 24.1 g of the following formula was obtained. (39) The compound represented.

20.00 g of the compound represented by the following formula (39), 17.70 g of potassium carbonate and 4 mg of methoxyphenol were mixed in 300 mL of DMF. 17.88 g of the compound represented by the following formula (28) was added dropwise thereto at 70 to 85 °C. Further, the mixture was stirred at 85 ° C for 7.5 hours. The mixture was cooled to room temperature and water was added to obtain a precipitate. This was filtered, and purified by silica gel chromatography (solvent: hexane-ethyl acetate mixed solvent) and recrystallization (EtOH) to obtain 25.06 g of the compound represented by the following formula (40).

10 g of the compound represented by the following formula (40) and 60 mL of CH ₂ Cl ₂ were mixed. 20 mL of trifluoroacetic acid was added dropwise thereto at 0 to 2 °C. After stirring at room temperature for 2 hours, the reaction solution was concentrated. Next, after dissolving the obtained solid in THF, hexane was added and reprecipitated to obtain 7.56 g of the compound represented by the following formula (m10).

<Synthesis Example 11>

20 g of the compound represented by the following formula (41) was suspended in 170 g of 10% hydrochloric acid. 12.63 g of sodium nitrite was dissolved in 120 mL of water, added at 2 to 3 ° C, and stirred at 2 to 3 ° C for a while. Next, 17.22 g of phenol was dissolved in 220 g of a 10% aqueous sodium hydroxide solution, and the mixture was added dropwise at 0 to 2 ° C, and further stirred at 0 to 2 ° C for a while. Concentrated hydrochloric acid was added at 2 to 7 °C. The precipitate obtained by filtration was purified by gelatin chromatography (solution: hexane-ethyl acetate mixed solvent), and further recrystallized in a mixed solvent of hexane and toluene to obtain 13.7 g of the following. a compound represented by the formula (42).

10.00 g of 4,4'-(diazene-1,2-diyl)diphenol, 6.45 g of potassium carbonate and 2 mg of methoxyphenol were mixed in 80 mL of DMF. 10.87 g of the compound represented by the following formula (28) was added dropwise thereto at 70 to 85 °C. Further, the mixture was stirred at 85 ° C for 7.5 hours. After cooling to room temperature and adding water, extraction was performed with ethyl acetate, and the organic layer was washed with 10% hydrochloric acid, and then the organic layer was washed with water and dried over anhydrous sodium sulfate. After distilling off the solvent under reduced pressure, the mixture was separated and purified by silica gel chromatography (solvent: hexane-ethyl acetate mixed solvent) to obtain 2.88 g of the compound represented by the following formula (m11). .

<Synthesis Example 12>

34 g of 10-bromo-1-nonanol, 22 g of methacrylic acid, 70 mg of 4-methoxyphenol, 2 g of p-toluenesulfonic acid monohydrate, 200 mL of cyclohexane, and 40 mL of diisopropyl ether were mixed by oil bath. Heating was carried out and refluxed for 8 hours. After the reaction solution was left to cool to 30 ° C, 100 mL of water was added to the reaction mixture, and the organic layer was extracted. The organic layer was washed twice with 100 mL of a 5% aqueous sodium hydrogen carbonate solution, and the organic layer was washed once with 100 mL of saturated brine. The organic layer after washing was concentrated under reduced pressure to obtain 50 g of the compound represented by the following formula (a-1-1) as a colorless liquid. In the reaction vessel, 23 g of p-hydroxybenzaldehyde, 46 g of potassium carbonate, and 46 g of the compound (a-1-1) were suspended in 300 mL of DMF, and stirred at 90 ° C for 6 hours, and the reaction was terminated. After cooling the reaction liquid to 10 ° C, 650 mL of water was added dropwise to the reaction liquid to precipitate a solid. The solid was collected by filtration to obtain 72 g of the compound represented by the following formula (a-1-2) as a brown granular solid. In the reaction vessel, 66 g of the compound represented by the following formula (a-1-2) was dissolved in 980 mL of methanol, and an aqueous solution of sodium dihydrogen phosphate was added thereto in that order (19 g of sodium dihydrogen phosphate dihydrate was dissolved in water). 250 mL of the solution), 30% of 30% hydrogen peroxide water. An aqueous solution of sodium chlorite (a solution obtained by dissolving 27 g of sodium chlorite having a purity of 80% in 220 mL of water) was added dropwise. After completion of the dropwise addition, the reaction mixture was stirred at 45 ° C for 3 hours, and the reaction was completed. After the reaction liquid was slowly cooled to 20 ° C, water was added dropwise to the reaction liquid to precipitate a solid. The solid was collected by filtration and the solid was spray washed with water. The crude product of the colorless scaly crystal obtained in the above manner was dried under reduced pressure for 8 hours to obtain 47 g of the compound (a-1-3) as colorless crystals.

On the other hand, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride 54 0.3 g of g,4-dimethylaminopyridine was dissolved in 406 mL of 2-cyanoethanol. A solution obtained by dissolving 50 g of ferulic acid in 203 mL of 2-cyanoethanol was added dropwise to the solution at 10 ° C for 1 hour, and the mixture was stirred at room temperature for 4 hours. The reaction solution was mixed with cold water of 15 ° C, and a toluene/THF mixed solvent was added to the mixture to extract an organic layer. The organic layer was washed with 200 mL of a saturated aqueous solution of sodium chloride, and the obtained solid solid was recrystallized to obtain 37 g of the compound represented by the following formula (a-1-4) as a white solid.

39 g of the compound represented by the following formula (a-1-3), 28 g of the compound represented by the following formula (a-1-4), and 0.3 g of 4-dimethylaminopyridine were suspended in 140 mL of dichloromethane. The internal temperature was kept below 10 ° C, and 172 g of diisopropylcarbodiimide was added dropwise, followed by stirring at 15 to 25 ° C for 3 hours. After confirming the disappearance of the raw material, the reaction was deactivated by adding water to the reaction liquid. The obtained precipitate was separated by filtration to obtain a dichloromethane solution, which was then purified by column chromatography. Methylene chloride was distilled off from the dichloromethane solution under reduced pressure, and methanol was added thereto, and the mixture was cooled to 0 ° C to precipitate crystals. The crystals were separated by filtration and dried under reduced pressure to obtain 51 g of a compound represented by the following formula (a-1) as a cinnamic acid methacrylate monomer.

<Synthesis Example 13>

The compound represented by the following formula (43) is added to a reaction vessel equipped with a thermometer and a stirring device, suspended in an aqueous hydrochloric acid solution, cooled in an ice bath, and reacted with sodium nitrite to form a phenol, The sodium hydroxide is reacted to obtain a compound represented by the following formula (44).

The compound represented by the following formula (44) and potassium carbonate are added to a reaction vessel equipped with a thermometer and a stirring device, and reacted with a compound represented by the following formula (4) to obtain the following formula (ref-m). ) the compound represented.

<Synthesis of Polymer> <Synthesis Example 14>

3.0 g of the monomer (a-1) obtained in Synthesis Example 12, 0.1 g of the monomer (m1) obtained in Synthesis Example 1, and 115 mg of V-65 (2,2'-Azobis (2.4-dimethylvaleronitrile) were used. After stirring at 50 ° C for 15 hours, the reaction mixture was cooled to room temperature and added to hexane to precipitate a polymer. The solvent was removed by decantation, and the precipitate was again dissolved in THF and precipitated by hexane. Further, this decantation operation was carried out seven times, and then dried under reduced pressure to obtain 1.5 g of the copolymer (P1) represented by the following formula (p1).

The obtained copolymer was determined by gel permeation chromatography (GPC) under the conditions described below. The molecular weight was found to have a weight average molecular weight (Mw) of 197,655 in terms of polystyrene standards, a dispersion ratio (Mw/Mn) of 2.96, and a monomer remaining amount of 0.02%.

<GPC measurement conditions>

Pipe column: Shodex KF-803L, KF-804L, KF-805, KF-806 manufactured by Showa Denko Co., Ltd.

(These are connected in series)

Lysate: THF

Sample solution concentration: 0.1 (w / v)% (solvent THF)

Sample injection amount: 200 μL

Column temperature: 40 ° C

Column flow: 1.0mL/min

Detector: RI

Hereinafter, the measurement conditions of GPC are the same.

<Synthesis Example 15>

3.0 g of the monomer (a-1) obtained in Synthesis Example 12, 0.175 g of the monomer (m2) obtained in Synthesis Example 2, 8.3 mg of AIBN and 15 mL of THF were used, and the mixture was stirred at 55 ° C for 8 hours. In the same manner as in Synthesis Example 14, a total of 1.1 g of the following formula (p2) was obtained. Polymer (P2).

The molecular weight of the obtained copolymer was measured by GPC, and as a result, the weight average molecular weight (Mw) was 194,288, the dispersion ratio (Mw/Mn) was 3.07, and the monomer remaining amount was 0.08% based on polystyrene standards.

<Synthesis Example 16>

5.756 g of the monomer (a-1) obtained in Synthesis Example 12, 244 mg of the monomer (m3) obtained in Synthesis Example 3, 67.3 mg of AIBN, and 16.0 ml of tetrahydrofuran (THF) were mixed in a flask. After stirring for 1.75 hours at 55 ° C under a nitrogen atmosphere, hexane (in the present synthesis example, 30 mL) was added in an amount of 5 times the amount of the monomer used (5 mL in terms of 1 g of the monomer), and the reaction mixture was allowed to precipitate. The supernatant was removed by decantation. The reaction mixture was redissolved in 3 times the amount of the monomer used (3 mL relative to 1 g of the monomer) of THF (18 mL in the present synthesis example), and 5 times the amount of the monomer used was added ( The reaction mixture was precipitated with 5 mL of hexane (30 mL in the present synthesis example) with respect to 1 g of the monomer, and the supernatant was removed by decantation. After further re-dissolving in THF, three times by leaching of hexane and decantation, the obtained reaction mixture was dried under reduced pressure at 20 ° C, 0.13 kPa for 24 hours under reduced pressure to obtain 1.46 g. The copolymer (P3) represented by the following formula (p3).

The molecular weight of the obtained copolymer was determined by GPC measurement, and the result was in the polystyrene standard. The weight average molecular weight (Mw) was 233, 911, the dispersion ratio (Mw/Mn) was 2.02, and the residual amount of the monomer was 0.15%.

<Synthesis Example 17>

5.756 g of the monomer (a-1) obtained in Synthesis Example 12, 244 mg of the monomer (m4) obtained in Synthesis Example 4, 16.8 mg of AIBN and 16.0 ml of THF were used, and the mixture was stirred at 60 ° C for 2 hours. In the same manner as in Synthesis Example 14, 1.28 g of the copolymer (P4) represented by the following formula (p4) was obtained.

The molecular weight of the obtained copolymer was measured by GPC, and as a result, the weight average molecular weight (Mw) was 224,302, the dispersion ratio (Mw/Mn) was 1.99, and the residual amount of the monomer was 0.01% based on polystyrene standards.

<Synthesis Example 18>

4.813 g of the monomer (a-1) obtained in Synthesis Example 12, 187 mg of the monomer (m5) obtained in Synthesis Example 5, 14.1 mg of AIBN and 16.0 ml of THF were stirred at 60 ° C for 4 hours. In the same manner as in Synthesis Example 14, 1.58 g of the following formula (p5) was obtained. Copolymer (P5).

The molecular weight of the copolymer obtained was measured by GPC. As a result, the weight average molecular weight (Mw) was 203,802, the dispersion ratio (Mw/Mn) was 1.97, and the residual amount of the monomer was 0.08% based on polystyrene standards.

<Synthesis Example 19>

4.791 g of the monomer (a-1) obtained in Synthesis Example 12, 209 mg of the monomer (m6) obtained in Synthesis Example 6, 14.0 mg of AIBN and 13.2 ml of THF were used, and the mixture was stirred at 60 ° C for 2 hours. In the same manner as in Synthesis Example 14, 0.97 g of the copolymer (P6) represented by the following formula (p6) was obtained.

The molecular weight of the copolymer obtained was measured by GPC. As a result, the weight average molecular weight (Mw) was 269,843, the dispersion ratio (Mw/Mn) was 1.76, and the monomer remaining amount was 0.01% based on polystyrene standards.

<Synthesis Example 20>

3.0 g of the monomer (a-1) obtained in Synthesis Example 12 and 0.12 g obtained in Synthesis Example 7 were used. In the same manner as in Synthesis Example 14, 1.0 g of the copolymer represented by the following formula (p7) was obtained in the same manner as in Synthesis Example 14 except that the monomer (m7), 26.1 mg of AIBN, and 10 mL of THF were stirred at 60 ° C for 2 hours. (P7).

The molecular weight of the obtained copolymer was measured by GPC, and as a result, the weight average molecular weight (Mw) was 157,437 and the dispersion ratio (Mw/Mn) was 1.95 based on polystyrene standards.

<Synthesis Example 21>

5.0 g of the monomer (a-1) obtained in Synthesis Example 12, 0.18 g of the monomer (m8) obtained in Synthesis Example 8, 14.6 mg of AIBN and 14 mL of THF were stirred at 60 ° C for 2 hours. In the same manner as in Synthesis Example 14, 1.4 g of the copolymer (P8) represented by the following formula (p8) was obtained.

The molecular weight of the obtained copolymer was measured by GPC, and as a result, the weight average molecular weight (Mw) was 241,740 and the dispersion ratio (Mw/Mn) was 1.93 based on polystyrene standards.

<Synthesis Example 22>

2.33 g of the monomer (a-1) obtained in Synthesis Example 12, 0.100 g of the monomer (m9) obtained in Synthesis Example 9, and 11.2 mg of AIBN were dissolved in THF, and the mixture was carried out under a nitrogen atmosphere at 60 ° C. After the reaction, the reaction mixture was cooled to room temperature and added to hexane to precipitate a polymer. The solvent was removed by a decantation method, and the precipitate was redissolved in THF and precipitated by hexane. Further, this decantation operation was carried out 7 times, and then dried under reduced pressure to obtain 0.73 g of a copolymer (P9) represented by the following formula (p9).

The molecular weight of the obtained copolymer was measured by GPC, and as a result, the weight average molecular weight (Mw) was 208,790 and the dispersion ratio (Mw/Mn) was 2.13 based on polystyrene standards.

<Synthesis Example 23>

3.73 g of the monomer (a-1) obtained in Synthesis Example 12, 0.150 g of the monomer (m10) obtained in Synthesis Example 10, and 15.2 mg of AIBN were dissolved in THF, and the mixture was carried out under a nitrogen atmosphere at 60 ° C. After the reaction, the reaction mixture was cooled to room temperature and added to hexane to precipitate a polymer. The solvent was removed by a decantation method, and the precipitate was redissolved in THF and precipitated by hexane. Further, this decantation operation was carried out 7 times, and then dried under reduced pressure to obtain 1.23 g of a copolymer (P10) represented by the following formula (p10).

The molecular weight of the obtained copolymer was measured by GPC, and as a result, the weight average molecular weight (Mw) was 217,725 and the dispersion ratio (Mw/Mn) was 2.04 based on polystyrene standards.

<Synthesis Example 24>

2.19 g of the monomer (a-1) obtained in Synthesis Example 12, 0.080 g of the monomer (m11) obtained in Synthesis Example 11, and 13.2 mg of AIBN were dissolved in THF, and the mixture was carried out under a nitrogen atmosphere at 60 ° C. After the reaction, the reaction mixture was cooled to room temperature and added to hexane to precipitate a polymer. The solvent was removed by a decantation method, and the precipitate was redissolved in THF and precipitated by hexane. Further, this decantation operation was carried out 7 times, and then dried under reduced pressure to obtain 0.63 g of a copolymer (P11) represented by the following formula (p11).

The molecular weight of the obtained copolymer was measured by GPC, and as a result, the weight average molecular weight (Mw) was 253,167 and the dispersion ratio (Mw/Mn) was 1.99.

<Synthesis Example 25>

20.0 g of the monomer (a-1) obtained in Synthesis Example 12, 0.78 g of the monomer (ref-m) obtained in Synthesis Example 13, 55.5 mg of AIBN, and 80 mL of tetrahydrofuran (THF) were mixed in a flask. After stirring for 7 hours at 55 ° C under a nitrogen atmosphere, 5 times the amount of the monomer used (5 mL relative to 1 g of the monomer) of hexane (100 mL in the present synthesis example) was added to precipitate the reaction mixture. The supernatant was removed by decantation. The reaction mixture was redissolved in 3 times the amount of the monomer used (3 mL relative to 1 g of the monomer) of THF (60 mL in the present synthesis example), and 5 times the amount of the monomer used was added ( The reaction mixture was precipitated with 5 mL of hexane (100 mL in the present synthesis example) with respect to 1 g of the monomer, and the supernatant was removed by decantation. Further, after re-dissolving in THF, three times by leaching of hexane, and decantation, the obtained reaction mixture was dried under reduced pressure at 20 ° C, 0.13 kPa for 24 hours under reduced pressure to obtain 9.1 g. A copolymer (Ref-p) represented by the following formula (Ref-p).

The molecular weight of the obtained copolymer was determined by GPC measurement. As a result, the weight average molecular weight (Mw) was 235, 306, the dispersion ratio (Mw/Mn) was 2.16, and the residual amount of the monomer was 0.24% based on polystyrene standards.

[Example 1]

After dissolving the copolymer (p1) in N-methyl-2-pyrrolidone (hereinafter referred to as NMP), 2-butoxyethanol is added to become NMP:2-butoxyethanol by weight ratio: In the manner of P1)=47.5:47.5:5, the polymer solution for the photo-alignment film was obtained by filtration using a MS PTFE syringe filter (5 μm, 1 μm, 0.45 μm) manufactured by Membrane Solution Co., Ltd. This solution was spin-coated on the IPS3035-2up substrate and the counter substrate manufactured by FPD Solution so as to have a thickness of about 90 nm using a spin coater IH-DX-2 manufactured by Mikasa Co., Ltd. Thereafter, it was dried at 80 ° C for 3 minutes on a heating plate digital hot plate NINOS ND1 manufactured by AS ONE, and further dried in an air atmosphere at 150 ° C for 5 minutes using an oven DO-600FA manufactured by AS ONE. After drying, slowly cool to room temperature. Then, the optical alignment film of Example 1 was produced by irradiating the dried film with a linear polarized light of 313 nm and 313 nm at 150 mJ/cm ² at a luminance of ²⁰ mW/cm ² using a polarizing irradiation apparatus manufactured by Mejiro Precision.

For the substrate on which the photo-alignment film was formed, the STRUCTBOND XN-21-S manufactured by Mitsui Chemicals, Inc. was applied to the IPS substrate side using a sealant dispenser manufactured by Musashi Engineering Co., Ltd. After coating, the sealant was dried at 90 ° C for 30 minutes to bond the substrate. After bonding the substrates, they were heated at 150 ° C for 90 minutes to form a glass tank. After slowly cooling to room temperature, the liquid crystal injection was performed using a vacuum injection device manufactured by Mikasa Co., Ltd. Into, the liquid crystal PA0500 manufactured by DIC Corporation was injected into the groove produced. After the injection, the sealing material 3026B manufactured by 3M Company was applied to the opening of the tank, and the UV irradiation device manufactured by Fujiwara Seisakusho Co., Ltd. was used to seal only the vicinity of the sealing agent by ultraviolet rays.

A wire was attached to the obtained liquid crystal cell and heated at 92 ° C for 2 minutes. Thereafter, the voltage holding ratio was measured at an ambient temperature of 60 ° C, a frame time of 16.6 msec, and an applied voltage of 5 V using a VHR measuring apparatus VHRAMP01 manufactured by Toyo Corporation. As a result, the VHR was 96.8%.

The nematic liquid crystal hybrid PA0500 manufactured by the above DIC Corporation was prepared by blending the liquid crystal compounds shown in the contract table with the blending amounts described in Table 2. The nematic-isotropic liquid phase transition temperature (clearing point) was 85.6 ° C as a result of thermal analysis of the obtained nematic liquid crystal mixture PA0500. Further, the extraordinary light refractive index n _e at a wavelength of 589 nm was 1.596, and the ordinary refractive index n _o at a wavelength of 589 nm was 1.491. Further, the dielectric anisotropy was +7.0, and K ₂₂ (torsion elastic modulus) was 7.4 pN.

[Examples 2 to 11]

A photo-alignment film and a liquid crystal cell using the copolymers (P2) to (P11) were produced in the same manner as in Example 1, and VHR was measured. The results are shown in Table 3.

[Comparative Example 1]

A photoalignment film using a copolymer (Ref-p) and a liquid crystal cell were produced in the same manner as in Example 1, and VHR was measured. The results are shown in Table 3.

From the above results, it was confirmed that the liquid crystal cell having the photo-alignment film of the example of the present invention exhibited an excellent voltage holding ratio (VHR). From this finding, it is understood that the photo-alignment film of the embodiment of the present invention exerts an excellent alignment regulating force. Further, when the photo-alignment film was produced, the amount of the polarized ultraviolet ray was small, and it was found that the photo-alignment polymer of the example of the present invention has a high sensitivity to the polarized ultraviolet ray.

<Preparation of optical alignment film and optical anisotropic body> [Example 12]

5 parts of the copolymer (p1) was dissolved in a mixed solvent of 47.5 parts of N-methyl-2-pyrrolidone and 47.5 parts of 2-butoxyethanol, and stirred at room temperature for 10 minutes. Then, the solution was separately applied to two glass plates as a substrate using a spin coater. Here, a comb-shaped pattern ITO electrode having an electrode spacing of 5 μm was formed on one of the pair of glass plates in the longitudinal direction of the glass plate. Then, the two glass plates coated with the above solution were heated at 80 ° C for 3 minutes. The bell was further heated at 180 ° C for 5 minutes to obtain a coating film of a polymer (P1) having a film thickness of about 0.1 μm. The polymer (P1) was uniformly coated on a glass plate to form a smooth film.

Secondly, the wavelength-cut filter, the band-pass filter and the polarizing filter are interposed, and the surface of the glass plate formed with the coating film is irradiated with ultraviolet light in the form of parallel light (313 nm, illuminance 20 mW/cm ^{2 ) in} the form of parallel light. ) to obtain a photo-alignment film (optical alignment layer). The ultraviolet light to be irradiated is linearly polarized, and the glass plate surface is irradiated with ultraviolet light from the normal direction so that the vibration direction of the linearly polarized electric field is parallel to the comb pattern ITO electrode (longitudinal direction of the glass plate). The ultraviolet light irradiation energy was 100 mJ/cm ² .

A polymerizable liquid crystal composition (LC-1) obtained by blending the liquid crystal compound shown in the contract table with the blending amount shown in Table 4 on the photoalignment film obtained above was applied to the optical alignment film obtained by the spin coater. After drying at ° C for 1 minute, ultraviolet rays of 1 J/cm ² were irradiated under a nitrogen atmosphere to polymerize the polymerizable liquid crystal composition (LC-1) to obtain an optical anisotropic body.

The obtained optically anisotropic body was evaluated by the following method, and as a result, the orientation was A, and a good alignment was obtained with a small amount of irradiation of 100 mJ/cm ² . Observing the direction of alignment, the result becomes horizontal alignment. Further, it is understood that the optically anisotropic body of the present invention can impart an orientation and a controllable alignment direction with a very small amount of ultraviolet radiation during production.

(Evaluation method of orientation)

The optically anisotropic body was evaluated by visual inspection of the appearance of the optically anisotropic body and observation by a polarizing microscope.

A: Uniform alignment can be obtained under visual observation, and it is completely defect-free even under the observation of a polarizing microscope.

B: Uniform alignment can be obtained under visual observation, but the alignment area under polarizing microscope observation is 90 ~100%.

C: The alignment such as A and B could not be obtained under visual observation, but the alignment area under the polarizing microscope observation was 60 to 90%.

D: It is close to no alignment under visual observation, but the alignment area under the polarizing microscope observation is 40 to 60%.

E: There is no alignment under visual observation, and the alignment area under the observation of a polarizing microscope is also 40% or less.

[Examples 13 to 22]

An optically anisotropic body was obtained in the same manner as in Example 12 except that the copolymer (P2) to (P11) were used instead of the copolymer (P1). The obtained optically anisotropic body was evaluated by the above method, and as a result, the orientation was A, and the alignment direction was observed, and as a result, it was horizontally aligned. Therefore, in the same manner as in the example 12, an optically anisotropic body having excellent alignment properties can be produced with a light irradiation amount of less than 100 mJ/cm ² .

[Comparative Example 2]

An optically anisotropic body was obtained in the same manner as in Example 12, except that the copolymer (Ref-p) was used instead of the copolymer (P1), and the polymerizable liquid crystal composition (LC-1) was used. The obtained optically anisotropic body was evaluated, and as a result, the orientation was B. Observing the direction of alignment, the result becomes horizontal alignment.

[Industrial availability]

The polymer for photoalignment film of the present invention can be widely used in the field of liquid crystal displays.

Claims (9)

A polymer for a photo-alignment film, which is represented by the following formula (X), (In the above formula (X), Sp ¹ and Sp ² each independently represent a spacer, and R ¹¹ represents a one-valent substituent or a halogen atom composed of two or more atoms, and the above monovalent substituents are bonded to each other. The absolute value of the difference between the electronegativity of the atoms in any combination of two atoms is 0.45 or more and 1.70 or less, and m is an integer of 1 to 5. When m is 2 or more, a plurality of R ^{11 are} mutually The same or different, A ²¹ , A ²² and A ²³ are each independently selected from (a) trans-1,4-cyclohexylene (one methylene group present in the group or not adjacent to 2) More than one methylene group may be substituted with -O-, -NH- or -S-), (b) 1,4-phenylene group (one or two or more present in the group -CH= Can be substituted with -N=), and (c) 1,4-cyclohexenylene, 2,5-thienthiophenyl, 2,5-extended furanyl, 1,4-bicyclo[2.2.2] Octyl, naphthalene-1,4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl and 1,2,3,4-tetrahydronaphthalene-2,6-diyl In the group formed, the above-mentioned group (a), group (b) or group (c) may be unsubstituted, respectively, or one or more hydrogen atoms may be substituted with a fluorine atom, a chlorine atom, a cyano group or an alkane. Base or alkane When group, p, q and r each independently represent an integer of 0 to 4, in the p, q and r are 2 or more of the case, a plurality of ^{A 21, A 22, A 23} , Z 22 and Z ²⁴ may be identical to each other also Alternatively, Z ²¹ , Z ²² , Z ²³ and Z ²⁴ are each independently selected from a single bond, -O-, -(CH ₂ ) _u - (wherein, u represents 1 to 20), -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -CH=CH-, -CF=CF-, -CF ₂ O-, -OCF ₂ -, -CF ₂ CF ₂ -, and -C≡C- At least one divalent linking group in the group satisfying the condition that D ¹ is -(L ¹ -A ¹ ) _k -C(=O)- and D ² is a single bond, or D ² is -C(=O - (A ^{1 -} L ¹ ) _f - and D ¹ is a single bond condition, L ¹ represents 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-contiguous -CH ₂ - groups constituting L ¹ may be independently substituted with -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 k, f is an integer of 0 to 3, and A ¹ is selected from (a) trans-1,4-cyclohexylene (one methylene group present in the group or two or more adjacent thereto) The methylene group may be substituted with -O-, -NH- or -S-), (b) 1,4-phenylene group (one or two or more present in the group -CH= may be substituted Is -N=), and (c) 1,4-cyclohexene, 2,5-thienyl, 2,5-extended furyl, 1,4-bicyclo[2.2.2] octyl, Naphthalene-1,4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl and 1,2,3,4-tetrahydronaphthalene-2,6-diyl The group in the group, the above group (a), the group (b) or the group (c) may be unsubstituted, respectively, or one or more hydrogen atoms may be substituted with a fluorine atom, a chlorine atom, a cyano group, a methyl group or a group. Oxy groups, X and Y each independently represent a hydrogen atom or a halogen atom, and Z represents a formula (IIa) or (IIb)----OR ¹ (IIa) (wherein, the dotted line indicates a bond with D ² , and R ¹ and R ² each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 50 carbon atoms, and R ¹ and R ² One -CH ₂ - group or two or more non-contiguous -CH ₂ - groups may be substituted from -O-, -CO-, -CO-O-, -O-CO-, -CO-NH- One or more of R ¹ and R ² , one of or more of -NH-CO-, -NCH ₃ -, -CH=CH-, -CF=CF-, and -C≡C- More than one -CH ₂ - group may be independently substituted with a cycloalkyl group having a ring number of 3 to 8, and a hydrogen atom of R ¹ and R ² may be substituted with an alkyl group having 1 to 20 carbon atoms and cyanide. A, b and c represent the molar fraction of the copolymer, in any case 0 < a ≦ 1 and 0 < b ≦ 1 and 0 ≦ c < 1, Ma, Mb and Md The arrangement of the monomer units may be the same as or different from the formula. The monomer units of Ma, Mb and Md may be independently one type, or may be two or more different units, and the individual units of Ma, Mb and Md are respectively Independently expresses the general formula (U-1)~(U-13) (In the above general formulae (U-1) to (U-13), when the expression represents Ma or Mb, the broken line indicates the bond with Sp ¹ and Sp ² , and when the expression indicates Md, The broken line indicates a bond with a hydrogen atom or a monovalent organic group, and R ^a independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, a halogen atom, and the above formula (U-1) to (U- Any hydrogen atom in 13) may be substituted with a fluorine atom, a chlorine atom, a methyl group, a phenyl group, or a methoxy group; R ^1a represents a tetravalent ring structure, R ^2a represents a trivalent organic group, and R ^3a represents a hydrogen atom, Any one of a repeating unit of a hydroxyl group, an alkyl group having 1 to 15 carbon atoms, or an alkoxy group having 1 to 15 carbon atoms). The polymer for a photo-alignment film according to the first aspect of the invention, wherein, in the above formula (X), R ¹¹ is a cyano group, a hydroxyl group, a carboxyl group, a decylamino group, a fluorine, a chlorine group, a thiol group or a nitro group. a sulfonic acid group, a linear or branched alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, or the following general formula (QX)-----S _aa -V _a (QX) (wherein, a broken line indicates a bond bond, _{Sa a} represents a spacer, and Va represents a side chain end), and one or more of the -CH ₂ - groups constituting the alkyl group and the alkoxy group are two or more Can be independently substituted from -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 a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), and one or more substituents in the divalent ring structure are bonded to the above alkyl group and the above alkoxy group One or more hydrogen atoms on the group represented by the above formula (QX) may be substituted with a fluorine atom, a chlorine atom, a cyano group, a hydroxyl group, a carboxyl group, a decylamino group, a fluorine group, a sulfonic acid group or a nitro group. The polymer for a photo-alignment film according to claim 1 or 2, wherein a ratio of a/(a+b+c)×100% is 0.1 to 20% in the above molar fraction. The polymer for a photo-alignment film according to any one of claims 1 to 3, wherein the Sp ¹ is a linear divalent linking group having 2 to 20 carbon atoms. A polymer solution which is an essential component of a photo-alignment polymer and an organic solvent according to any one of claims 1 to 4. The polymer solution of the fourth aspect of the patent application has a solid concentration of 1 to 20% by mass. A photo-alignment film formed of a polymer for a photo-alignment film according to any one of claims 1 to 4. An optically oriented body having the photoalignment film of claim 7 of the patent application. A liquid crystal display element having the photoalignment film of claim 7 of the patent application.