TWI719984B - Polymer composition, liquid crystal alignment agent, liquid crystal alignment film, substrate with the liquid crystal alignment film, and liquid crystal display element with the liquid crystal alignment film - Google Patents

Abstract

The present invention provides a polymer composition for the production of a liquid crystal alignment film that can efficiently obtain a stable alignment control ability, expand the amount of light generated, and have a higher voltage retention rate, specifically a horizontal electric field A polymer composition for the manufacture of liquid crystal alignment films for drive-type liquid crystal display elements.

The present invention provides a polymer composition containing (A) at least two types of polymers having a structure exhibiting photoreactivity and a structure exhibiting liquid crystallinity; and (B) a polymer composition of an organic solvent, and one of the at least two types of polymers The polymer has a crosslinkable group.

Description

Polymer composition, liquid crystal alignment agent, liquid crystal alignment film, substrate with the liquid crystal alignment film, and liquid crystal display element with the liquid crystal alignment film

The present invention relates to a polymer composition for a liquid crystal alignment agent, especially a liquid crystal alignment agent for a horizontal electric field drive type liquid crystal display element, which is composed only of the composition, or is substantially composed of the composition or has the composition Liquid crystal alignment agent, especially liquid crystal alignment agent for horizontal electric field drive type liquid crystal display element, liquid crystal alignment film formed by the liquid crystal alignment agent, especially liquid crystal alignment film for horizontal electric field drive type liquid crystal display element, and liquid crystal alignment film having the liquid crystal alignment film A substrate, especially a substrate for a horizontal electric field drive type liquid crystal display element, and a liquid crystal display element having the substrate, especially a horizontal electric field drive type liquid crystal display element.

The liquid crystal display element is known as a light-weight, thin, and low-power display device. In recent years, it has achieved remarkable development such as being used in large-scale television applications. The liquid crystal display element is constituted by, for example, a pair of transparent substrates provided with electrodes sandwiching a liquid crystal layer. However, in the liquid crystal display element, an organic film made of an organic material is used as the liquid crystal alignment film to bring the liquid crystal into a desired alignment state between the substrates.

That is, the liquid crystal alignment film is a constituent member of the liquid crystal display element, and is formed on the surface of the substrate holding the liquid crystal that contacts the liquid crystal. Between the substrates, it plays a role of aligning the liquid crystal in a certain direction. However, in the liquid crystal alignment film, in addition to the role of aligning the liquid crystal in a certain direction, such as the parallel direction with respect to the substrate, there are also pursuits to play the role of controlling the pretilt angle of the liquid crystal. The ability to control the alignment of liquid crystals in such a liquid crystal alignment film (hereinafter referred to as alignment control ability.) can be obtained by performing alignment processing on the organic film constituting the liquid crystal alignment film.

As an alignment treatment method of a liquid crystal alignment film for imparting alignment control ability, in addition to the conventional rubbing method, a photo-alignment method is known. Compared with the conventional rubbing method, the photo-alignment method has the advantage that no rubbing is required, dust or static electricity is generated, and the alignment treatment can be applied even to the substrate of the liquid crystal display element with uneven surface.

The photo-alignment method has various methods, but linearly polarized light or parallel light is used to form anisotropy in the organic film constituting the liquid crystal alignment film, and the liquid crystal is aligned according to the anisotropy.

As the photo-alignment method, a decomposition-type photo-alignment method, a photo-crosslinking type or a photo-isomerization-type photo-alignment method, and the like are known.

The decomposition-type photo-alignment method, for example, is to irradiate polarized ultraviolet rays on the polyimide film, and use the polarization direction dependence of the ultraviolet absorption of the molecular structure to produce anisotropic decomposition. The method of liquid crystal alignment (for example, Patent Document 1 as a reference).

The photo-crosslinking type or photo-isomerization type photo-alignment method, for example, using polyvinyl cinnamate, irradiating polarized ultraviolet light, The double bond part of the two side chains of the two side chains produces a dimerization reaction (cross-linking reaction) to align the liquid crystal in a direction perpendicular to the polarization direction (for example, Non-Patent Document 1 is used as a reference). In addition, when using a side chain type polymer with azobenzene in the side chain, irradiating polarized ultraviolet light will cause an isomerization reaction at the azobenzene part of the side chain parallel to the polarized light, and make the liquid crystal in the direction perpendicular to the polarized light direction. Alignment (for example, Non-Patent Document 2 as a reference). Furthermore, Patent Document 3 discloses a liquid crystal alignment film obtained by using a photo-alignment method caused by photo-crosslinking, photo-isomerization, or photo-Friesian rearrangement.

[Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 3893659

[Patent Document 2] Japanese Patent Application Laid-Open No. 2-37324

[Patent Document 3] WO2014/054785

[Non-Patent Literature]

[Non-Patent Document 1] M. Shadt et al., Jpn. J. Appl. Phys. 31, 2155 (1992).

[Non-Patent Document 2] K. Ichimura et al., Chem. Rev. 100, 1847 (2000).

As mentioned above, the photo-alignment method and the liquid crystal display element Compared with the conventional rubbing method used in the industry, the alignment treatment method does not require a rubbing step, and has great advantages. However, compared with the rubbing method in which the alignment control ability is almost constant by rubbing, in the optical alignment method, the alignment control ability can be controlled by changing the irradiation amount of polarized light.

However, if the alignment control ability of the main component used in the photo-alignment method is too sensitive to the amount of polarized light, the alignment of a part or the whole of the liquid crystal alignment film will become incomplete, and the alignment of stable liquid crystals cannot be achieved. situation.

The object of the present invention is to provide a substrate having a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display element that imparts alignment control ability with high efficiency and excellent afterimage characteristics, and a horizontal electric field drive type liquid crystal display element having the substrate.

Specifically, the purpose of the present invention is to provide a polymer composition for the production of a liquid crystal alignment film that can efficiently obtain a stable alignment control ability, expand the amount of light generated, and produce a high-quality liquid crystal alignment film. Specifically, it is horizontal A composition for manufacturing a liquid crystal alignment film for an electric field drive type liquid crystal display element.

In addition, the object of the present invention is to provide a horizontal electric field drive type liquid crystal element with improved voltage holding ratio and a polymer composition for the production of a liquid crystal alignment film for the element, specifically a horizontal electric field drive type liquid crystal display Composition for manufacturing liquid crystal alignment film for element.

Further, the object of the present invention is to provide a liquid crystal alignment agent that is composed of the composition only, or essentially composed of the composition, or has the composition, and uses the liquid crystal Orientation A liquid crystal alignment film manufactured by an agent, a substrate having the liquid crystal alignment film, a liquid crystal display element having the liquid crystal alignment film and/or the substrate, especially a horizontal electric field drive type liquid crystal display element.

In addition, the object of the present invention is to provide, in addition to or in addition to the above-mentioned objects, a method for manufacturing the aforementioned liquid crystal alignment film, a method for manufacturing a substrate having the liquid crystal alignment film, and a liquid crystal display having the liquid crystal alignment film and/or the substrate A method of manufacturing a device, especially a horizontal electric field drive type liquid crystal display device.

The inventors discovered the following invention.

<1> A polymer composition containing at least two types of (A) polymers having a structure exhibiting photoreactivity and a structure exhibiting liquid crystallinity; and (B) an organic solvent; a polymer composition of at least two types of polymers, one The polymer has a crosslinkable group.

<2> In the above-mentioned <1>, among at least two kinds of polymers, it is preferable that one polymer (A1) and the other polymer (A2) have different amounts of structures that exhibit photoreactivity with each other.

<3> In the above <2>, the amount of the structure expressing photoreactivity of the polymer (A1) is preferably more than the amount of the structure expressing photoreactivity of the polymer (A2).

<4> In any of the above <1>~<3>, the crosslinkable group is defined by the following formulas (G-1), (G-2), (G-3) and (G-4) (where , The dashed line indicates the bonding bond, R ⁵⁰ is a group selected from a hydrogen atom, a halogen atom, an alkyl group with 1 to 3 carbons, and a phenyl group. When R ⁵⁰ is a plural number, they can be the same or different from each other, and t is 1~ It is an integer of 7, J is O, S, NH or NR ⁵¹ , and R ⁵¹ is an alkyl group with 1 to 3 carbon atoms and a group selected from the phenyl group.) At least one group selected from the group is preferred.

<5> In any of the above <2> to <4>, it is preferable that the polymer (A1) has a crosslinkable group.

<6> In any of the above <2> to <5>, the polymer (A1) further has at least 1 selected from the group consisting of a nitrogen-containing aromatic heterocyclic group, an amide group, and a urethane group The seed base is better.

<7> In any of the above <2> to <6>, the polymer (A2) further has at least 1 selected from the group consisting of a nitrogen-containing aromatic heterocyclic group, an amide group, and a urethane group The seed base is better.

<8> In any of the above-mentioned <1> to <7>, at least two kinds of polymers are preferably each having a structure expressing photoreactivity and liquid crystallinity, and a structure expressing only liquid crystallinity.

<9> The structure expressing photoreactivity in the above <1>~<8>, especially the structure expressing photoreactivity and liquid crystallinity in <8> can be The following formulas (1)~(6)

(In the formula, A, B, and D are independent of each other and are single bonds, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO- O-, or -O-CO-CH=CH-; S is an alkylene group with 1 to 12 carbons, and the hydrogen atoms bonded to them can be substituted by halogen groups; T is a single bond or 1 to 12 carbons The hydrogen atoms bonded to them can be substituted by halogen groups; Y _{1 is} composed of monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic ring with carbon number 5~8 The rings selected by the hydrocarbons, or the same or different 2-6 rings selected by their substituents, are bonded through the bonding group B, which are bonded to their hydrogen atoms, each independently of which can be -COOR ₀ (where R ₀ is a hydrogen atom or an alkyl group with 1 to 5 carbon atoms), -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen group, carbon alkyl group, or an alkyl group having a carbon number of 1 to 5 substituted with 1 to 5; the Y ₂ by a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, a 5 to 8 carbon atoms, The groups selected from the group consisting of alicyclic hydrocarbons, and, are bonded to their hydrogen atoms, each independently, and can be -NO ₂ , -CN, -CH=C(CN) ₂ ,- CH=CH-CN, halogen group, alkyl group with 1 to 5 carbons, or alkyloxy group with 1 to 5 carbons; R is hydroxyl, alkoxy with 1 to 6 carbons, or with Y ₁ Same definition; X is a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O-, or -O-CO- CH=CH-, when the number of X is 2, X can be the same or different from each other; Cou is coumarin-6-yl or coumarin-7-yl, bonded to their hydrogen atoms, and each is independent , Can be replaced by -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen group, alkyl group with 1 to 5 carbons, or alkyloxy group with 1 to 5 carbons Substitution; q1 and q2, one is 1 and the other is 0; q3 is 0 or 1; P and Q, each independently, are composed of divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, A group selected from the group consisting of alicyclic hydrocarbons with 5 to 8 carbon atoms and their combination; however, when X is -CH=CH-CO-O-, -O-CO-CH=CH-, -CH=CH- P or Q on the bonding side is an aromatic ring. When the number of P is 2 or more, P can be the same or different from each other, and when the number of Q is 2 or more, Q can be the same or different from each other; l1 is 0 or 1; l2 is an integer from 0 to 2; when both l1 and l2 are 0, when T is a single bond, A is also a single bond; when l1 is 1, when T is a single bond, B is also a single bond ; H and I, each independently, are groups selected from divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, and combinations thereof.)

Any one of the structures selected from the group is better.

<10> The structure expressing photoreactivity in the above <1>~<8>, especially the structure expressing photoreactivity and liquid crystallinity in <8> can be represented by the following formulas (7)~(10)

(In the formula, A, B, and D are independent of each other and are single bonds, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO- O-, or -O-CO-CH=CH-; Y _{1 is a} ring selected from monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon with carbon number 5~8 , Or the same or different 2~6 rings selected by their substituents bonded through the bonding group B, bonded to their hydrogen atoms, each independently can be -COOR ₀ (formula Where R ₀ is a hydrogen atom or an alkyl group with 1 to 5 carbons), -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen group, and carbon 1 to 5 Alkyl group, or C1-C5 alkyloxy group; X is a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH =CH-CO-O-, or -O-CO-CH=CH-, when the number of X is 2, X can be the same or different from each other; l is an integer from 1 to 12; m is an integer from 0 to 2 , M1 and m2 are integers from 1 to 3; n is an integer from 0 to 12 (but when n=0, B is a single bond); Y _{2 is} composed of divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, The pyrrole ring, the alicyclic hydrocarbon with 5 to 8 carbon atoms, and the group selected from the combination of them are bonded to their hydrogen atoms. They are independent of each other and can be controlled by -NO ₂ , -CN,- CH=C(CN) ₂ , -CH=CH-CN, halogen group, alkyl group with 1 to 5 carbons, or alkyloxy group with 1 to 5 carbons; R is a hydroxyl group, with 1 to 6 carbons的alkoxy, or the same definition _{as Y 1)}

Any one of the structures selected from the group is better.

<11> The structure expressing photoreactivity in the above <1>~<8>, especially the structure expressing photoreactivity and liquid crystallinity in <8> can be represented by the following formulas (11)~(13)

(In the formula, A, each independently, is a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O-, Or -O-CO-CH=CH-; X is a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O -, or -O-CO-CH=CH-, when the number of X is 2, X can be the same or different from each other; l is an integer from 1 to 12, m is an integer from 0 to 2, m1 is 1 to 3 R is a ring selected from monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon with carbon number of 5 to 8, or the same or the same selected from their substituents Two to six different rings are bonded through the bonding group B. They are bonded to their hydrogen atoms. Each independently can be -COOR ₀ (where R ₀ is a hydrogen atom or carbon number 1~ 5), -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen group, alkyl group with 1 to 5 carbons, or alkyl group with 1 to 5 carbons Any one structure selected from the group consisting of oxy-substituted or hydroxy or alkoxy having 1 to 6 carbon atoms is preferred.

<12> The structure expressing photoreactivity in the above <1>~<8>, especially the structure expressing photoreactivity and liquid crystallinity in <8>, is given by the following formula (14) or (15)

(In the formula, A is independent of each other and is a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O-, or -O-CO-CH=CH-; Y _{1 is a} ring selected from monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon with carbon number 5 to 8, or The same or different 2~6 rings selected by the substituents are bonded through the bonding group B, which are bonded to their hydrogen atoms, and each independently can be -COOR ₀ (where R ₀ Is a hydrogen atom or an alkyl group with 1 to 5 carbon atoms), -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, an alkyl group with 1 to 5 carbon atoms, or It is preferably substituted by an alkyloxy group having 1 to 5 carbon atoms; l is an integer of 1 to 12, m1 and m2 are an integer of 1 to 3).

<13> The structure expressing photoreactivity in the above <1>~<8>, especially the structure expressing photoreactivity and liquid crystallinity in <8>, can be expressed by the following formula (16) or (17) (wherein, A is a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O-, or -O-CO-CH= CH-; X is a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O-, or -O-CO- CH=CH-, when the number of X is 2, X can be the same or different from each other; l is an integer from 1 to 12, m is an integer from 0 to 2).

<14> The structure expressing photoreactivity in the above <1>~<8>, especially the structure expressing photoreactivity and liquid crystallinity in <8>, is given by the following formula (18) or (19)

(In the formula, A and B are independent of each other and are single bonds, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O- , Or -O-CO-CH=CH-; Y _{1 is a} ring selected from monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon with carbon number 5-8, or The same or different 2~6 rings selected by their substituents are bonded through the bonding group B, which are bonded to their hydrogen atoms, and each independently can be -COOR ₀ (where, R ₀ is a hydrogen atom or an alkyl group with 1 to 5 carbon atoms), -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen group, alkyl group with 1 to 5 carbon atoms , Or substituted by an alkyloxy group with 1 to 5 carbon atoms; q1 and q2, one is 1 and the other is 0; l is an integer from 1 to 12, m1 and m2 are an integer from 1 to 3; R ₁ It is a hydrogen atom, -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen group, alkyl group with 1 to 5 carbons, or alkyloxy group with 1 to 5 carbons ) Any one of the structures selected from the group is better.

<15> The structure expressing photoreactivity in the above <1>~<8>, especially the structure expressing photoreactivity and liquid crystallinity in <8> is represented by the following formula (20) (where A is a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O-, or -O-CO-CH=CH-; Y ₁ It is a ring selected from monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon with carbon number of 5-8, or the same or different ones selected from their substituents. ~6 rings are formed by bonding through the bonding group B, bonded to their hydrogen atoms, each independently can be -COOR ₀ (where R ₀ is a hydrogen atom or an alkyl group with 1 to 5 carbon atoms ), -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen group, alkyl group with 1 to 5 carbons, or alkyloxy group with 1 to 5 carbons ; X is a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O-, or -O-CO-CH= When the number of CH- and X is 2, X can be the same or different from each other; l is an integer from 1 to 12, and m is an integer from 0 to 2).

<16> In any of the above <8>~<15>, the structure that only exhibits liquid crystallinity is represented by the following formulas (21)~(31)

(In the formula, A and B have the same definition as above; Y _{3 is} composed of monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocyclic ring, and alicyclic hydrocarbon with 5 to 8 carbon atoms, and, The groups selected from the group formed by their combination are bonded to their hydrogen atoms, each independently, and can be -NO ₂ , -CN, halogen groups, alkyl groups with 1 to 5 carbons, or 1 to carbon atoms. 5 is substituted by an alkyloxy group; R ₃ is a hydrogen atom, -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen group, monovalent benzene ring, naphthalene ring, bivalent Benzene ring, furan ring, nitrogen-containing heterocyclic ring, alicyclic hydrocarbon with 5 to 8 carbons, alkyl with 1 to 12 carbons, or alkoxy with 1 to 12 carbons; q1 and q2, one of them is 1 The other is 0; l is an integer from 1 to 12, and m is an integer from 0 to 2. However, in formulas (23) to (24), the sum of all m is 2 or more, and formulas (25) to (26) In ), the total of all m is 1 or more, m1, m2, and m3 are each independently an integer of 1 to 3; R ₂ is a hydrogen atom, -NO ₂ , -CN, halogen group, monovalent benzene ring, naphthalene ring , Biphenyl ring, furan ring, nitrogen-containing heterocyclic ring, and alicyclic hydrocarbon with 5 to 8 carbons, and, alkyl, or alkyloxy; Z ₁ , Z ₂ are single bonds, -CO-,- Any one structure selected from the group consisting of CH ₂ O-, -CH=N-, -CF _{2 -) is preferred.}

<17> In any of the above <2>~<16>, use the polymer (A1) The amount of the structure exhibiting photoreactivity, when the total of the structure exhibiting photoreactivity and the structure exhibiting liquid crystallinity of the polymer (A1) is 100 mol%, it is α mol% (α is 15 or more, preferably 15~100, more preferably 20~80), the polymer (A2) has a photoreactive structure, when the polymer (A2) has a photoreactive structure and a liquid crystal structure at 100 When mol%, it is 0.95αmol% or less, preferably 0.1α~0.8αmol%, more preferably 0.25α~0.5αmol%.

<18> In any of the above <2>~<17>, the weight average molecular weight of the polymer (A1) is β (β is 30,000 or more, preferably 30,000 to 300,000, more preferably 40,000 to 20 The weight average molecular weight of the polymer (A2) is 0.1 β to 0.9 β, preferably 0.2 β to 0.8 β, and more preferably 0.3 β to 0.7 β.

<19> In any of the above <2>~<18>, if the total weight of polymer (A1) and polymer (A2) is 100wt%, then polymer (A1) is 20~95wt%, preferably 50 ~90wt%, more preferably 60~80wt%.

<20> In any of the above <1>~<19>, at least two kinds of polymers have (M-1) a monomer (M1) having a structure that exhibits photoreactivity and liquid crystallinity; and (M-2) ) A monomer (M2) with a structure that only exhibits liquid crystallinity; the one formed is better.

<21> In the above <20>, the monomer (M1) preferably has a structure represented by any of the above formulas (1) to (20).

<22> In the above <20> or <21>, the monomer (M2) preferably has the structure represented by the above formulas (21) to (31).

<23> In any of the above <20>~<22>, the monomer (M1) can be determined by At least one selected from the group consisting of the following formulas MA1, MA3, MA4, MA5, MA14, MA16~MA23, MA25, MA28~MA30, MA32, MA34, MA36, MA38~MA42, MA44, and MA46 is preferred.

<24> In any of the above <20>~<23>, the monomer (M2) is composed of the following formulas MA2, MA9~MA13, MA15, MA24, MA26, MA27, MA31, MA35, MA37, MA43 and MA45 At least one selected from the group is preferred.

<25> In any of the above <1>~<24>, the polymer (A1) has (M-1) a monomer (M1) having a structure that exhibits photoreactivity and liquid crystallinity; (M-2) has Monomer (M2) with a structure that only exhibits liquid crystallinity; and (M-3) have the following formulas (G-1), (G-2), (G-3) and (G-4) (where, the dotted line Represents a bonding bond, R ⁵⁰ is a group selected from a hydrogen atom, a halogen atom, an alkyl group with 1 to 3 carbons, and a phenyl group. When R ⁵⁰ is a plural number, they can be the same or different from each other, and t is 1 to 7. Integer, J is O, S, NH or NR ⁵¹ , and R ⁵¹ is a group selected from an alkyl group with 1 to 3 carbons and a phenyl group) at least one monomer (M3) selected from the group; And the formation is better.

<26> In the above <25>, (M-3) monomer (M3) has the following formula (0)

(In formula (0), A and B are independent of each other and are single bonds, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO -O-, or -O-CO-CH=CH-; S is an alkylene group with 1 to 12 carbon atoms, and the hydrogen atoms bonded to them can be substituted by halogen groups; T is a single bond or carbon number 1~ In the alkylene group of 12, the hydrogen atoms bonded to them can be substituted by halogen groups; X is a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C- , -CH=CH-CO-O-, or -O-CO-CH=CH-, when the number of X is 2, X can be the same or different from each other; P and Q, independent of each other, are made of divalent benzene Ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon with 5 to 8 carbon atoms, and a group selected from the group consisting of combinations thereof; however, X is -CH=CH-CO When -O-, -O-CO-CH=CH-, P or Q on the bonding side of -CH=CH- is an aromatic ring; l1 is 0 or 1; l2 is an integer from 0 to 2; l1 and l2 are both When 0, when T is a single bond, A is also a single bond; when l1 is 1, when T is a single bond, B is also a single bond; G is represented by the following formulas (G-1), (G-2), (G-3) and (G-4) (In the formula, the dotted line represents the bonding bond, R ⁵⁰ is a group selected from a hydrogen atom, a halogen atom, an alkyl group with 1 to 3 carbons, and a phenyl group, and R ⁵⁰ is a plural number When, they can be the same or different from each other, t is an integer from 1 to 7, J is O, S, NH or NR ⁵¹ , R ⁵¹ is an alkyl group with 1 to 3 carbons and a group selected from phenyl) selected Base)

The indicated structure is better.

<27> In the above <25> or <26>, the polymer (A1) is selected from the group consisting of (M-4) having a nitrogen-containing aromatic heterocyclic group, an amide group and a urethane group At least 1 type of monomer (M4); and the one that is formed is preferred.

<28> In any of the above <1>~<27>, the polymer (A2) has (M-1) a monomer (M1) with a structure that exhibits photoreactivity and liquid crystallinity; (M-2) has Monomer (M2) with a structure that only exhibits liquid crystallinity; and (M-4) having at least one group selected from the group consisting of a nitrogen-containing aromatic heterocyclic group, an amino group, and a urethane group Monomer (M4); the formed one is better.

<29> In the above <27> or <28>, (M-4) has a single group of at least one selected from the group consisting of a nitrogen-containing aromatic heterocyclic group, an amino group and a urethane group The body (M4) is preferably at least one selected from the group consisting of the following formulas MA6~MA8 and MA33.

<30> In any of the above <25>~<29>, when the total of monomer (M1) and monomer (M2) is 100 mol%, polymer (A1) uses monomer (M1) as α mol% % (α is 15 or more, preferably 15-100, more preferably 20-80), and the rest is formed by monomer (M2), For the polymer (A2), the monomer (M1) is 0.95αmol% or less, preferably 0.1α~0.8αmol%, more preferably 0.25α~0.5αmol%, and the rest is monomer (M2 ) Is better.

<31> A liquid crystal alignment agent having a polymer composition of any one of the above <1> to <30>.

<32> A liquid crystal alignment film formed by the liquid crystal alignment agent of the above <31>.

<33> The step of forming a coating film by coating the polymer composition of the above <1>~<30> on a substrate with a conductive film for driving a horizontal electric field by having [I]; [II] vs. [I ] The step of irradiating the obtained coating film with polarized ultraviolet rays; and [III] the step of heating [II] the obtained coating film; and the method of manufacturing a liquid crystal alignment film to obtain a liquid crystal alignment film endowed with alignment control capabilities.

<34> A substrate having the liquid crystal alignment film of the above <32>.

<35> The step of forming a coating film by coating any of the polymer composition of any one of the above <1>~<30> on a substrate having a conductive film for driving a horizontal electric field by having [I]; [II] [I] the step of irradiating the obtained coating film with polarized ultraviolet rays; and [III] the step of heating the obtained coating film [II]; to obtain a liquid crystal alignment film endowed with alignment control ability. Production method.

<36> A liquid crystal display element having the substrate of the above <34>.

<37> By having the step of preparing the substrate (the first substrate) of the above <34> Step; The step of forming a coating film by coating the polymer composition described in any one of Claims 1 to 26 on the second substrate with [I']; [II'] to [I'] The step of irradiating the coating film with polarized ultraviolet rays; [III'] the step of heating the coating film obtained by [II']; the step of obtaining the liquid crystal alignment film endowed with alignment control ability; the step of obtaining the second substrate with the aforementioned liquid crystal alignment film; And [IV] the step of arranging the first and second substrates to obtain a liquid crystal display element by opposing the liquid crystal alignment films of the first and second substrates to obtain a liquid crystal display element; and obtaining a liquid crystal display of the liquid crystal display element Component manufacturing method.

According to the present invention, it is possible to provide a substrate having a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display element that imparts alignment control ability with high efficiency and excellent afterimage characteristics, and a horizontal electric field drive type liquid crystal display element having the substrate.

Specifically, according to the present invention, it is possible to provide a polymer composition for the production of a liquid crystal alignment film of a high-quality liquid crystal alignment film, which can efficiently obtain a stable alignment control ability, expand the range of the generated light irradiation, and, specifically, is level. A composition for manufacturing a liquid crystal alignment film for an electric field drive type liquid crystal display element.

Furthermore, according to the present invention, in addition to the above effects, a horizontal electric field drive type liquid crystal element with improved voltage holding ratio and a liquid crystal arrangement for the element are provided. The polymer composition for the production of the alignment film is specifically a composition for the production of a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display element.

Further, according to the present invention, in addition to or in addition to the above-mentioned effects, it is possible to provide a liquid crystal alignment agent composed only of the composition, or substantially composed of the composition only, or having the composition, using the liquid crystal alignment agent A liquid crystal alignment film manufactured by an agent, a substrate having the liquid crystal alignment film, a liquid crystal display element having the liquid crystal alignment film and/or the substrate, especially a horizontal electric field drive type liquid crystal display element.

Furthermore, according to the present invention, in addition to or in addition to the above effects, the method for manufacturing the aforementioned liquid crystal alignment film, the method for manufacturing a substrate with the liquid crystal alignment film, and the liquid crystal display with the liquid crystal alignment film and/or the substrate can be provided A method of manufacturing a device, especially a horizontal electric field drive type liquid crystal display device.

The liquid crystal display element of the present invention, especially the horizontal electric field drive type liquid crystal display element, is efficiently endowed with the alignment control ability, and the display characteristics will not be impaired even if it is continuously driven for a long time.

Furthermore, according to the present invention, in addition to or in addition to the above effects, it is possible to provide a liquid crystal display element, especially a horizontal electric field drive type liquid crystal element, which adsorbs ionic impurities in the liquid crystal at the interface of the liquid crystal alignment film and has an improved voltage holding ratio. The liquid crystal alignment film for the device.

[Best form to implement the invention]

The present invention provides a polymer composition for a liquid crystal alignment agent, especially a liquid crystal alignment agent for a horizontal electric field drive type liquid crystal display element.

In addition, the present invention provides a liquid crystal alignment agent composed only of the composition, or substantially composed only of the composition or having the composition, especially a liquid crystal alignment agent for a horizontal electric field drive type liquid crystal display element.

Further, the present invention provides a liquid crystal alignment film formed by the liquid crystal alignment agent, especially a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display element, a substrate having the liquid crystal alignment film, especially a substrate for a horizontal electric field drive type liquid crystal display element, and A liquid crystal display element having the substrate, especially a horizontal electric field drive type liquid crystal display element.

Hereinafter, detailed description will be given in order.

<Polymer composition for liquid crystal alignment agent>

The present invention provides a polymer composition for a liquid crystal alignment agent, especially a liquid crystal alignment agent for a horizontal electric field drive type liquid crystal display element.

The polymer composition of the present invention has at least two types of (A) polymers having a structure exhibiting photoreactivity and a structure exhibiting liquid crystallinity; and (B) an organic solvent.

In addition, among at least two types of polymers, one type of polymer has a crosslinkable group.

Furthermore, among at least two kinds of polymers, one polymer (A1) and the other polymer (A2) differ in the amount of the structure exhibiting photoreactivity with each other. In particular, the amount of the structure exhibiting photoreactivity of one polymer (A1) is better than the amount of structure exhibiting photoreactivity of the other polymer (A2).

<<Crosslinkable base>>

In this specification, the crosslinkable group refers to a substituent that can be crosslinked with a carboxyl group by heat.

Among at least two types of polymers, when one type of polymer has a crosslinkable group, when the polymer composition is formed into a liquid crystal alignment film, high reliability such as voltage retention (VHR) can be imparted to the liquid crystal alignment film. This is believed to be because when the liquid crystal alignment film is made, the crosslinkable group acts like a crosslinking agent, and the density of the film is increased and the elution of ionic impurities into the liquid crystal is reduced.

As a crosslinkable group, an epoxy group, an oxetanyl group, a blocked isocyanate group, a thipropanyl group, a thietane group, etc. are mentioned, for example, but it is not limited to these.

Specifically, the crosslinkable group is preferably at least one group selected from the group consisting of the following formulas (G-1), (G-2), (G-3), and (G-4).

In the formula, the dotted line represents the bonding bond, R ⁵⁰ is a group selected from a hydrogen atom, a halogen atom, an alkyl group with 1 to 3 carbons, and a phenyl group. When R ⁵⁰ is a plural number, they can be the same or different from each other, and t is An integer from 1 to 7, J is O, S, NH or NR ⁵¹ , and R ⁵¹ is a group selected from an alkyl group with 1 to 3 carbon atoms and a phenyl group.

It is preferable that a part of the side chain end of the polymer has a crosslinkable group.

In addition, the crosslinkable group is preferably a polymer having a relatively large amount at least for a structure expressing photoreactivity, that is, the polymer (A1). In addition, the crosslinkable group is preferably a polymer (A2) that is not substantially contained in a structure exhibiting photoreactivity in a relatively small amount.

<<Nitrogen-containing aromatic heterocyclic group, etc.>>

Among the at least two polymers of the present invention, at least one polymer further contains at least one group selected from the group consisting of a nitrogen-containing aromatic heterocyclic group, an amide group, and a urethane group. good. In addition, both of the at least two types of polymers may further have at least one type selected from the group consisting of a nitrogen-containing aromatic heterocyclic group, an amide group, and a urethane group. In this case, each polymer may have a nitrogen-containing aromatic heterocyclic group, etc., which may be the same or different.

The nitrogen-containing aromatic heterocyclic ring contains at least one of the following formula [20a], formula [20b] and formula [20c] (where Z ₂ is a linear or branched alkyl group with 1 to 5 carbons) The structure selected from the group preferably contains 1 to 4 aromatic cyclic hydrocarbons of the structure.

Specifically, for example, pyrrole ring, imidazole ring, oxazole Ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, thiadiazole ring, pyridazine ring, pyrazoline ring, Triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, quinoline ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, Thiodiphenylamine ring, oxadiazole ring, acridine ring, etc. Furthermore, the carbon atoms of these nitrogen-containing aromatic heterocycles may have heteroatom-containing substituents.

Among these, for example, a pyridine ring is preferable.

Among at least two types of polymers, one type of polymer has a group selected from a nitrogen-containing aromatic heterocyclic group, an amide group, and a urethane group, so that the voltage retention rate (VHR) can be trusted Sex is improved. It is believed that this system captures ionic impurities.

At least two kinds of polymers are preferably each having a structure expressing photoreactivity and liquid crystallinity, and a structure expressing only liquid crystallinity. In addition, in this manual, the term "only liquid crystallinity" in "structures that express only liquid crystallinity" refers to the term used when considering "photoreactivity" and "liquid crystallinity". It will not express "photoreactivity" but express "liquid crystallinity". "Sex" is expressed in terms of "only".

<(A) Polymer with a structure that exhibits photoreactivity and a structure that exhibits liquid crystallinity>

In this specification, "a structure that exhibits photoreactivity" refers to a structure that reacts with light in a certain wavelength range, especially in the wavelength range of 250 nm to 400 nm. For example, it is preferable that the polymer side chain has this structure.

In addition, in this specification, although the "photoreactivity" is not particularly limited, it means It reacts with light to show a cross-linking reaction, an isomerization reaction, or a light-Friesian rearrangement, and it is preferable to show a cross-linking reaction. When using a polymer with a "structure that exhibits photoreactivity", even if exposed to external pressure such as heat, the achieved alignment control ability can be stably maintained for a long period of time.

In this specification, "structure that exhibits liquid crystallinity" refers to a structure that exhibits liquid crystallinity in a certain temperature range, especially in the temperature range of 100 to 300°C. For example, a structure in which the side chain of a polymer has mesogen groups or mesogen components Better.

When a polymer having a "structure expressing liquid crystallinity" is used, when the polymer is used as a liquid crystal alignment film, stable liquid crystal alignment can be obtained.

The structure of the polymer, for example, has a main chain and a side chain bonded to it, and the side chain has a "structure expressing photoreactivity" and "a structure expressing liquid crystallinity". In addition, the "structure expressing photoreactivity" and "structure expressing liquid crystallinity" may exist in the same side chain or different side chains. It is preferable that a certain side chain has a structure expressing photoreactivity and liquid crystallinity, and another side chain has a structure-like polymer expressing only liquid crystallinity.

There are cases where the "structure that expresses photoreactivity" and "the structure that expresses liquid crystallinity" exist in the same side chain, and the side chain has biphenyl, triphenyl, phenylcyclohexyl, phenyl benzoate groups, In the case of the "structure expressing photoreactivity" where the mesogen components such as azophenyl and the induced light bonded to the tip show cross-linking reaction or isomerization reaction, the side chain is also a "structure expressing liquid crystallinity" The mesogenic component of "and the structure of the phenyl benzoate group undergoing the photo-Friesian rearrangement reaction of the "structure expressing photoreactivity", etc.

Specific examples of the main chain of at least two kinds of polymers of the present invention Aspects, although not particularly limited, are independent of each other, consisting of hydrocarbon, (meth)acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene It is preferable to be composed of at least one selected from the group consisting of radical polymerizable groups such as vinyl, maleimide, norbornene, and silicone.

<<A structure that expresses light reactivity>>

The structure expressing photoreactivity, especially the structure expressing photoreactivity and liquid crystallinity, is preferably a structure represented by any one selected from the group consisting of formulas (1) to (6). In the formula, A, B, D, S, Y ₁ , Y ₂ , R, X, Cou, q1 and q2, q3, P and Q, 11, 12, H, and I have the same definitions as above.

The structure expressing photoreactivity, especially the structure expressing photoreactivity and liquid crystallinity, is preferably a structure represented by any one selected from the group consisting of formulas (7) to (10). In addition, in the formula, A, B, D, Y ₁ , X, 1, m, m1, m2, n, Y ₂ , and R have the same definitions as described above.

The structure expressing photoreactivity, especially the structure expressing photoreactivity and liquid crystallinity, is preferably a structure represented by any one selected from the group consisting of formulas (11) to (13). In addition, in the formula, A, X, 1, m, m1, and R have the same definitions as above.

The structure that exhibits photoreactivity, especially the structure that exhibits photoreactivity and liquid crystallinity, is preferably a structure represented by formula (14) or (15). In addition, in the formula, A, Y ₁ , l, m1, and m2 have the same definitions as above.

The structure that exhibits photoreactivity, especially the structure that exhibits photoreactivity and liquid crystallinity, is preferably a structure represented by formula (16) or (17). In addition, in the formula, A, X, l, and m have the same definitions as above.

The structure that exhibits photoreactivity, especially the structure that exhibits photoreactivity and liquid crystallinity, is preferably a structure represented by formula (18) or (19). In addition, in the formula, A, B, Y ₁ , q1, q2, l, m1, m2, and R ₁ have the same definitions as above.

A structure expressing photoreactivity, especially a structure expressing photoreactivity and liquid crystallinity, is preferably a structure represented by formula (20). In addition, in the formula, A, Y ₁ , X, l, and m have the same definitions as above.

<<Structure that only exhibits liquid crystallinity>>

A structure that only exhibits liquid crystallinity is preferably a structure represented by any one selected from the group formed by equations (21) to (31). In the formula, A, B, Y ₃ , R ₃ , q1, q2, l, m, m1, m2, m3, R ₂ , Z ₁ , and Z ₂ have the same definitions as above.

<<The amount of each of at least two kinds of polymers exhibiting photoreactivity structure>>

In each of at least two types of polymers, when the total of the structure exhibiting photoreactivity and the structure exhibiting only liquid crystallinity is 100 mol%, the amount of the structure exhibiting photoreactivity of the polymer (A1) is α mol %(α is 15 or more, preferably 15-100, more preferably 20-80), the amount of the structure exhibiting photoreactivity of the polymer (A2) is higher than the structure exhibiting photoreactivity of the polymer (A1) The lesser amount is better, specifically 0.95αmol% or less, preferably 0.1α~0.8αmol%, more preferably 0.25α~0.5αmol%.

It is thought that the use of polymers with different amounts of structures expressing photoreactivity has the following general effects. That is, a polymer (polymer (A1)) with a relatively large number of structures exhibiting photoreactivity determines the orientation due to ultraviolet irradiation. On the other hand, a polymer (polymer (A2)) with relatively few structures exhibiting photoreactivity but relatively many structures exhibiting liquid crystallinity is aligned according to the alignment determined by the polymer (A1). Among the at least two types of polymers, each polymer shares the role it has, and can effectively perform the role.

<<Each weight average molecular weight of at least 2 kinds of polymers>>

In addition, among at least two kinds of polymers, one has a weight average molecular weight of β (β is 30,000 or more, preferably 30,000 to 300,000, more preferably 40,000 to 200,000, and even more preferably 60,000 to 60,000. 150,000), the weight average molecular weight of the other is 0.1β to 0.9β, preferably 0.2β to 0.8β, more preferably 0.3β to 0.7β.

In addition, in this specification, when there is no special description, the weight average molecular weight is Measured by GPC (Gel Permeation Chromatography) method.

In particular, the polymer (A1) having a relatively large amount of a structure that exhibits photoreactivity has a weight average molecular weight β (β is 30,000 or more, preferably 30,000 to 300,000, more preferably 40,000 to 200,000 , More preferably 60,000~150,000), a polymer (A2) with a relatively small amount of structure that exhibits photoreactivity, and its weight average molecular weight is 0.1β~0.9β, preferably 0.2β~0.8β, more preferably It is better to be 0.3β~0.7β.

By using at least two polymers with different weight average molecular weights, when the polymer is formed into a liquid crystal alignment film, the polymer with a large weight average molecular weight is formed on the lower layer (the layer relatively close to the substrate) of the liquid crystal alignment film. Tendency, on the other hand, a polymer with a low weight average molecular weight tends to be formed on a relatively upper layer (a layer relatively far from the substrate) of the liquid crystal alignment film.

It is believed that by having such a structure, the following functions are achieved.

That is, the polymer (A1) with relatively many structures exhibiting photoreactivity and a large weight average molecular weight is formed on the relatively lower layer (layer relatively close to the substrate) of the liquid crystal alignment film. On the other hand, a polymer (A2) with relatively few structures exhibiting photoreactivity and a small weight average molecular weight is formed on the relatively upper layer (layer relatively far from the substrate) of the liquid crystal alignment film. In this situation, the polarized ultraviolet light is irradiated, and the polymer (A1) of the lower layer (the layer relatively close to the substrate) is aligned according to the polarized ultraviolet light. On the other hand, it is considered that the polymer (A2) of the relatively upper layer (the layer relatively far away from the substrate) is responsible for generating alignment along the alignment of the polymer (A1).

<<The weight ratio of at least 2 kinds of polymers>>

Taking the total weight of the polymer (A1) and the polymer (A2) as 100wt%, the polymer (A1) is 20~95wt%, preferably 50~90wt%, more preferably 60~80wt%, and the polymerization The thing (A2) is better than the others.

Polymer (A1) and polymer (A2) have two or more of the above three characteristics, namely, "amount of structure expressing photoreactivity", "weight average molecular weight", and "weight ratio". Characteristics, it is preferable to have all three characteristics.

<Each manufacturing method of at least 2 kinds of polymers>

At least two kinds of polymers of the present invention have the above-mentioned constitution, and the production method is not particularly limited.

For example, at least two polymers of the present invention have (M-1) monomers (M1) having a structure that exhibits photoreactivity and liquid crystallinity; and (M-2) a monomer having a structure that only exhibits liquid crystallinity. Body (M2); and the form is better.

Specifically, the polymer (A1) has (M-1) a monomer (M1) with a structure that exhibits photoreactivity and liquid crystallinity; (M-2) a monomer (M2) with a structure that only exhibits liquid crystallinity ; And (M-3) a monomer having a crosslinkable group, specifically a group consisting of the above formulas (G-1), (G-2), (G-3) and (G-4) A monomer (M3) of at least one group selected from the group, more specifically having the following formula (0) (in formula (0), A, B, S, T, X, P, Q, 11, 12, G has the same definition as the monomer of the structure represented by); The former is better.

In addition, when the polymer (A1) has at least one group selected from the group consisting of a nitrogen-containing aromatic heterocyclic group, an amido group, and a urethane group, the polymer (A1) may further have (M -4) A monomer (M4) having at least one group selected from the group consisting of a nitrogen-containing aromatic heterocyclic group, an amide group and a urethane group; and the one formed is preferred.

The polymer (A2) has (M-1) a monomer (M1) with a structure exhibiting photoreactivity and liquid crystallinity; and (M-2) a monomer (M2) with a structure exhibiting only liquid crystallinity; and Former is better.

In addition, when the polymer (A2) has at least one group selected from the group consisting of a nitrogen-containing aromatic heterocyclic group, an amido group, and a urethane group, the polymer (A2) may further have (M-4) A monomer (M4) having at least one group selected from the group consisting of a nitrogen-containing aromatic heterocyclic group, an amide group and a urethane group; and the one formed is preferred.

In addition, when the polymer (A2) has a crosslinkable group, the polymer (A2) may further have the above-mentioned (M-3) monomer (M3).

In addition, the polymer (A1) and the polymer (A2) can be formed by copolymerizing other monomers in addition to the above-mentioned monomers, within a range that does not impair the expressive ability of photoreactivity and/or liquid crystallinity.

As mentioned above, at least two kinds of polymers of the present invention are formed by having monomer (M1) and monomer (M2), but when the total of monomer (M1) and monomer (M2) is 100 mol%, at least In the polymer (A1) of the two polymers, the monomer (M1) is α mol% (α is 15 or more, preferably 15 to 100, more preferably 20 to 80) and the rest is monomer ( M2) is better.

In addition, for the polymer (A2), the monomer (M1) is 0.95αmol% or less, preferably 0.1α~0.8αmol%, more preferably 0.25α~0.5αmol%, and the rest is monomer The method of (M2) is better.

Moreover, it is preferable that the monomer (M1) and the monomer (M2) used in the polymer (A1) and the polymer (A2) are in common with each other.

<<Monomer (M1) with a structure that exhibits photoreactivity and liquid crystallinity and its preparation method>>

At least two kinds of polymers of the present invention have the above-mentioned monomer (M1) having a structure expressing photoreactivity and liquid crystallinity; and (M-2) a monomer (M2) having a structure expressing only liquid crystallinity; and Formation, specifically obtained by copolymerization, is better.

[Monomer with a structure that exhibits photoreactivity and liquid crystallinity (M1)]

The monomer (M1) with a structure that exhibits photoreactivity and liquid crystallinity refers to a monomer that can form a polymer with a structure that exhibits photoreactivity and liquid crystallinity at the side chain portion of the polymer when forming a polymer.

The structure that exhibits photoreactivity at the side chain portion is preferably the following structure and its derivatives.

More specific examples of the monomer (M1) include hydrocarbon, (meth)acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, benzene Radical polymerizable groups such as ethylene, vinyl, maleimide, norbornene, and at least one polymerizable group selected from the group consisting of silicone, and the above formula (1)~( 6) A structure expressing photoreactivity and liquid crystallinity constituted by at least one type, preferably, for example, a structure expressing photoreactivity and liquid crystallinity constituted by at least one of the above formulas (7) to (10), The structure expressing photoreactivity and liquid crystallinity constituted by at least one of the above formulas (11) to (13), the structure expressing photoreactivity and liquid crystallinity expressed by the above formula (14) or (15), the above formula (16) or (17) shows photoreactivity and liquid crystal It is preferable that the structure expresses the photoreactivity and liquid crystallinity represented by the above formula (18) or (19), and the structure expresses the photoreactivity and liquid crystallinity as expressed by the above formula (20).

The monomer (M1) is in the following formulas MA1, MA3, MA4, MA5, MA14, MA16~MA23, MA25, MA28~MA30, MA32, MA34, MA36, MA38~MA42, MA44 and MA46, and their compounds as The polymerizable group of the compound having methacrylate is acrylate, itaconate, fumarate, maleate, α-ethylene-γ-butyrolactone, styrene, vinyl At least one selected from the group of compounds substituted with a polymerizable group selected from the group consisting of maleimine, norbornene, and silicone is preferred. In particular, the monomer (M1) preferably has a (meth)acrylate as a polymerizable group, and it is preferable that, for example, the end of the side chain is COOH.

In addition, MA1 to MA46 can be synthesized as follows.

MA1 can be synthesized according to the synthesis method described in the patent document (WO2011-084546).

MA2 can be synthesized according to the synthesis method described in the patent document (Japanese Patent Application Laid-Open No. 9-118717).

MA3 was synthesized according to the synthesis method described in the non-patent literature (Macromolecules 2002, 35, 706-713).

MA4 can be synthesized according to the synthesis method described in the patent document (WO2014/054785).

MA5 can be synthesized according to the synthesis method described in the patent document (JP 2010-18807).

MA6~MA9 can be synthesized according to the synthesis method described in the patent document (WO2014/054785).

For MA10, M6BC (manufactured by Green Chemical Co., Ltd.), which can be purchased commercially, can be used.

MA11~13 can be synthesized according to the synthesis method described in the patent document (WO2014/054785).

MA14~18 can use commercially available M4CA, M4BA, M2CA, M3CA, and M5CA (all of which are manufactured by Green Chemical Co., Ltd.).

MA19-23 can be synthesized according to the synthesis method described in the patent document (WO2014/054785).

MA24 can be synthesized according to the synthesis method described in the non-patent literature (Polymer Journal, Vol. 29, No. 4, pp303-308 (1997)).

MA25 can be synthesized according to the synthesis method described in the patent document (WO2014/054785).

MA26 and MA27 can be synthesized according to the synthesis method described in non-patent literature (Macromolecules (2012), 45(21), 8547-8554) and non-patent literature (Liquid Crystals (1995), 19(4), 433-40). .

MA28~33 can be synthesized according to the synthesis method described in the patent document (WO2014/054785).

MA34~39 can be synthesized according to the synthesis method described in the patent document (WO2014/054785).

MA40 and 41 can be synthesized according to the synthesis method described in the patent document (Special Form No. 2009-511431).

MA42 can be synthesized according to the synthesis method described in the patent document (WO2014/054785).

MA43 can be synthesized according to the synthesis method described in the patent document (WO2012-115129).

MA44 can be synthesized according to the synthesis method described in the patent document (WO2013-133078).

MA45 can be synthesized according to the synthesis method described in the patent document (WO2008-072652).

MA46 can be synthesized according to the synthesis method described in the patent document (WO2014/054785).

[Monomer (M2) with a structure that only exhibits liquid crystallinity and its manufacturing method]

A monomer (M2) having a structure that only exhibits liquid crystallinity means that a polymer derived from the monomer exhibits liquid crystallinity, and the polymer can form mesogens at the side chain portion The monomer of the base.

The mesogen group in the side chain can be biphenyl or phenyl benzoate alone to form the base of the mesogen structure, or it can be benzoic acid, etc. by hydrogen bonding between side chains to form liquid crystal The basis of meta-structure. The mesogen group of the side chain preferably has the following structure.

More specific examples of the monomer (M2) having a structure that only exhibits liquid crystallinity include hydrocarbon, (meth)acrylate, itaconate, fumarate, maleate, and α-methylidene -Radical polymerizable groups such as γ-butyrolactone, styrene, vinyl, maleimide, norbornene, and at least one polymerizable group selected from the group consisting of silicone, It is preferable to have a structure composed of at least one of the above formulas (21) to (31).

The monomer (M2) is based on the above formulas MA2, MA9~MA13, MA15, MA24, MA26, MA27, MA31, MA35, MA37, The polymerizable groups of MA43 and MA45, and those compounds having methacrylate as polymerizable groups are acrylate, itaconate, fumarate, maleate, α-ethylene- At least one selected from the group consisting of γ-butyrolactone, styrene, vinyl, maleimide, norbornene, and silicone is preferably substituted with a polymerizable group. . In particular, the monomer (M2) preferably has a (meth)acrylate as a polymerizable group, and preferably, for example, the end of the side chain is COOH.

<<Monomer with crosslinkable group (M3)>>

In general, the polymer (A1), or the polymer (A2) as desired, has (M-3) a monomer having a crosslinkable group, specifically, the following formula (G-1), (G- 2) A monomer (M3) of at least one group selected from the group consisting of (G-3) and (G-4), more specifically a monomer having a structure represented by the following formula (0) ; And the form is better.

[Monomer having the structure represented by formula (0)]

More specific examples of monomers having the structure represented by the above formula (0) include hydrocarbons, (meth)acrylates, itaconates, fumarates, maleates, and α-methylenes. -Radical polymerizable groups such as γ-butyrolactone, styrene, vinyl, maleimide, norbornene, and at least one polymerizable group selected from the group consisting of silicone, The structure represented by the above formula (0) is preferred.

Among such monomers, monomers having epoxy groups, specifically, for example, glycidyl (meth)acrylate, (3,4-epoxycyclohexyl)methyl (meth)acrylate, and alkene Examples of compounds such as propyl glycidyl ether include glycidyl (meth)acrylate, (3,4-epoxycyclohexyl)methyl (meth)acrylate, and 3-vinyl- 7-oxabicyclo[4.1.0]heptane, 1,2-epoxy-5-hexene, 1,7-octadiene monoepoxide, etc.

Specific examples of the monomer having a thipropane ring include those in which the epoxy structure of the above-mentioned epoxy group-containing monomer is substituted with thipropane.

Specific examples of the monomer having aziridine include those in which the epoxy structure of the monomer having an epoxy group is substituted with aziridine or 1-methylaziridine.

In terms of monomers having oxetanyl groups, for example, (meth)acrylates having oxetanyl groups and the like. Among such monomers, for example, 3-(methacryloxymethyl)oxetane, 3-(acryloxymethyl)oxetane, 3-(methacryloxymethyl)oxetane, 3-(methacryloxymethyl)oxetane, 3-(methacryloxymethyl)oxetane, 3-(methacryloxymethyl)oxetane, 3-(methacryloxymethyl)oxetane, 3-(methacryloxymethyl)oxetane, 3-(methacryloxymethyl)oxetane Acetyloxymethyl)-3-methyl-oxetane, 3-(propenyloxymethyl)-3-methyl-oxetane, 3- (Methacryloxymethyl)-3-ethyl-oxetane, 3-(acryloxymethyl)-3-ethyl-oxetane, 3-(methyl Allyloxymethyl)-2-trifluoromethyloxetane, 3-(propenyloxymethyl)-2-trifluoromethyloxetane, 3-(methacryl) Acetyloxymethyl)-2-phenyl-oxetane, 3-(propenyloxymethyl)-2-phenyl-oxetane, 2-(methacryloxyl Methyl)oxetane, 2-(acryloxymethyl)oxetane, 2-(methacryloxymethyl)-4-trifluoromethyloxetane , 2-(acryloxymethyl)-4-trifluoromethyloxetane is better, 3-(methacryloxymethyl)-3-ethyl-oxetane , 3-(propenyloxymethyl)-3-ethyl-oxetane and the like.

Regarding the monomer having a thietane group, for example, the oxetanyl group of the monomer having an oxetanyl group is substituted with a thietane group.

Regarding the monomer having an azetidinyl group, for example, a monomer having an oxetanyl group substituted with an azetidinyl group is preferred.

Among the above, from the viewpoint of availability and the like, a monomer having an epoxy group and a monomer having an oxetanyl group are preferable, and a monomer having an epoxy group is more preferable. Among them, from the viewpoint of availability, glycidyl (meth)acrylate is preferred.

<<Monomers with nitrogen-containing aromatic heterocyclic groups (M4)>>

As mentioned above, the polymer (A1) or the polymer (A2) can have a nitrogen-containing aromatic heterocyclic group, an amide group and a urethane group as desired. At least one monomer (M4) selected from the group; the one that is formed is preferred.

A nitrogen-containing aromatic heterocyclic ring containing at least one of the following formula [20a], formula [20b] and formula [20c] (where Z ₂ is a linear or branched alkyl group with 1 to 5 carbon atoms) The structure selected in the group preferably contains 1 to 4 aromatic cyclic hydrocarbons of the structure.

Specifically, for example, pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, Thiadiazole ring, pyridazine ring, pyrazoline ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, quinoline ring, phenanthroline ring, Indole ring, quinoxaline ring, benzothiazole ring, thiodiphenylamine ring, oxadiazole ring, acridine ring, etc. Furthermore, the carbon atoms of these nitrogen-containing aromatic heterocycles may have heteroatom-containing substituents.

Among these, for example, a pyridine ring is preferable.

The polymer (A1) or the polymer (A2) has a group selected from a nitrogen-containing aromatic heterocyclic group, an amide group, and a urethane group, and the polymer composition of the present invention is used as a liquid crystal alignment film At the same time, the elution of ionic impurities is reduced, and the cross-linking reaction of the above-mentioned cross-linkable group is promoted, more specifically the cross-linking reaction of the group represented by the above formula (0), so that a liquid with higher durability can be obtained. 晶Alignment film. When manufacturing a polymer having a group selected from a nitrogen-containing aromatic heterocyclic group, an amide group, and a urethane group, the monomer (M4) is combined with the above-mentioned monomer (M1) and monomer (M2), The desired monomer (M3) can be copolymerized.

As the monomer (M4), it has hydrocarbon, (meth)acrylate, itaconate, fumarate, maleate, α-ethylene-γ-butyrolactone, styrene, vinyl , Maleimine, norbornene and other radical polymerizable groups, and at least one selected from the group consisting of silicone, and having a nitrogen-containing aromatic heterocyclic group, amide The structure of the urethane group and the urethane group is preferred. The NH of the amide group and the urethane group may be substituted or unsubstituted. As for the substituents which may be substituted, for example, an alkyl group, a protecting group for an amino group, a benzyl group, etc.

Among such monomers, monomers having a nitrogen-containing aromatic heterocyclic group, specifically, for example, 2-(2-pyridylcarbonyloxy)ethyl (meth)acrylate, 2-(3-pyridyl) Carbonyloxy)ethyl (meth)acrylate, 2-(4-pyridylcarbonyloxy)ethyl (meth)acrylate, and the like.

Specific examples of monomers having an amide group or urethane group include 2-(4-methylpiperidin-1-ylcarbonylamino)ethyl (meth)acrylate, 4-( 6-methacryloxyhexyloxy)benzoic acid N-(tert-butyloxycarbonyl)piperidin-4-yl ester, 4-(6-methacryloxyhexyloxy)benzoic acid 2-(tertiary butyloxycarbonylamino) ethyl ester and the like.

(M-4) A monomer (M4) having at least one group selected from the group consisting of a nitrogen-containing aromatic heterocyclic group, an amino group and a urethane group, in the following formulas MA6~MA8, and The polymerizable group of the compound having methacrylate ester as the polymerizable group in MA33, and their compounds is acrylic acid Consisting of ester, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene and silicone At least one selected from the group consisting of the polymerizable group-substituted compound selected from the group is preferred.

As mentioned above, it can be copolymerized with other monomers without compromising the performance capability of photoreactivity and/or liquid crystallinity.

Other monomers, such as those that are commercially available and can undergo radical polymerization.

Specific examples of other monomers include unsaturated carboxylic acids, acrylate compounds, methacrylate compounds, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds, and vinyl compounds.

As a specific example of an unsaturated carboxylic acid, acrylic acid, methacrylic acid, itaconic acid, maleic acid ester, fumaric acid, etc. are mentioned, for example.

Acrylate compounds, for example, methacrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methacrylate, phenyl acrylate, 2,2,2-Trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate , 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantane Methyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and 8-ethyl-8-tricyclodecyl acrylate, etc.

Methacrylate compounds, for example, methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate Esters, anthracenyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl Methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecane Methacrylic acid Acid ester, and, 8-ethyl-8-tricyclodecyl methacrylate, etc.

In terms of vinyl compounds, for example, vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether.

In terms of styrene compounds, for example, styrene, methylstyrene, chlorostyrene, bromostyrene, and the like.

Regarding the maleimide compound, for example, maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

The method for producing at least two types of polymers of the present invention is not particularly limited, and methods widely used in industry can be used. Specifically, the monomer (M1) having a structure expressing photoreactivity and liquid crystallinity; and the monomer (M2) having a structure expressing only liquid crystallinity, as desired, a monomer having a crosslinkable group can be used. Monomer (M3), and, as desired, a vinyl group having at least one monomer (M4) selected from the group consisting of a nitrogen-containing aromatic heterocyclic group, an amide group and a urethane group It can be produced by cationic polymerization, radical polymerization, and anionic polymerization. Among these, from the viewpoint of difficulty of reaction control, etc., radical polymerization is particularly preferred.

Regarding the polymerization initiator for radical polymerization, conventional compounds such as a radical polymerization initiator or a reversible addition-cracking type chain transfer (RAFT) polymerization reagent can be used.

The radical thermal polymerization initiator is a compound that generates free radicals by heating above the decomposition temperature. Such radical thermal polymerization initiators, such as ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxides, etc.) , Benzyl peroxide, etc.), hydroperoxides (hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, etc.), dialkyl peroxides (di-tert -Butyl peroxide, dicumyl peroxide, dilaurel peroxide, etc.), peroxy ketals (dibutylperoxycyclohexane, etc.), alkyl peresters (Peroxyneodecanoic acid-tert-butyl ester, peroxypivalic acid-tert-butyl ester, peroxy2-ethylcyclohexane acid-tert-pentyl ester, etc.), persulfuric acid Salts (potassium persulfate, sodium persulfate, ammonium persulfate, etc.), azo compounds (azobisisobutyronitrile, and 2,2 ' -bis(2-hydroxyethyl)azobisisobutyronitrile, etc. ). Such a radical thermal polymerization initiator can be used singly or in combination of two or more kinds.

The radical photopolymerization initiator is a compound that starts radical polymerization by light irradiation, and is not particularly limited. Such radical photopolymerization initiators include, for example, benzophenone, Michler’s ketone, 4,4'-bis(diethylamino)benzophenone, xanthone, thioxanthone, iso Propylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-4' -Isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2 -Phenylacetophenone, camphorquinone, benzoanthrone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, 2-benzyl-2 -Dimethylamino-1-(4-morpholinophenyl)-butanone-1, 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid isoamyl ester , 4,4'-bis(t-butylperoxycarbonyl)benzophenone, 3,4,4'-tris(t-butylperoxycarbonyl)benzophenone, 2,4,6 -Trimethylbenzyldiphenylphosphine oxide, 2-(4'-methyl Oxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxystyryl)-4,6-bis(trichloro Methyl)-s-triazine, 2-(2',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2'- Methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-pentyloxystyryl)-4,6-bis(trichloromethyl) )-s-triazine, 4-[pN,N-bis(ethoxycarbonylmethyl)]-2,6-bis(trichloromethyl)-s-triazine, 1,3-bis(trichloro Methyl)-5-(2'-chlorophenyl)-s-triazine, 1,3-bis(trichloromethyl)-5-(4'-methoxyphenyl)-s-triazine, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-mercaptobenzothiazole, 3,3'-carbonyl bis( 7-diethylaminocoumarin), 2-(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2-Chlorophenyl)-4,4',5,5'-Four (4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2,4-di Chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'bis(2,4-dibromophenyl)-4,4',5, 5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1, 2'-Biimidazole, 3-(2-methyl-2-dimethylaminopropionyl)carbazole, 3,6-bis(2-methyl-2-morpholinopropionyl)-9 -n-Dodecylcarbazole, 1-hydroxycyclohexyl phenyl ketone, bis(5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H -Pyrrol-1-yl)-phenyl)titanium, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra (t-hexylperoxycarbonyl)benzophenone, 3,3'-bis(methoxycarbonyl)-4,4'-bis(t-butylperoxycarbonyl)benzophenone, 3, 4'-bis(methoxycarbonyl)-4,3'-bis(t-butylperoxycarbonyl)benzophenone, 4,4'-bis(methoxycarbonyl)-3,3'- Bis(t-butylperoxycarbonyl)benzophenone, 2-(3-methyl-3H-benzothiazole-2-ylidene)-1-naphthalene-2-yl-ethanone, or 2-( 3-Methyl-1,3-benzothiazole-2(3H)-ylidene)-1-(2-benzyl)ethanone and the like. Of these The compound can be used alone or in combination of two or more kinds.

The radical polymerization method is not particularly limited, and an emulsion polymerization method, a suspension polymerization method, a dispersion polymerization method, a precipitation polymerization method, a bulk polymerization method, a solution polymerization method, etc. can be used.

As a monomer (M1) that has a structure that exhibits photoreactivity and liquid crystallinity; and a monomer (M2) that has a structure that only exhibits liquid crystallinity, a monomer (M3) that has a crosslinkable group as desired, and Then according to the desired monomer (M4) having at least one group selected from the group consisting of a nitrogen-containing aromatic heterocyclic group, an amide group and a urethane group are copolymerized to obtain at least 2 of the present invention. The organic solvent used for the reaction of the polymer of this kind is not particularly limited if it dissolves the produced polymer. The specific example is as follows.

N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactone Amide, dimethyl sulfide, tetramethyl urea, pyridine, dimethyl sulfide, hexamethyl sulfide, γ-butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, Ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve B Ester, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl Base ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol Dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol Monoacetate Monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl Base ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane , N-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, acetic acid n -Butyl ester, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, 3- Ethyl methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diethylene glycol Dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy-N,N-dimethylpropanamide, 3-ethoxy-N,N-dimethylpropanone Amine, 3-butoxy-N,N-dimethylpropanamide, etc.

These organic solvents can be used alone or in combination. Furthermore, even if it is a solvent that does not dissolve the produced polymer, it can be used in combination with the above-mentioned organic solvent in the range where the produced polymer does not precipitate.

In addition, in radical polymerization, oxygen in the organic solvent is a cause of hindering the polymerization reaction. Therefore, it is better to use the organic solvent that has been degassed as much as possible.

The polymerization temperature during radical polymerization can be selected from any temperature of 30°C to 150°C, but is preferably in the range of 50°C to 100°C. In addition, although the reaction can be carried out at any concentration, it becomes difficult to obtain a high molecular weight polymer if the concentration is too low. If the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring becomes difficult, so the monomer concentration is relatively high. It is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 30% by mass. The initial stage of the reaction can be carried out at a high concentration, which After that, add organic solvent.

In the above-mentioned free radical polymerization reaction, if the ratio of the radical polymerization initiator is higher than that of the monomer, the molecular weight of the obtained polymer becomes smaller, and the molecular weight of the obtained polymer becomes larger. Therefore, the ratio of the radical initiator is relatively For the monomer to be polymerized, 0.1 mol% to 10 mol% is preferred. In addition, various monomer components, solvents, initiators, etc. may be added during polymerization.

[Recycling of polymers]

When recovering the polymer produced from the reaction solution obtained by the above reaction, the reaction solution is poured into a poor solvent and the polymer is precipitated. Examples of poor solvents used for precipitation include methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and diethyl ether. , Methyl ethyl ether, water, etc. The polymer precipitated after being put into the poor solvent can be dried under normal pressure or reduced pressure, normal temperature or heating after filtration and recovery. In addition, by repeating the operation of re-dissolving the polymer recovered by precipitation in an organic solvent and performing the re-precipitation recovery operation 2 to 10 times, the impurities in the polymer can be reduced. The poor solvents at this time include, for example, alcohols, ketones, hydrocarbons, etc. If three or more types of poor solvents selected from these are used, it is better to further improve the efficiency of purification.

[Preparation of polymer composition]

The polymer composition used in the present invention is preferably prepared as a coating liquid in a manner suitable for the formation of the liquid crystal alignment film. That is, the polymer composition used in the present invention is prepared so that the resin component for forming a resin film is dissolved in an organic solvent The solution is better. Here, the resin component refers to a resin component containing at least two (A) polymers having a structure exhibiting photoreactivity and a structure exhibiting liquid crystallinity, and one of the polymers contains a crosslinkable group. At this time, the content of the resin component is preferably 1% by mass to 20% by mass, more preferably 1% by mass to 15% by mass, and particularly preferably 1% by mass to 10% by mass.

In the polymer composition of this embodiment, the aforementioned resin components may all be at least two of the above-mentioned (A) polymers having a structure that exhibits photoreactivity and a structure that exhibits liquid crystallinity, but without impairing the ability of liquid crystal expression And the range of photosensitive performance, other polymers other than them can be mixed. At this time, the content of other polymers in the resin component is 0.5% by mass to 80% by mass, preferably 1% by mass to 50% by mass.

Such other polymers, such as those composed of poly(meth)acrylate, polyamide acid, or polyimide, etc., are not polymers having a structure that exhibits photoreactivity and a structure that exhibits liquid crystallinity. Wait.

<(B) Organic solvent>

The organic solvent used in the polymer composition used in the present invention is an organic solvent that dissolves the resin component and is not particularly limited. The specific example is as follows.

For example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactone, 2-pyrrolidone , N-ethylpyrrolidone, N-vinylpyrrolidone, dimethyl sulfide, tetramethylurea, pyridine, dimethyl sulfide, hexamethyl pyrrolidone, γ-butyrolactone, 3-methyl Oxy-N,N-dimethylpropanamide, 3-ethoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, 1, 3-Dimethyl-imidazolinone, ethyl Amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diglyme, 4 -Hydroxy-4-methyl-2-pentanone, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol mono Acetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, two Propylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, etc. These can be used alone or in combination.

The polymer composition used in the present invention may contain components other than the above-mentioned (A) and (B) components. In particular, when the polymer composition of the present invention is used in a liquid crystal alignment film for a liquid crystal display device, especially a horizontal electric field drive type liquid crystal display device, it may contain components other than the above-mentioned (A) and (B) components. Examples include, for example, a solvent that improves film thickness uniformity or surface smoothness when the polymer composition is applied to a substrate, especially a substrate for liquid crystal display devices, and more particularly a substrate for horizontal electric field drive type liquid crystal display devices. Or compounds, compounds that improve the adhesion between the liquid crystal alignment film and the substrate, etc., but not limited thereto.

<(C) Amine compound>

The polymer composition used in the present invention may have (C) a specific amine compound as a component other than the above-mentioned (A) and (B) components.

As the specific amine compound of the component (C), specifically, it may have a primary amine group and a nitrogen-containing aromatic heterocyclic ring in the molecule, and the aforementioned primary amine group is bonded Amine compounds bound to aliphatic hydrocarbon groups or non-aromatic cyclic hydrocarbon groups. When the polymer composition of the present invention contains the amine compound, when the polymer composition of the present invention is used as a liquid crystal alignment film, the elution of ionic impurities is reduced, and the crosslinking reaction of the above-mentioned crosslinkable group is promoted, more specifically, By promoting the crosslinking reaction of the group represented by the above formula (0), a liquid crystal alignment film with higher durability can be obtained.

When the specific amine compound is the polymer composition used in the present invention to form a liquid crystal alignment film, it is only necessary to achieve the following effects i) and/or ii), and it is not particularly limited. Achieve i) at the interface of the liquid crystal alignment film, adsorb ionic impurities in the liquid crystal, or and/or ii) increase the voltage retention rate.

The amount of the specific amine compound is not particularly limited as long as the above-mentioned effect is achieved, but in 100 parts by mass of the polymer composition used in the present invention, it is 0.01 to 10 parts by mass, preferably 0.1 to 5 parts by mass.

Specific examples of the aliphatic hydrocarbon group include, for example, a linear alkylene group, an alkylene group having a branched structure, and a divalent hydrocarbon group having an unsaturated bond. The carbon number of the aliphatic hydrocarbon group is preferably 1-20, more preferably 1-15, and still more preferably 1-10.

Specific examples of divalent non-aromatic cyclic hydrocarbon groups include, for example, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, ring Decane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecan ring, cyclooctadecane ring Ring, cyclonadecane ring, cycloeicosane ring, tricycloeicosane ring, tricyclodocosane ring, bicycloheptane ring, decahydronaphthalene ring, norbornene ring, adamantane ring, etc. It is preferably a ring composed of 3 to 20 carbons, and more It is preferably a ring composed of 3 to 15 carbon atoms, and more preferably a non-aromatic cyclic hydrocarbon group composed of 3 to 10 carbon atoms.

The nitrogen-containing aromatic heterocyclic ring contained in the amine compound contains at least one of the following formula [20a], formula [20b] and formula [20c] (where Z ₂ is a straight chain or fraction of carbon number 1 to 5) The structure selected from the group consisting of branch alkyl) preferably contains 1 to 4 aromatic cyclic hydrocarbons of the structure.

Specifically, for example, pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, Thiadiazole ring, pyridazine ring, pyrazoline ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, quinoline ring, phenanthroline ring, Indole ring, quinoxaline ring, benzothiazole ring, thiodiphenylamine ring, oxadiazole ring, acridine ring, etc. Furthermore, the carbon atoms of these nitrogen-containing aromatic heterocycles may have heteroatom-containing substituents.

More preferably, the amine compound is represented by the following formula A-[1] (where Y ₁₁ is a divalent organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, and Y ₁₂ is a nitrogen-containing aromatic heterocyclic ring) Amine compounds are preferred. In formula A-[1], Y ₁₂ is a divalent organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, and it is not particularly limited.

_{Preferred Y 11} in the formula A-[1] is a divalent organic group selected from one type of aliphatic hydrocarbon group having 1 to 20 carbon atoms and a non-aromatic cyclic hydrocarbon group having 3 to 20 carbon atoms. Examples of the non-aromatic cyclic hydrocarbon group include the above-mentioned structures. More _{preferably Y 11} includes, for example, an aliphatic hydrocarbon group having 1 to 15 carbon atoms, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, and a cyclononane ring. , Cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, norbornene ring, adamantane ring, etc. Y _{11 is} particularly preferably a straight chain or branched alkylene group with 1 to 10 carbon atoms.

In addition, _{-CH 2} -in any aliphatic hydrocarbon group or non-aromatic cyclic hydrocarbon group not adjacent to the amino group contained in _{Y 11} can be replaced by -O-, -NH-, -CO-O-, -O -CO-, -CO-NH-, -NH-CO-, -CO-, -S-, -S(O) ₂ -, -CF ₂ -, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -O-Si(CH ₃ ) ₂ -, -Si(CH ₃ ) ₂ -O-, -O-Si(CH ₃ ) ₂ -O-, 2 Valence cyclic hydrocarbon group or heterocyclic substitution. In addition, the hydrogen atom bonded to any carbon atom can be a linear or branched alkylene group with 1 to 20 carbons, a cyclic hydrocarbon group, a fluorine-containing alkyl group with 1 to 10 carbons, a heterocyclic ring, a fluorine atom, Hydroxyl substitution.

Specific examples of the bivalent cyclic hydrocarbon group include benzene ring, naphthalene ring, tetrahydronaphthalene ring, azulene ring, indene ring, stilbene ring, anthracene ring, phenanthrene ring, phenalene ring, cyclopropane ring, cyclobutane Alkyl ring, cyclopentane ring, cyclohexane ring, Cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, Cyclohexadecane ring, cycloheptadecan ring, cyclooctadecane ring, cyclononadecane ring, cycloeicosane ring, tricycloeicosane ring, tricyclodocosane ring, bicycloheptane ring, Decahydronaphthalene ring, norbornene ring, adamantane ring, etc.

In addition, specific examples of the divalent heterocyclic ring include pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, and isoquinoline ring. , Carbazole ring, purine ring, thiadiazole ring, pyridazine ring, pyrazoline ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, quine A morpholine ring, a phenanthroline ring, an indole ring, a quinoxaline ring, a benzothiazole ring, a thiodiphenylamine ring, an oxadiazole ring, an acridine ring, etc.

_{Y 12} in formula A-[1] is a nitrogen-containing aromatic heterocyclic ring, which is the same as above, and contains at least one structure selected from the group consisting of formula [20a], formula [20b], and formula [20c] The aromatic cyclic hydrocarbon is preferred. As for the specific example, the above-mentioned structure can be mentioned, for example. Among these, pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, quinoxaline Ring, nitrogen heterocycle, diaza heterocycle, naphthalene ring, phenazine ring, and phthalazine ring are preferred.

In addition, from the viewpoint of the difficulty of the so-called electrostatic interaction formed by the nitrogen-containing aromatic heterocyclic ring and the salt of the carboxyl group in the specific polyimine or hydrogen bonding, Y ₁₁ is the formula contained in the discordant Y _{12 [20a]} , Formula [20b], and formula [20c] adjacent substituents are preferably bonded.

_{Furthermore, Y 12 of the} formula A-[1], that is, the carbon atom of the nitrogen-containing aromatic heterocyclic ring, may have a halogen atom and/or a substituent of an organic group, and the organic group may contain an oxygen atom, a sulfur atom, a nitrogen atom, etc. The heteroatoms.

The preferred combination of Y ₁₁ and Y ₁₂ in the _{formula A-[1] Y 11} is a group consisting of an aliphatic hydrocarbon group with 1 to 20 carbon atoms and a non-aromatic cyclic hydrocarbon group with 3 to 20 carbon atoms One selected divalent organic group, Y ₁₂ is a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a triazole ring, a pyrazine ring, a benzimidazole ring, Benzimidazole ring, quinoxaline ring, nitrogen heterocycle, diaza heterocycle, naphthalene ring, phenazine ring, or phthalazine ring. In addition, _{the carbon atom of the nitrogen-containing aromatic heterocyclic ring of Y 12} may have a halogen atom and/or a substituent of an organic group, and the organic group may contain a hetero atom such as an oxygen atom, a sulfur atom, and a nitrogen atom.

More preferably the aspect of the amine compound, the following formula A- [2] (wherein, Y ₁₃ carbon atoms is a divalent aliphatic hydrocarbon group or non-aromatic cyclic hydrocarbon group of 1 to 10, Y ₁ 4 is a single bond, or - O-, -NH-, -S-, -SO ₂ -or a divalent organic group having 1 to 19 carbon atoms. In addition, the total number of carbon atoms in _{Y 13} and Y _{14 is 1 to 20. Y 15} is nitrogen-containing Aromatic heterocyclic ring.) The amine compound represented.

_{Y 13} in the formula A-[2] is a divalent aliphatic hydrocarbon group with 1 to 10 carbons or a non-aromatic cyclic hydrocarbon group. Specific examples thereof include, for example, linear or branched alkylene groups having 1 to 10 carbon atoms, unsaturated alkylene groups having 1 to 10 carbon atoms, cyclopropane ring, cyclobutane ring, cyclopentane ring, and cyclohexene ring. Alkane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring Alkane ring, cyclohexadecane ring, cycloheptadecan ring, cyclooctadecane ring, cyclononadecane ring, cycloeicosane ring, tricycloeicosane ring, tricyclodocosane ring, bicycloheptane Alkyl ring, decahydronaphthalene ring, norbornene ring, adamantane ring, etc. More preferably, straight-chain or branched alkylene having 1 to 10 carbon atoms, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane Ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, norbornene ring, adamantane ring. Particularly preferred is a straight chain or branched alkylene group with 1 to 10 carbon atoms.

_{-CH 2} -in any aliphatic hydrocarbon group or non-aromatic cyclic hydrocarbon group that is not adjacent to the amine group contained in Y ₁₃ can be -O-, -NH-, -CO-O-, -O-CO -, -CO-NH-, -NH-CO-, -CO-, -S-, -S(O) ₂ -, -CF ₂ -, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -O-Si(CH ₃ ) ₂ -, -Si(CH ₃ ) ₂ -O-, -O-Si(CH ₃ ) ₂ -O-, divalent ring Like hydrocarbyl or heterocyclic substitution. In addition, the hydrogen atom bonded to any carbon atom can be substituted by a linear or branched alkyl group with 1 to 20 carbons, a cyclic hydrocarbon group, a fluorine-containing alkyl group with 1 to 10 carbons, a heterocyclic ring, a fluorine atom, and a hydroxyl group. replace. The so-called cyclic hydrocarbon group and heterocyclic ring herein have the same definitions as described for _{Y 11 in formula A-[1].}

_{Y 14} in the formula A-[2] is a single bond, or -O-, -NH-, -S-, -SO ₂ -or a divalent organic group with 1 to 19 carbon atoms. The divalent organic group having 1 to 19 carbon atoms is a divalent organic group having 1 to 19 carbon atoms, and may contain an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, and the like. The specific example of Y ₁₄ is as follows.

For example, single bond, -O-, -NH-, -S-, -SO ₂ -, hydrocarbon group with 1 to 19 carbons, -CO-O-, -O-CO-, -CO-NH-, -NH -CO-, -CO-, -CF ₂ -, -C(CF ₃ ) ₂ -, -CH(OH)-, -C(CH ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -O- Si(CH ₃ ) ₂ -, -Si(CH ₃ ) ₂ -O-, -O-Si(CH ₃ ) ₂ -O-, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring , Cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring , Cyclohexadecane ring, cycloheptadecan ring, cyclooctadecane ring, cyclononadecane ring, cycloeicosane ring, tricycloeicosane ring, tricyclodocosane ring, bicycloheptane ring , Decahydronaphthalene ring, norbornene ring, adamantane ring, benzene ring, naphthalene ring, tetrahydronaphthalene ring, azulene ring, indene ring, stilbene ring, anthracene ring, phenanthrene ring, phenalene ring, pyrrole ring, imidazole Ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, thiadiazole ring, pyridazine ring, three Pyrazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, quinoline ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, sulfur Substituted diphenylamine ring, oxadiazole ring, acridine ring, oxazole ring, piperazine ring, piperidine ring, dioxane ring, morpholine ring, etc. Y ₁₄ may contain two or more of these.

Specific examples of the two or more types include -NH-CH ₂ -, -NH-C ₂ H ₄ -, -NH-C ₃ H ₆ -, -NH-C ₄ H ₈ -, -S -CH ₂ -, -SC ₂ H ₄ -, -SC ₃ H ₆ -, -SC ₄ H ₈ -, -O-CH ₂ -, -OC ₂ H ₄ -, -OC ₃ H ₆ -, -OC ₄ H ₈ -, -NH-CO-CH ₂ -, -NH-CO-C ₂ H ₄ -, -NH-CO-C ₃ H ₆ -, -NH-CO-C ₄ H ₈ -, -CO-CH ₂ -, -CO-C ₂ H ₄ -, -CO-C ₃ H ₆ -, -CO-C ₄ H ₈ -, -CO-NH-CH ₂ -, -CO-NH-C ₂ H ₄ -, -CO-NH-C ₃ H ₆ -, -CO-NH-C ₄ H ₈ -, -NH-CH ₂ -CH(CH ₃ )-, -NH-C ₂ H ₄ -CH(CH ₃ )-, -NH-C ₃ H ₆ -CH(CH ₃ )-, -NH-C ₄ H ₈ -CH(CH ₃ )-, -S-CH ₂ -CH(CH ₃ )-, -SC ₂ H ₄ -CH (CH ₃ )-, -SC ₃ H ₆ -CH(CH ₃ )-, -SC ₄ H ₈ -CH(CH ₃ )-, -O-CH ₃ -CH(CH ₃ )-, -OC ₂ H ₄ -CH(CH ₃ )-, -OC ₃ H ₆ -CH(CH ₃ )-, -OC ₄ H ₈ -CH(CH ₃ )-, -NH-CO-CH ₂ -CH(CH ₃ )-,- NH-CO-C ₂ H ₄ -CH(CH ₃ )-, -NH-CO-C ₃ H ₆ -CH(CH ₃ )-, -NH-CO-C ₄ H ₈ -CH(CH ₃ )-, -CH(OH)-CH ₂ -, -CH(OH)-C ₂ H ₄ -, -CH(OH)-C ₃ H ₆ -, -CH(OH)-C ₄ H ₈ -, -CH(CH ₂ OH)-CH ₂ -, -CH(CH ₂ OH)-C ₂ H ₄ -, -CH(CH ₂ OH)-C ₃ H ₆ -, -CH(CH ₂ OH)-C ₄ H ₈ -, -NH-CH(CH ₂ OH)-CH ₂ -, -CO-NH-CH(CH ₂ OH)-CH ₂ -, -NH-CO-CH(CH ₂ OH)-CH ₂ -, -CO-CH (CH ₂ OH)-CH ₂ -, -S-CH(CH ₂ OH)-CH ₂ -, -O-C H(CH ₂ OH)-CH ₂ -, -CH(N(CH ₃ ) ₂ )-, -C ₆ H ₄ -O-, -C ₆ H ₄ -NH-, -C ₆ H ₄ -CO-NH -, -C ₆ H ₄ -NH-CO-, -C ₆ H ₄ -CO-, -C ₆ H ₄ -CH ₂ -, -C ₆ H ₄ -S-, etc.

_{Y 15} in formula A-[2] is a nitrogen-containing aromatic heterocyclic ring, which has the same definition as _{Y 12 in formula A-[1].} In terms of specific examples, for example, the same structure _{as that of Y 12 described above can be given.} Among these, pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, quinoxaline A ring, a nitrogen heterocyclic ring, a diaza heterocyclic ring, a naphthalene ring, a phenazine ring, or a phthalazine ring are preferred.

In addition, salts formed from the viewpoint of difficulty of the nitrogen-containing aromatic heterocyclic carboxy specific polyimide in the static or so-called hydrogen bonding interactions, with the formula Y14 and Y ₁₅ is not contained in [20a], of formula Adjacent carbon atoms in [20b] or formula [20c] are preferably bonded.

_{Furthermore, Y 15 of} formula A-[2] is the carbon atom of the nitrogen-containing aromatic heterocyclic ring, which may have halogen atoms and/or substituents of organic groups, and the organic groups may contain oxygen atoms, sulfur atoms, nitrogen atoms, etc. Heteroatom.

_{The preferred combination of Y 13} , Y ₁₄ and Y ₁₅ in the formula A-[2] is that Y ₁₃ is a linear or branched alkylene group with 1 to 10 carbon atoms, a cyclopropane ring, a cyclobutane ring, and a cyclopentane ring. Alkane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring Ring, norbornene ring or adamantane ring, Y ₁₄ is a single bond, straight chain or branched alkyl group with carbon number 1~10, -O-, -NH-, -CO-O-, -O-CO -, -CO-NH-, -NH-CO-, -CO-, -S-, -SO ₂ -, -CF ₂ -, -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -O-Si(CH ₃ ) ₂ -, -Si(CH ₃ ) ₂ -O-, -O-Si(CH ₃ ) ₂ -O-, -CH(OH)-, -NH-CH ₂ -,- NH-C ₂ H ₄ -, -NH-C ₃ H ₆ -, -NH-C ₄ H ₈ -, -S-CH ₂ -, -SC ₂ H ₄ -, -SC ₃ H ₆ -, -SC ₄ H ₈ -, -O-CH ₂ -, -OC ₂ H ₄ -, -OC ₃ H ₆ -, -OC ₄ H ₈ -, -NH-CO-CH ₂ -, -NH-CO-C ₂ H ₄ -, -NH-CO-C ₃ H ₆ -, -NH-CO-C ₄ H ₈ -, -CO-CH ₂ -, -CO-C ₂ H ₄ -, -CO-C ₃ H ₆ -,- CO-C ₄ H ₈ -, -CO-NH-CH ₂ -, -CO-NH-C ₂ H ₄ -, -CO-NH-C ₃ H ₆ -, -CO-NH-C ₄ H ₈ -, -NH-CH ₂ -CH(CH ₃ )-, -NH-C ₂ H ₄ -CH(CH ₃ )-, -NH-C ₃ H ₆ -CH(CH ₃ )-, -NH-C ₄ H _{8 -CH (CH 3) -, -} S-CH 2 -CH (CH 3) -, - SC 2 H 4 -CH (CH 3) -, - SC 3 H 6 -CH (CH 3) -, -SC 4 H ₈ -CH(CH ₃ )-, -O-CH ₃ -CH(CH ₃ )-, -OC ₂ H ₄ -CH(CH ₃ )-, -OC ₃ H ₆ -CH(CH ₃ )-,- OC ₄ H ₈ -CH(CH ₃ )-, -NH-CO-CH ₂ -CH(CH ₃ )-, -NH-CO-C ₂ H ₄ -CH(CH ₃ )-, -NH-CO-C ₃ H ₆ -CH(CH ₃ )-, -NH-CO-C ₄ H ₈ -CH(CH ₃ )-, -CH(OH)-CH ₂ -, -CH(OH)-C ₂ H ₄ -, -CH(OH)-C ₃ H ₆ -, -CH(OH)-C ₄ H ₈ -,- CH(CH ₂ OH)-CH ₂ -, -CH(CH ₂ OH)-C ₂ H ₄ -, -CH(CH ₂ OH)-C ₃ H ₆ -, -CH(CH ₂ OH)-C ₄ H ₈ -, -NH-CH(CH ₂ OH)-CH ₂ -, -CO-NH-CH(CH ₂ OH)-CH ₂ -, -NH-CO-CH(CH ₂ OH)-CH ₂ -,- CO-CH(CH ₂ OH)-CH ₂ -, -S-CH(CH ₂ OH)-CH ₂ -, -O-CH(CH ₂ OH)-CH ₂ -, -CH(N(CH ₃ ) ₂ )-, -C ₆ H ₄ -O-, -C ₆ H ₄ -NH-, -C ₆ H ₄ -CO-NH-, -C ₆ H ₄ -NH-CO-, -C ₆ H ₄ -CO -, -C ₆ H ₄ -CH ₂ -, -C ₆ H ₄ -S-, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, Cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, norbornene ring, adamantane ring, benzene ring, naphthalene ring, tetrahydronaphthalene ring, azulene ring, indene ring, stilbene ring , Anthracene ring, phenanthrene ring, phenalene ring, Y ₁₅ is pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole Ring, benzimidazole ring, quinoxaline ring, nitrogen heterocyclic ring, diaza heterocyclic ring, naphthalene ring, phenazine ring, or phthalazine ring. In addition, _{the carbon atom of the nitrogen-containing aromatic heterocyclic ring of Y 15} may have a substituent of a halogen atom and/or an organic group, and the organic group may contain a hetero atom such as an oxygen atom, a sulfur atom, and a nitrogen atom.

A more preferable combination _{of Y 13} , Y ₁₄ and Y ₁₅ in formula A-[2] _{is that Y 13} is a straight chain or branched alkylene group with 1 to 5 carbon atoms, a cyclopropane ring, a cyclobutane ring, and a ring Pentane ring, cyclohexane ring, cycloheptane ring, norbornene ring, or adamantane ring, Y ₁₄ is a single bond, linear or branched alkylene group with carbon number 1 to 5, -O-,- NH-, -CO-O-, -O-CO-, -CO-NH-, -NH-CO-, -CO-, -S-, -S(O) ₂ -, -CH(OH)-, -NH-CH ₂ -, -S-CH ₂ -, -O-CH ₂ -, -OC ₂ H ₄ -, -NH-CO-CH ₂ -, -CO-CH ₂ -, -CO-NH-CH ₂ -, -NH-CH ₂ -CH(CH ₃ )-, -S-CH ₂ -CH(CH ₃ )-, -O-CH ₃ -CH(CH ₃ )-, -NH-CO-CH _2- CH(CH ₃ )-, -CH(OH)-CH ₂ -, -CH(OH)-C ₂ H ₄ -, -CH(CH ₂ OH)-CH ₂ -, -NH-CH(CH ₂ OH) -CH ₂ -, -CO-NH-CH(CH ₂ OH)-CH ₂ -, -NH-CO-CH(CH ₂ OH)-CH ₂ -, -CO-CH(CH ₂ OH)-CH _2- , -S-CH(CH ₂ OH)-CH ₂ -, -O-CH(CH ₂ OH)-CH ₂ -, -CH(N(CH ₃ ) ₂ )-, -C ₆ H ₄ -O-, -C ₆ H ₄ -NH-, -C ₆ H ₄ -CO-NH-, -C ₆ H ₄ -NH-CO-, -C ₆ H ₄ -CO-, -C ₆ H ₄ -CH ₂ -, -C ₆ H ₄ -S-, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, norbornene ring, adamantane ring, benzene ring, naphthalene ring, tetrahydro Naphthalene ring, azulene ring, indene ring, pyrrolidone ring, anthracene ring, phenanthrene ring, or phenalene ring, Y ₁₅ is pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring , Triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, quinoxaline ring, nitrogen heterocyclic ring, diaza heterocyclic ring, naphthalene ring, phenazine ring, or phthalazine ring. In addition, _{the carbon atom of the nitrogen-containing aromatic heterocyclic ring of Y 15} may have a substituent of a halogen atom and/or an organic group, and the organic group may contain a hetero atom such as an oxygen atom, a sulfur atom, and a nitrogen atom.

A more preferable combination _{of Y 13} , Y ₁₄ and Y ₁₅ in the formula A-[2] _{is that Y 13} is a linear or branched alkylene group with 1 to 5 carbon atoms, a cyclopropane ring, a cyclobutane ring, and a ring Pentane ring or cyclohexane ring, Y ₁₄ is a single bond, linear or branched alkylene group with carbon number 1~5, -O-, -NH-, -CO-O-, -O-CO- , -CO-NH-, -NH-CO-, -CO-, -CH(OH)-, -NH-CH ₂ -, -S-CH ₂ -, -O-CH ₂ -, -NH-CO- CH ₂ -, -CO-CH ₂ -, -CO-NH-CH ₂ -, -NH-CH ₂ -CH(CH ₃ )-, -S-CH ₂ -CH(CH ₃ )-, -O-CH ₃ -CH(CH ₃ )-, -NH-CO-CH ₂ -CH(CH ₃ )-, -CH(OH)-CH ₂ -, -CH(OH)-C ₂ H ₄ -, -CH(CH ₂ OH)-CH ₂ -, -NH-CH(CH ₂ OH)-CH ₂ -, -CO-NH-CH(CH ₂ OH)-CH ₂ -, -NH-CO-CH(CH ₂ OH)- CH ₂ -, -CO-CH(CH ₂ OH)-CH ₂ -, -S-CH(CH ₂ OH)-CH ₂ -, -O-CH(CH ₂ OH)-CH ₂ -, -CH(N (CH ₃ ) ₂ )-, -C ₆ H ₄ -O-, -C ₆ H ₄ -NH-, -C ₆ H ₄ -CO-NH-, -C ₆ H ₄ -NH-CO-, -C ₆ H ₄ -CO-, -C ₆ H ₄ -CH ₂ -, -C ₆ H ₄ -S-, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, Norbornene ring, adamantane ring, benzene ring, naphthalene ring, tetrahydronaphthalene _{ring, pyridine ring, or anthracene ring, Y 15} is pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, Triazine ring, triazole ring, pyrazine ring, benzimidazole ring, or benzimidazole ring. In addition, _{the carbon atom of the nitrogen-containing aromatic heterocyclic ring of Y 15} may have a substituent of a halogen atom and/or an organic group, and the organic group may contain a hetero atom such as an oxygen atom, a sulfur atom, and a nitrogen atom.

A particularly preferred combination _{of Y 13} , Y ₁₄ and Y ₁₅ in formula A-[2] _{is that Y 13} is a linear or branched alkylene ring with 1 to 5 carbon atoms, a cyclobutane ring, or a cyclohexane ring, Y ₁₄ is a single bond, -O-, -CO-O-, -O-CO-, -CO-NH-, -NH-CO-, -CH(OH)-, benzene ring, naphthalene ring, sulphur ring, Or anthracene ring, Y ₁₅ is pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, or pyrimidine ring. In addition, _{the carbon atom of the nitrogen-containing aromatic heterocyclic ring of Y 15} may have a substituent of a halogen atom and/or an organic group, and the organic group may contain a hetero atom such as an oxygen atom, a sulfur atom, and a nitrogen atom.

Specific examples of the specific amine compound of the component (C) of the present invention include, for example, compounds of M1 to M156.

More preferable compounds include, for example, M6~M8, M10, M16~M21, M31~M36, M40~M45, M47~M57, M59~M63, M68, M69, M72~M82, M95~M98, M100~M103, M108~M125, M128~M137, M139~M143, M149~M156. More preferred ones are M6~M8, M16~M20, M32~M36, M40, M41, M44, M49~M54, M59~M62, M68, M69, M75~M82, M100~M103, M108~M112, M114~M116 , M118~M121, M125, M134~M136, M139, M140, M143, M150, M152~M156.

<(D) Ingredients>

The polymer composition used in the present invention is used as the above-mentioned (A) and (B) components Other components may have the following (D) component.

That is, the component (D) is a compound having an alkoxysilyl group and a urea structure in which both the 1-position and the 3-position are substituted (hereinafter, also referred to as compound D).

Compound D has one or more alkoxysilyl groups in the compound and one or more urea structures in which both 1- and 3-positions are substituted. Other structures are not particularly limited, but from the viewpoint of availability, etc. The compound represented by the following formula (d) is one of preferable examples.

(In the formula, X ¹⁰² is an aliphatic hydrocarbon group with 1 to 20 carbons or an n-valent organic group containing an aromatic hydrocarbon group, n is an integer of 1 to 6, R ¹⁰² is a hydrogen atom or an alkyl group, and n is 2 or more when, R ¹⁰² with R ¹⁰² becomes the other alkylene, n is 1, or even 6, can also by bonding with X ^102, X ¹⁰² and together form a ring structure, L 2 carbon atoms or even 20 Alkylene, R ¹⁰³ and R ¹⁰⁴ are independent of each other, and are an alkyl group with 1 to 4 carbons, an alkenyl group with 2 to 4 carbons, or an alkynyl group with 2 to 4 carbons, and q is a natural number from 1 to 3. )

^{Regarding R 103} and R ¹⁰⁴ in formula (d), each independently includes, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and sec-butyl. From the viewpoint of availability or reactivity, methyl or ethyl is preferred.

Regarding L in the formula (d), for example, an alkylene group having 2 to 20 carbon atoms, but from the viewpoint of obtaining a raw material, a trimethylene group is preferred.

Regarding q in formula (d), 2 or 3 is preferred, and 3 is particularly preferred.

Regarding n in formula (d), 1, 2, or 3 is preferred, and 1 or 2 is particularly preferred.

One aspect of the compound of component (D) is a compound in which X ¹⁰² is a divalent organic group, R ¹⁰² is a hydrogen atom, and L is a trimethylene group.

The compound represented by the formula (2-1) is obtained by reacting diamine with 2.05 equivalents of trialkoxysilylpropyl isocyanate.

The X in the compound represented by the formula (2-1) is preferably a structure selected by the following structural formula.

One aspect of the compound of component (D) is a compound in which X ¹⁰² is a divalent organic group, R ¹⁰² forms an alkylene group together with each other, and L is a trimethylene group.

Such a compound represented by the formula (2-2) has a cyclic compound containing 2 NH and 2.05 equivalents of trialkoxysilylpropyl isocyanide The ester is obtained by reaction.

The X in the compound represented by the formula (2-2) is preferably a structure selected by the following structural formula. In addition, it is conveniently described as containing a nitrogen atom in the ring.

One aspect of the compound of component (D) is that X ¹⁰² is a divalent organic group, one of R ¹⁰² is a hydrogen atom, the other is also ^{bonded to X 102} to form a ring, and L is a trimethylene group Compound.

The compound represented by the formula (2-3) is obtained by reacting diamine with 2.05 equivalents of trialkoxysilylpropyl isocyanate.

The X in the compound represented by the formula (2-3) is preferably a structure selected by the following structural formula. In addition, it is conveniently described as containing a nitrogen atom in the ring.

One aspect of the compound of component (D) is a compound in which X ¹⁰² is a trivalent organic group, R ¹⁰² is a hydrogen atom, and L is a trimethylene group.

The compound represented by the formula (2-4) is obtained by reacting a triamine compound with 3.05 equivalents of trialkoxysilylpropyl isocyanate.

The X in the compound represented by the formula (2-4) is preferably a structure selected by the following structural formula.

One aspect of the compound of the component (D) is a compound in which X ¹⁰² is a monovalent organic group, R ¹⁰² is a hydrogen atom, and L is a trimethylene group.

The compound represented by the formula (2-5) is obtained by reacting a monoamine compound with 1.05 equivalent of trialkoxysilylpropyl isocyanate.

The X in the compound represented by the formula (2-5) is preferably a structure selected by the following structural formula.

One aspect of the compound of component (D) is a compound in which X ¹⁰² is a monovalent organic group, R ¹⁰² and X ^{102 are} bonded to form a ring, and L is a trimethylene group.

Such a compound represented by formula (2-6), by containing 1 The cyclic compound of NH is obtained by reacting with 1.05 equivalent of trialkoxysilylpropyl isocyanate.

The X in the compound represented by the formula (2-6) is preferably a structure selected by the following structural formula. In addition, it is conveniently described as containing a nitrogen atom in the ring.

In addition, in the reaction of the above-mentioned amine and isocyanate, the amount of the isocyanate compound used may be 0.98 equivalent times to 1.2 equivalent times _{with respect to NH or NH 2 group 1 group.} More preferably, it is 1.0 equivalent times to 1.05 equivalent times.

The reaction solvent is not particularly limited if it is inert to the reaction. For example, hydrocarbons such as hexane, cyclohexane, benzene, toluene, etc.; halogens such as carbon tetrachloride, chloroform, 1,2-dichloroethane, etc. Hydrocarbons; ethers such as diethyl ether, diisopropyl ether, 1,4-dioxane, tetrahydrofuran, etc.; acetone, methyl Ketones such as ethyl ketone and methyl isobutyl ketone; nitriles such as acetonitrile and propionitrile; carboxylic acid esters such as ethyl acetate and ethyl propionate; N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone and other nitrogen-containing aprotic polar solvents; dimethylsulfide , Cyclobutane and other sulfur-containing aprotic polar solvents; pyridine, picoline and other pyridines. These solvents can be used alone, or two or more of them can be mixed and used. Toluene, acetonitrile, ethyl acetate, tetrahydrofuran are preferred, and acetonitrile and tetrahydrofuran are more preferred.

Although the amount of solvent used (reaction concentration) is not particularly limited, the reaction can be carried out without using a solvent, and when a solvent is used, the solvent can be used in an amount of 0.1 to 100 times by mass relative to the isocyanate compound. It is preferably 0.5 to 30 times by mass, and even more preferably 1 to 10 times by mass.

Although the reaction temperature is not particularly limited, it is, for example, -90 to 150°C, preferably -30 to 100°C, and more preferably 0°C to 80°C.

The reaction time is usually 0.05 to 200 hours, preferably 0.5 to 100 hours.

In order to shorten the reaction time, a catalyst may be added. Examples thereof include dibutyltin dilaurate, dioctyltin bis(isooctylethanethiolate), and dibutyltin bis(isooctylethylsulfide). Alkyd), dibutyltin diacetate and other organotin compounds; triethylamine, trimethylamine, tripropylamine, tributylamine, diisopropylethylamine, N,N-di Methylcyclohexylamine, pyridine, tetramethylbutanediamine, N-methylmorpholine, 1,4-diazabicyclo-2.2.2-octane, 1,8-diazabicyclo[5.4. 0]Undecene, 1,5-diazabicyclo[4.3.0]nonene-5 and other amines; p-toluenesulfonic acid, methanesulfonic acid, fluorosulfur Organic sulfonic acids such as acids; inorganic acids such as sulfuric acid, phosphoric acid, and perchloric acid; titanium compounds such as tetrabutyl titanate, tetraethyl titanate, and tetraisopropyl titanate; bismuth ginseng (2- Ethylhexanoate) and other bismuth compounds; quaternary ammonium salts, etc. These catalysts can be used alone or in combination of two or more. In addition, these catalysts may be liquid, or they may be dissolved in the reaction solvent.

When adding a catalyst, relative to the total usage (mass) of compounds with isocyanate groups, the catalyst can be used in an amount of 0.005wt%~100wt%, preferably 0.05wt%~10wt%, more preferably 0.1wt% ~5wt%. As the catalyst, if an organotin compound, a titanium compound, or a bismuth compound is used, the same is preferably 0.005wt% to 0.1wt%.

This reaction can be carried out under normal pressure or under pressure, and can be batch or continuous.

Preferable examples of the component (D) include compounds represented by any one of S1 to S4.

Too much compound of component (D) affects the liquid crystal alignment or pretilt angle, and too little will result in the effect of the present invention. Therefore, the addition amount of the compound of component (D) is preferably 0.1-20% by mass, and more preferably 1-10% by mass relative to the polymer of component (A).

Furthermore, the polymer composition used in the present invention may be exemplified as components other than the above-mentioned (A) and (B) components, but is not limited to these.

Specific examples of the solvent (lean solvent) that improves the uniformity of the film thickness or the surface smoothness include the following.

For example, isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve Acetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol mono Butyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene two Alcohol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, two Propylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether , Ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methyl cyclohexene, propyl ether, dihexyl ether, 1-hexyl Alcohol, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, acetic acid Propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate Base ester, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid propyl ester, 3-methoxypropionic acid butyl ester, 1-methoxy-2-propane Alcohol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1 -Monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, methyl lactate, Solvents with low surface tension such as ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, etc.

These poor solvents can be mixed with one type or multiple types use. When using the above-mentioned general solvents, in order not to significantly reduce the solubility of the entire solvent contained in the polymer composition, 5 mass% to 80 mass% of the total solvent is preferred, and more preferably 20 mass% to 60 mass%.

Examples of compounds that improve the uniformity or surface smoothness of the film thickness include fluorine-based surfactants, silicone-based surfactants, and non-ionic surfactants.

More specifically, for example, EFTOP (registered trademark) 301, EF303, EF352 (manufactured by Tochem Products.), MEGAFAC (registered trademark) F171, F173, R-30 (manufactured by DIC Corporation), Fluorad FC430, FC431 (manufactured by Sumitomo 3M) ), Asahiguard (registered trademark) AG710 (manufactured by Asahi Glass Co., Ltd.), Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Seimi Chemical Co.), etc. The use ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass relative to 100 parts by mass of the resin component contained in the polymer composition.

As for specific examples of the compound that improves the adhesion between the liquid crystal alignment film and the substrate, the following functional silane-containing compounds can be exemplified.

For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-( 2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyl Trimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethyl Oxy Silane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane , 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilane Benzyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N- Phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis(oxyethylene)-3-aminopropyltrimethoxysilane, N-bis(oxyethylene)-3-aminopropyl triethoxysilane and the like.

Furthermore, in addition to the improvement of the adhesion between the substrate and the liquid crystal alignment film, for the purpose of preventing the reduction in electrical characteristics caused by the backlight when constituting the liquid crystal display element, the polymer composition may contain the following phenolic resin or containing Additive for epoxy-based compounds. Specific phenol resin additives are shown below, but are not limited to this structure.

Specific epoxy-containing compounds include, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and propylene glycol Diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether Base ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N',N' -Tetraglycidyl-m-xylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl -4, 4'-Diaminodiphenylmethane, etc.

When using a compound that improves the adhesion to the substrate, the amount used is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass relative to 100 parts by mass of the resin component contained in the polymer composition Mass parts. If the usage amount is less than 0.1 parts by mass, the effect of improving the adhesion cannot be expected, and if it is more than 30 parts by mass, the orientation of the liquid crystal may deteriorate.

Additives, photosensitizers can also be used. Colorless sensitizers and triplet sensitizers are preferred.

In terms of photosensitizers, there are aromatic nitro compounds, coumarins (7-diethylamino-4-methylcoumarin, 7-hydroxy4-methylcoumarin), coumarin ketones, Carbonyl biscoumarins, aromatic 2-hydroxy ketones, and aromatic 2-hydroxy ketones substituted with amino groups (2-hydroxybenzophenone, mono- or di-p-(dimethylamino)-2 -Hydroxybenzophenone), acetophenone, anthraquinone, xanthone, thioxanthone, benzoanthrone, thiazoline (2-benzyl methionine-3-methyl-β-naphthazoline , 2-(β-naphthylmethylene)-3-methylbenzothiazoline, 2-(α-naphthylmethylene)-3-methylbenzothiazoline, 2-(4- Bisphenol-methyl)-3-methylbenzothiazolin, 2-(β-naphthylmethyl)-3-methyl-β-naphthiazole Phytoline, 2-(4-bisphenol ethylene methyl)-3-methyl-β-naphthiazoline, 2-(p-fluorobenzyl ethylene methyl)-3-methyl-β-naphthiazole Morpholine), oxazoline (2-benzylene-3-methyl-β-naphthoxazoline, 2-(β-naphthylene)-3-methylbenzoxazole Morpholine, 2-(α-naphthylmethylidene)-3-methylbenzoxazoline, 2-(4-bisphenolidenemethyl)-3-methylbenzoxazoline, 2-( β-naphthomethylidene)-3-methyl-β-naphthoxazoline, 2-(4-bisphenolidene)-3-methyl-β-naphthoxazoline, 2- (p-fluorobenzamethylene)-3-methyl-β-naphthoxazoline), benzothiazole, nitroaniline (m- or p-nitroaniline, 2,4,6-tri Nitroaniline) or nitroacenaphthene (5-nitroacenaphthene), (2-[(m-hydroxy-p-methoxy)styryl]benzothiazole, benzoin alkyl ether, N-alkylated phthalate Ketones, acetophenone ketals (2,2-dimethoxyphenyl ethyl ketone), naphthalene, anthracene (2-naphthalene methanol, 2-naphthalene carboxylic acid, 9-anthracene methanol, and 9-anthracene carboxylic acid), Benzopyran, azoindoleazine, methyl coumarin, etc.

Preferably aromatic 2-hydroxy ketone (benzophenone), coumarin, coumarin ketone, carbonyl biscoumarin, acetophenone, anthraquinone, xanthone, thioxanthone, and acetophenone Ketal.

In the polymer composition, in addition to the above, a dielectric or conductive substance can be added for the purpose of changing the dielectric constant or electrical properties of the liquid crystal alignment film without impairing the scope of the present invention. For the purpose of increasing the hardness or density of the film when forming a liquid crystal alignment film, a crosslinking compound may be added.

<Liquid crystal alignment agent>

The present invention provides a polymer composition having the above, or essentially consisting of the above A liquid crystal alignment agent composed of the aforementioned polymer composition or composed only of the aforementioned polymer composition, especially a liquid crystal alignment agent for liquid crystal display devices, and more particularly a liquid crystal alignment agent for horizontal electric field drive type liquid crystal display devices.

<Liquid crystal alignment film> or <Substrate with liquid crystal alignment film>

The present invention provides a liquid crystal alignment film formed from the above-mentioned liquid crystal alignment agent, especially a liquid crystal alignment film for liquid crystal display elements, and more particularly a liquid crystal alignment film for horizontal electric field drive type liquid crystal display elements.

In addition, the present invention provides a substrate having a liquid crystal alignment film formed by the above-mentioned liquid crystal alignment agent, especially for liquid crystal display devices, and more particularly for horizontal electric field drive type liquid crystal display devices, especially for liquid crystal display devices. In particular, it is a substrate for horizontal electric field drive type liquid crystal display elements.

<Method for manufacturing liquid crystal alignment film> or <Method for manufacturing substrate with liquid crystal alignment film>

The above-mentioned liquid crystal alignment film is a step of coating the above-mentioned polymer composition or the above-mentioned liquid crystal alignment agent on a substrate, such as a substrate with a conductive film for driving a horizontal electric field, by having [I]; [II] ] The step of irradiating the coating film obtained in [I] with polarized ultraviolet rays; and [III] the step of heating the coating film obtained in [II]; it is possible to obtain a liquid crystal alignment film imparted with alignment control ability, especially for liquid crystal display elements , More particularly, it is a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display element or a substrate with the liquid crystal alignment film.

<<Substrate>>

Although the substrate is not particularly limited, when the liquid crystal display element to be manufactured is a transmissive type, it is preferable to use a highly transparent substrate. At this time, although not particularly limited, a glass substrate, or a plastic substrate such as an acrylic substrate or a polycarbonate substrate can be used.

In addition, considering that it is suitable for reflective liquid crystal display elements, opaque substrates such as silicon wafers can also be used.

<<Conductive film for horizontal electric field drive>>

When the substrate is used in a horizontal electric field drive type liquid crystal display element, it has a conductive film for horizontal electric field drive.

As the conductive film, when the liquid crystal display element is a transmissive type, for example, ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide: indium zinc oxide), etc. may be mentioned, but it is not limited to these.

In addition, in the case of a reflective liquid crystal display element, as the conductive film, for example, a light-reflecting material such as aluminum can be mentioned, but it is not limited to these.

The method of forming a conductive film on the substrate can use a conventionally known method.

<<Step [I]>>

In step [I], the polymer composition of the present invention exhibiting liquid crystallinity in a specified temperature range is coated on a substrate having a conductive film for driving a horizontal electric field to form a coating film.

Coating the above polymer composition or the above liquid crystal alignment agent The method on a substrate having a conductive film for driving a horizontal electric field is not particularly limited.

The coating method is generally carried out by screen printing, offset printing, flexographic printing, or inkjet method in the industry. In terms of other coating methods, there are dipping, roll coating, slit coating, spin coating (spin coating), or spraying methods. These can also be used depending on the purpose.

After coating a polymer composition or liquid crystal alignment agent on a substrate with a conductive film for driving a horizontal electric field, it can be heated by heating means such as a heating plate, a thermal cycle oven or an IR (infrared) oven. The solvent is evaporated at 200°C, preferably 50 to 150°C, to obtain a coating film. The drying temperature at this time is preferably lower than the liquid crystal phase expression temperature of the polymer of the component (A) of the present invention. In addition, the expression temperature of the liquid crystal phase of the polymer of the (A) component here means the temperature at which the polymer of at least two types of the (A) component as a whole expresses the liquid crystal phase.

If the thickness of the coating film is too thick, it is disadvantageous on the power consumption side of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may decrease. Therefore, it is preferably 5 nm to 300 nm, more preferably 10 nm to 150 nm.

In addition, after the step [I], a step of cooling the substrate on which the coating film is formed to room temperature may be provided before the next step [II].

<<Step [II]>>

In step [II], the coating film obtained in step [I] is irradiated with polarized ultraviolet rays. When the film surface of the coating film is irradiated with polarized ultraviolet rays, the substrate is irradiated with ultraviolet rays that pass through the polarizing plate in a certain direction. In terms of ultraviolet light used, Use ultraviolet light in the range of 100nm~400nm. It is preferable to select the most appropriate wavelength according to the type of coating film used, and the transmission filter or the like. However, for example, ultraviolet rays with a wavelength in the range of 290 nm to 400 nm can be selected to selectively initiate the photo-crosslinking reaction. Regarding ultraviolet rays, for example, light emitted from a high-pressure mercury lamp can be used.

The amount of polarized ultraviolet radiation depends on the coating film used. The irradiation amount is 1 of the amount of polarized ultraviolet light that can achieve the difference between the ultraviolet absorbance in the direction parallel to the polarization direction of the polarized ultraviolet light and the ultraviolet absorbance in the vertical direction in the coating film △A maximum (hereinafter, also referred to as △Amax) The range of %~70% is better, and the range of 1%~50% is better.

<<Step [III]>>

In step [III], the coating film irradiated with polarized ultraviolet rays in step [II] is heated. By heating, the alignment control ability can be imparted to the coating film.

For heating, heating means such as a hot plate, thermal cycle oven or IR (infrared) oven can be used. The heating temperature can be determined by considering the temperature that expresses the liquid crystallinity of the coating film used.

The heating temperature is preferably within the temperature range at which the polymer of the component (A) of the present invention exhibits liquid crystallinity (hereinafter referred to as liquid crystallinity expression temperature). When it is a thin film surface like a coating film, the liquid crystal display temperature of the coating film surface is predicted to be lower than the liquid crystal display temperature of the polymer of the component (A) of the present invention when it is observed in bulk. Therefore, the heating temperature is preferably within the temperature range where the liquid crystallinity of the coating film surface is expressed. That is, the temperature range of the heating temperature after polarized ultraviolet radiation is higher than the liquid crystallinity expression temperature of the chain polymer used. The lower limit of the temperature range is 10°C lower as the lower limit, and the temperature lower than the upper limit of the liquid crystal temperature range is 10°C lower than the upper limit. If the heating temperature is lower than the above temperature range, the amplifying effect of the heat-induced anisotropy in the coating film tends to become insufficient, and if the heating temperature is too high than the above temperature range, the state of the coating film may become close to The tendency of isotropic liquid state (isotropic phase), at this time, it may become difficult to realign in one direction from self-organization.

In addition, the liquid crystal expression temperature refers to the glass transition temperature (Tg) or higher at which the polymer or coating film surface of the component (A) of the present invention undergoes phase transition from a solid phase to a liquid crystal phase, and is a phase transition from liquid crystal phase to The temperature below the isotropic phase transition temperature (Tiso) of the isotropic phase (isotropic phase).

The thickness of the coating film formed after heating is preferably 5 nm to 300 nm, more preferably 50 nm to 150 nm for the same reason as described in step [I].

By having the above steps, in the manufacturing method of the present invention, an anisotropy can be introduced into the coating film with high efficiency. However, the substrate with the liquid crystal alignment film can be manufactured efficiently.

<Liquid crystal display element> and <Method of manufacturing liquid crystal display element>

The present invention provides a liquid crystal display element having a substrate with a liquid crystal alignment film obtained as described above, particularly a horizontal electric field drive type liquid crystal display element.

Specifically, in addition to the substrate (first substrate) having a liquid crystal alignment film obtained above, by preparing a second substrate, a horizontal electric field drive type liquid crystal display element can be obtained.

The second substrate is replacing the substrate with a conductive film for driving a horizontal electric field. When a substrate without a conductive film for horizontal electric field driving is used, a substrate with a conductive film for horizontal electric field driving may be used in the same manner as the first substrate. In addition, the second substrate is preferably one having a liquid crystal alignment film similarly to the first substrate.

The method for manufacturing liquid crystal display elements, especially horizontal electric field drive type liquid crystal display elements, has [IV] the first and second substrates obtained above through the liquid crystal and the liquid crystal alignment films of the first and second substrates are opposed to each other. The step of arranging to obtain a liquid crystal display element. By this, a liquid crystal display element, especially a horizontal electric field drive type liquid crystal display element can be obtained.

<Step [IV]>

[IV] The step is to make the substrate (first substrate) with a liquid crystal alignment film on the conductive film for horizontal electric field driving obtained in [III], and the same as the above-mentioned [I']~[III'] with liquid crystal The substrate (second substrate) of the alignment film transmits the liquid crystal, and after the two liquid crystal alignment films are opposed to each other, the liquid crystal cell is fabricated by a known method to fabricate a horizontal electric field drive type liquid crystal display element. In addition, steps [I'] to [III'] can be performed in the same manner as steps [I] to [III], except for the difference in the presence or absence of the conductive film for horizontal electric field driving in step [I]. Because the difference between steps [I]~[III] and steps [I’]~[III’] is only the presence or absence of the above-mentioned conductive film, the description of steps [I’]~[III’] is omitted.

Examples of the production of a liquid crystal cell or a liquid crystal display element include, for example, the preparation of the above-mentioned first and second substrates, and the liquid crystal arrangement on one of the substrates Spread spacers on the film, and attach another piece of substrate with the liquid crystal alignment film surface as the inner side, and inject the liquid crystal under reduced pressure and then seal it, or drop the liquid crystal on the liquid crystal alignment film surface with the spacers Then, the method of sealing after bonding the substrate. At this time, when manufacturing a horizontal electric field drive type liquid crystal display element, it is preferable to use a substrate having a comb-like structure electrode for horizontal electric field drive on one side of the substrate.

The diameter of the spacer is preferably 1 μm to 30 μm, more preferably 2 μm to 10 μm. The diameter of the spacer determines the distance between a pair of substrates that hold the liquid crystal layer, that is, the thickness of the liquid crystal layer.

As mentioned above, the polymer composition or the liquid crystal alignment agent of the present invention, the liquid crystal alignment film formed using the composition or the liquid crystal alignment agent or the substrate having the alignment film, and the liquid crystal display formed by the liquid crystal alignment film or the substrate The device, especially the horizontal electric field drive type liquid crystal display device, has excellent reliability and is suitable for use in large-screen and high-definition liquid crystal televisions.

[Example]

The monomer M1 having a photoreactive group, the monomer M2 having a liquid crystal group, the monomer HBAGE having a crosslinking group, and the monomer A1 having an amido group used in the examples are as shown below.

Each of M1 and M2 is synthesized as follows. That is, M1 is synthesized by the synthesis method described in the patent document (WO2011-084546). M2 was synthesized in accordance with the synthesis method described in the patent document (Japanese Patent Application Laid-Open No. 9-118717). In addition, the polymer formed with M1 as a monomer has photoreactivity and liquid crystallinity, and M2 The polymer formed as a monomer has only liquid crystallinity.

The copolymerized monomer A1 was synthesized by the synthesis method described in Synthesis Example 1 below.

HBAGE (hydroxybutyl acrylate glycidyl ether) is commercially available.

In addition, the abbreviations of reagents used in this example are as follows.

(Organic solvents)

THF: Tetrahydrofuran.

NMP: N-ethyl-2-pyrrolidone.

EDC: N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide (condensing agent).

DMAP: 4-dimethylaminopyridine.

PB: Propylene glycol monobutyl ether.

(Polymerization initiator)

AIBN: 2,2'-azobisisobutyronitrile.

<Synthesis Example 1>

Synthesis of compound A1

In a 1L four-necked flask, add compound [A] (63.42g, 287mmol), compound [B] (50.00g, 406mmol), EDC (93.43g, 487mmol), DMAP (4.96g, 40.6mmol), THF (500g) , The reaction was carried out at 23°C. Reaction tracking was performed by HPLC, and after confirming that the reaction was completed, the reaction solution was poured into distilled water (3 L), ethyl acetate (1 L) was added, and the aqueous layer was removed by a liquid separation operation. After that, the organic layer was washed twice with distilled water (1 L), and then the organic layer was dried with magnesium sulfate. After that, the solvent was distilled off by filtration and an evaporator to obtain 86.3 g of the oily compound [A1] (yield 92%).

¹ H-NMR (400MHz, CDCl3, δppm): 8.81-8.79 (2H, dd), 7.86-7.85 (2H, dd), 6.16-6.14 (1H, m), 5.62-5.60 (1H, m), 4.63 4.61 (2H, m), 5.62-5.60 (2H, m), 4.63-4.61 (2H, m), 4.52-4.60 (2H, m), 1.97-1.95 (3H, m).

<Polymer Synthesis Example P1>

M1 (1.66 g: 0.1 mol%) and M2 (13.79 g: 0.9 mol%) were dissolved in THF (146.42 g), and after degassing with a diaphragm pump, AIBN (0.82 g) was added, followed by degassing. After that, the reaction was carried out at 60°C for 8 hours to obtain a polymer solution of methacrylate. The polymer solution was dropped into methanol (300 ml), and the obtained precipitate was filtered. This deposit was washed with methanol and dried under reduced pressure to obtain methacrylate polymer powder P1.

<Polymer synthesis examples P2~P4>

Except for using the composition shown in Table 1, the same method as in Polymer Synthesis Example P1 was used to synthesize methacrylate polymer powders P2 to P4.

<Example 1>

To NMP (5.65g), add the methacrylate polymer powder P1 (0.105g) obtained in polymer synthesis example P1, and the methacrylate polymer powder P2 (0.245g) obtained in polymer synthesis example P2, in Stir for 1 hour at room temperature to dissolve. With this solution, PB (4.0 g) was added and stirred to obtain a polymer solution T1. The polymer solution T1 is directly used as a liquid crystal alignment agent for forming a liquid crystal alignment film.

<Control Group 1>

To NMP (5.65g), the methacrylate polymer powder P2 (0.35g) obtained in Polymer Synthesis Example P2 was added, and the mixture was stirred at room temperature for 1 hour to dissolve. With this solution, PB (4.0 g) was added and stirred to obtain a control group polymer solution CT1. The polymer solution is directly used as a liquid crystal alignment agent for forming a liquid crystal alignment film.

<Control Group 2>

To NMP (5.65g), the methacrylate polymer powder P3 (0.35g) obtained in Polymer Synthesis Example P3 was added, and the mixture was stirred at room temperature for 1 hour to dissolve. With this solution, PB (4.0 g) was added and stirred to obtain a control group polymer solution CT2. The polymer solution is directly used as a liquid crystal alignment agent for forming a liquid crystal alignment film.

<Control Group 3>

To NMP (5.65g), the methacrylate polymer powder P4 (0.35g) obtained in Polymer Synthesis Example P4 was added, and the mixture was stirred at room temperature for 1 hour to dissolve. With this solution, PB (4.0 g) was added and stirred to obtain a control group polymer solution CT3. The polymer solution is directly used as a liquid crystal alignment agent for forming a liquid crystal alignment film.

Regarding the liquid crystal alignment agent T1 of Example 1 and the liquid crystal alignment agents CT1~CT3 of the control groups 1 to 3, the polymer species used and its wt%, and Example 1 uses two types of polymers, and the light in each polymer reacts The amount of reactive groups, the monomer species from which the "photoreactive group" and the "liquid crystal group" in each polymer come from, the "amount of photoreactive group" in the monomer, and the liquid crystal alignment derived from them The "all photoreactive base amount" in the agent is summarized in Table 2 below.

In addition, the "amount of photoreactive groups in each polymer" and "amount of all photoreactive groups" in Table 2 can be obtained, for example, as follows.

That is, in the liquid crystal alignment agent T1 of Example 1, the polymerization In the total weight of the species P1 and P2, 30wt% of P1 and 70wt% of P2 are used. The monomer derived from the "photoreactive group" in the polymer species P1, as described above, is M1. M2 only has a "liquid crystal base". "The amount of photoreactive groups in each polymer" is the mol% value of the "photoreactive groups" when the total of "liquid crystal groups" and "photoreactive groups" is 100 mol%, so the "photoreactive group" of polymer species P1 The amount of reactive groups" is 100×{0.1/(0.1+0.9)}, which is 10 mol%. Also, similarly, the "photoreactive group amount" in the polymer species P2 is 20 mol%.

"Total photoreactive group amount" is calculated from the weight ratio of polymer species P1 and P2 and the "photoreactive group amount" in the above-mentioned polymer species P1 and P2, and is calculated by 0.1mol%×0.3 (derived from P1 species is 30wt %)+0.2mol%×0.7 (70wt% derived from P2 species), to obtain 0.17mol%.

<Production of Liquid Crystal Cell>

After filtering the liquid crystal alignment agent (T1) obtained in Example 1 with a 0.45 μm filter, spin coating was performed on a glass substrate with a transparent electrode and dried on a hot plate at 70°C for 90 seconds. A liquid crystal alignment film with a film thickness of 100 nm was formed. Then, the coating film surface was passed through a polarizing plate, irradiated with 10~80mJ/cm ² of 313nm ultraviolet rays, and heated on a heating plate at 140°C for 10 minutes to obtain a substrate with a liquid crystal alignment film. Prepare two such substrates with liquid crystal alignment film. After placing a 6μm spacer on the liquid crystal alignment film surface of one of the substrates, combine the two substrates so that the rubbing directions of the two substrates are parallel, leaving the liquid crystal injection port and surrounding Sealing to produce an empty cell with a cell gap of 4 μm. The liquid crystal MLC-3019 (manufactured by Merck & Co., Ltd.) was injected into the empty cell by a reduced-pressure injection method, and the injection port was sealed to obtain a liquid crystal cell in which the liquid crystal was aligned in parallel.

Similarly, the liquid crystal alignment agents CT1, CT2, and CT3 obtained in the control groups 1 to 3 were used to fabricate liquid crystal cells.

<Alignment Evaluation>

The liquid crystal cells produced in Example 1, Control Groups 1 to 3 were placed between the two polarizing plates arranged perpendicular to the polarization axis, and the backlight was lighted in advance in a state of no applied voltage, and the liquid crystal crystal was adjusted to minimize the brightness of the transmitted light. The configuration angle of the cell. The liquid crystal cell is visually confirmed. If the liquid crystal cell is well aligned and no flow alignment is confirmed, it is "○", although the alignment is confirmed, it is "△", and if there is no flow alignment, it is "×".

<Voltage Holding Rate (VHR) Evaluation>

Using the above-produced liquid crystal cell, a voltage of 5V was applied at a temperature of 70°C for 60 μs, the voltage after 16.67 ms was measured, and the voltage holding rate (VHR) was calculated as the voltage holding rate (VHR). In addition, for the measurement of the voltage holding ratio, a voltage holding ratio measuring device VHR-1 manufactured by TOYO Corporation was used.

The VHR results of Example 1 and the control groups 1 to 3 are recorded in Table 3 together with the results of <Orientation Evaluation> and the "All-photoreactive base amount".

From Table 3, it can be seen that in Example 1, by using two types of polymers with different amounts of photoreactive groups, and using a relatively large amount of photoreactive groups, a polymer having an epoxy group (derived from HBAGE) polymer, and in a wide range of UV irradiation, showing good alignment and good VHR.

Specifically, comparing Example 1 with the control group 1, the amount of all photoreactive groups of the two is almost the same (Example 1: 0.17; control group 1: 0.20) and in the two, the epoxy group (derived from HBAGE ) And a polymer containing a nitrogen-containing aromatic heterocyclic group, and thus the VHR shows almost the same value. However, of the two, in Example 1, two types (P1 and P2) were used as the polymer species, and on the other hand, in the control group 1, only one type (P2) was used as the polymer species. From this difference, In Example 1, UV irradiation dose of 50mJ / cm ² and 80mJ / cm ² was confirmed that excellent alignment property, and in the control group 1, UV irradiation dose of 50mJ / cm ² and 80mJ / cm ² for the non-oriented Compared with the control group 1, Example 1 shows good alignment in a wide range of UV irradiation and the VHR also becomes the expected value.

Comparing Example 1 and Control Group 2, the total photoreactivity of the two groups is almost the same (Example 1: 0.17; Control Group 2: 0.20), so that both show good results in a wide range of UV exposure. Orientation. However, of the two, in Example 1, two types (P1 and P2) were used as the polymer species, and among the two types of polymers, one having an epoxy group (derived from HBAGE) and a nitrogen-containing aromatic heterocyclic group was used Polymer, and control group 2, as the polymer species, only one species (P3) was used. Because of this difference, in Example 1, the VHR showed the expected value, while in the control group 2, the VHR was lower than the expected value, and compared with the control group 2, Example 1 showed good alignment in a wide range of UV irradiation. VHR has also become the expected value.

Comparing Example 1 and Control Group 3, the amount of all-photoreactive groups is the same (Example 1: 0.17; Control Group 3: 0.17), but as the polymer species, two types (P1 and P2) are used and these two types Among the polymers, polymers with epoxy groups (derived from HBAGE) and nitrogen-containing aromatic heterocyclic groups are used, while in control group 3, as the polymer species, only one (P4) is used, and the P4 does not have Epoxy groups (derived from HBAGE) and nitrogen-containing aromatic heterocyclic groups are different in this regard. It can be seen from this difference that in Example 1, in a wide range of UV exposure, good alignment is shown and VHR is also the expected value, while in control group 3, The VHR is lower than the expected value, and the UV radiation dose cannot achieve the desired characteristics regardless of the radiation dose.

Claims (29)

A polymer composition containing at least two (A) polymers having a structure exhibiting photoreactivity and a structure exhibiting liquid crystallinity; and (B) an organic solvent; characterized by the aforementioned at least two polymers Among them, one type of polymer has a crosslinkable group, and among the aforementioned at least two types of polymers, one polymer (A1) and the other polymer (A2) have different amounts of structure exhibiting photoreactivity. The amount of the structure exhibiting photoreactivity of the aforementioned polymer (A1) is greater than the amount of the structure exhibiting photoreactivity of the aforementioned polymer (A2), and the aforementioned crosslinkable group is represented by the following formula (G-1), (G-2), (G-3) and (G-4) (In the formula, the dashed line represents the bonding bond, and R ⁵⁰ is selected by hydrogen atom, halogen atom, alkyl group with 1 to 3 carbons, and phenyl group When R ⁵⁰ is a plural number, they can be the same or different from each other, t is an integer from 1 to 7, J is O, S, NH or NR ⁵¹ , and R ⁵¹ is an alkyl group with 1 to 3 carbons and a phenyl group. Selected base) at least one base selected from the group,

The aforementioned polymer (A1) has the aforementioned crosslinkable group, and the aforementioned structure exhibiting photoreactivity is represented by the following formula (9)

(In the formula, A, B, and D are independent of each other and are single bonds, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO- O-, or -O-CO-CH=CH-; Y _{1 is a} ring selected from monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon with carbon number 5~8 , Or the same or different 2~6 rings selected by their substituents are bonded through the bonding group B, bonded to their hydrogen atoms, each independently can be -COOR ₀ (formula Where R ₀ is a hydrogen atom or an alkyl group with 1 to 5 carbons), -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen group, and carbon 1 to 5 Alkyl group, or C1-C5 alkyloxy group; X is a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH =CH-CO-O-, or -O-CO-CH=CH-, when the number of X is 2, X can be the same or different from each other; l is an integer from 1 to 12; m is an integer from 0 to 2 , M1 and m2 are integers from 1 to 3; n is an integer from 0 to 12 (but when n=0, B is a single bond); Y _{2 is} composed of divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, The pyrrole ring, the alicyclic hydrocarbon with 5 to 8 carbon atoms, and the group selected from the combination of them are bonded to their hydrogen atoms. They are independent of each other and can be controlled by -NO ₂ , -CN,- CH=C(CN) ₂ , -CH=CH-CN, halogen group, alkyl group with 1 to 5 carbons, or alkyloxy group with 1 to 5 carbons; R is a hydroxyl group) In any of the selected structures, the weight average molecular weight of the aforementioned polymer (A1) is β (β is 30,000 or more), and the weight average molecular weight of the aforementioned polymer (A2) is 0.1β to 0.9β. The composition according to claim 1, wherein the polymer (A1) further has at least one group selected from the group consisting of a nitrogen-containing aromatic heterocyclic group, an amide group, and a urethane group. The composition of claim 1 or 2, wherein the polymer (A2) further has at least one group selected from the group consisting of a nitrogen-containing aromatic heterocyclic group, an amide group, and a urethane group. The composition according to claim 1 or 2, wherein the aforementioned at least two types of polymers each have a structure expressing photoreactivity and liquid crystallinity, and a structure expressing only liquid crystallinity. Such as the composition of claim 1 or 2, wherein the aforementioned structure exhibiting photoreactivity is composed of the following formulas (1) to (6) (wherein, A, B, and D are independent of each other and are single bonds, -O- , -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O-, or -O-CO-CH=CH-; S is carbon number 1 ~12 alkylene groups, the hydrogen atoms bonded to them can be substituted by halogen groups; T is a single bond or C1-C12 alkylene groups, and the hydrogen atoms bonded to them can be substituted by halogen groups; Y _{1 is a} ring selected from monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon with carbon number of 5-8, or the same or different ones selected by their substituents The 2~6 rings are formed by bonding through the bonding group B, which are bonded to their hydrogen atoms, each independently can be -COOR ₀ (where R ₀ is a hydrogen atom or a carbon number of 1~5 Alkyl), -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen group, alkyl group with 1 to 5 carbons, or alkyloxy group with 1 to 5 carbons Substituted; Y ₂ is a group selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon with 5 to 8 carbon atoms, and a combination of them, The hydrogen atoms bonded to them, independently of each other, can be -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen group, C1-C5 alkyl group, or Substituted by an alkyloxy group with a carbon number of 1 to 5; R is a hydroxyl group, an alkoxy group with a carbon number of 1 to 6, or the _{same definition as Y 1} ; X is a single bond, -COO-, -OCO-, -N= N-, -CH=CH-, -C≡C-, -CH=CH-CO-O-, or -O-CO-CH=CH-, when the number of X is 2, X can be the same or the same as each other Iso; Cou is coumarin-6-yl or coumarin-7-yl, bonded to their hydrogen atoms, each independently, can be -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen group, alkyl group with 1 to 5 carbons, or alkyloxy group with 1 to 5 carbons; q1 and q2, one is 1 and the other is 0; q3 is 0 or 1; P and Q, each independently, are a group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, alicyclic hydrocarbons with 5 to 8 carbon atoms, and a combination of them The group selected from the group; however, when X is -CH=CH-CO-O-, -O-CO-CH=CH-, P or Q on the bonding side of -CH=CH- is an aromatic ring, the number of P When it is 2 or more, P can be the same or different from each other, and when the number of Q is 2 or more, Q can be the same or different from each other; l1 is 0 or 1; l2 is an integer from 0 to 2; l1 and 12 are both When 0, when T is a single bond, A is also a single bond; when l1 is 1, when T is a single bond, B is also a single bond; H and I are independent of each other and are composed of a divalent benzene ring, a naphthalene ring, and a bivalent benzene ring. Any one structure selected from the group consisting of benzene ring, furan ring, pyrrole ring, and groups selected by their combination),

Such as the composition of claim 1 or 2, wherein the aforementioned structure exhibiting photoreactivity is composed of the following formulas (11) to (13) (where A, each independently, is a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O-, or -O-CO-CH=CH-; X is a single bond, -COO- , -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O-, or -O-CO-CH=CH-, when the number of X is 2 , X can be the same or different from each other; l is an integer from 1 to 12, m is an integer from 0 to 2, m1 is an integer from 1 to 3; R is composed of monovalent benzene ring, naphthalene ring, biphenyl ring, furan Rings, pyrrole rings and alicyclic hydrocarbons with 5 to 8 carbon atoms, or the same or different 2-6 rings selected by their substituents, which are bonded through the bonding group B. , The hydrogen atoms bonded to them, each independently can be -COOR ₀ (where R ₀ is a hydrogen atom or an alkyl group with 1 to 5 carbon atoms), -NO ₂ , -CN, -CH=C(CN ) ₂ , -CH=CH-CN, halogen group, C1-C5 alkyl group, or C1-C5 alkyloxy group substituted, or hydroxy group or C1-C6 alkoxy group) Any one structure selected from the group,

The composition of claim 1 or 2, wherein the aforementioned structure exhibiting photoreactivity is the following formula (14) or (15) (where A is independent of each other and is a single bond, -O-, -CH _2- , -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O-, or -O-CO-CH=CH-; Y _{1 is} composed of monovalent benzene ring, naphthalene Ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon ring with 5-8 carbon atoms, or the same or different 2-6 rings selected by their substituents through bonding groups The group formed by the bonding of B is bonded to their hydrogen atoms, each independently can be -COOR ₀ (where R ₀ is a hydrogen atom or an alkyl group with 1 to 5 carbon atoms), -NO ₂ , -CN , -CH=C(CN) ₂ , -CH=CH-CN, halogen group, C1-C5 alkyl group, or C1-C5 alkyloxy group substituted; l is an integer of 1-12 , M1 and m2 are integers from 1 to 3),

The composition of claim 1 or 2, wherein the aforementioned structure exhibiting photoreactivity is the following formula (16) or (17) (where A is a single bond, -O-, -CH ₂ -, -COO -, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O-, or -O-CO-CH=CH-; X is a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O-, or -O-CO-CH=CH-, when the number of X is 2, X can be each other Same or different; l is an integer from 1 to 12, m is an integer from 0 to 2),

Such as the composition of claim 1 or 2, wherein the aforementioned structure exhibiting photoreactivity is the following formula (18) or (19) (where A and B are independent of each other and are a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O-, or -O-CO-CH=CH-; Y _{1 is} composed of monovalent benzene ring , Naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon with 5-8 carbon atoms, or the same or different 2-6 rings selected by their substituents through bond The group formed by the bonding group B is bonded to their hydrogen atoms, each independently can be -COOR ₀ (where R ₀ is a hydrogen atom or an alkyl group with 1 to 5 carbon atoms), -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen group, alkyl group with 1 to 5 carbons, or alkyloxy group with 1 to 5 carbons; q1 and q2, one One is 1 and the other is 0; 1 is an integer from 1 to 12, m1 and m2 are an integer from 1 to 3; R ₁ is a hydrogen atom, -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, an alkyl group with 1 to 5 carbons, or an alkyloxy group with 1 to 5 carbons), any structure selected from the group,

The composition of claim 1 or 2, wherein the aforementioned structure exhibiting photoreactivity is the following formula (20) (where A is a single bond, -O-, -CH ₂ -, -COO-, -OCO -, -CONH-, -NH-CO-, -CH=CH-CO-O-, or -O-CO-CH=CH-; Y _{1 is} composed of monovalent benzene ring, naphthalene ring, biphenyl ring, furan Rings, pyrrole rings and alicyclic hydrocarbons with 5 to 8 carbon atoms, or the same or different 2-6 rings selected by their substituents, which are bonded through the bonding group B. , The hydrogen atoms bonded to them, each independently can be -COOR ₀ (where R ₀ is a hydrogen atom or an alkyl group with 1 to 5 carbon atoms), -NO ₂ , -CN, -CH=C(CN ) ₂ , -CH=CH-CN, halogen group, C1-C5 alkyl group, or C1-C5 alkyloxy group substituted; X is a single bond, -COO-, -OCO-,- N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O-, or -O-CO-CH=CH-, when the number of X is 2, X can be the same Or different; l is an integer from 1 to 12, m is an integer from 0 to 2),

Such as the composition of claim 1 or 2, wherein the aforementioned structure that only exhibits liquid crystallinity is the following formula (21) to (31) (where A and B are the same as defined above; Y _{3 is} composed of a monovalent benzene ring , Naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocyclic ring, and alicyclic hydrocarbon with 5 to 8 carbon atoms, and groups selected from the group consisting of, naphthalene ring, biphenyl ring, furan ring, bonded to their hydrogen atom , Each independently, may be substituted by -NO ₂ , -CN, halogen group, alkyl group with 1 to 5 carbons, or alkyloxy group with 1 to 5 carbons; R ₃ is a hydrogen atom, -NO ₂ ,- CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen group, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocyclic ring, alicyclic type with carbon number 5-8 Hydrocarbon, C1-C12 alkyl group, or C1-C12 alkoxy group; q1 and q2, one is 1 and the other is 0; l is an integer from 1 to 12, and m is 0 to 2 However, in formulas (23) to (24), the total of all m is 2 or more, and in formulas (25) to (26), the total of all m is 1 or greater, m1, m2, and m3 are independent of each other. It is an integer of 1 to 3; R ₂ is a hydrogen atom, -NO ₂ , -CN, halogen group, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocyclic ring, and carbon number 5-8 Alicyclic hydrocarbon, and, alkyl, or alkyloxy; Z ₁ and Z ₂ are single bonds, -CO-, -CH ₂ O-, -CH=N-, -CF ₂ -) Any one of the selected structures,

The composition of claim 1 or 2, wherein the amount of the structure exhibiting photoreactivity of the aforementioned polymer (A1) is the sum of the structure exhibiting photoreactivity of the aforementioned polymer (A1) and the structure exhibiting liquid crystallinity 100 mol %, it is α mol% (α is 15 or more), the amount of the photoreactive structure of the aforementioned polymer (A2), when the aforementioned polymer (A2) has the photoreactive structure and the amount of liquid crystal When the structure is 100 mol%, it is 0.95α mol% or less. For the composition of claim 1 or 2, wherein the total weight of the aforementioned polymer (A1) and the aforementioned polymer (A2) is 100% by weight, the aforementioned polymer (A1) is 20 to 95% by weight. The composition of claim 1 or 2, wherein the aforementioned at least two kinds of polymers are monomers (M1) having (M-1) having a structure exhibiting photoreactivity and liquid crystallinity; and (M-2) having Only a monomer (M2) with a liquid crystal structure; formed. Such as the composition of claim 14, wherein the aforementioned monomer (M1) has the structure represented by any one of the aforementioned formulas (1) to (20), and the aforementioned monomer (M2) has the aforementioned formula (21) to ( 31) The structure indicated. Such as the composition of claim 1 or 2, wherein the aforementioned monomer (M1) is the following formula: MA1, MA3, MA4, MA5, MA14, MA16~MA23, MA25, MA28~MA30, MA32, MA34, MA36, MA38~ At least one selected from the group consisting of MA42, MA44 and MA46, the aforementioned monomer (M2) is represented by the following formulas MA2, MA9~MA13, MA15, MA24, MA26, MA27, MA31, MA35, MA37, MA43 and MA45 At least one selected from the group,

The composition of claim 1 or 2, wherein the aforementioned polymer (A1) has (M-1) a monomer (M1) having a structure that exhibits photoreactivity and liquid crystallinity; (M-2) has only Liquid crystal structure monomer (M2); and (M-3) have the formula (G-1), (G-2), (G-3) and (G-4) (where the dotted line represents the bond Bonding, R ⁵⁰ is a group selected from a hydrogen atom, a halogen atom, an alkyl group with 1 to 3 carbons, and a phenyl group. When R ⁵⁰ is a plural number, they may be the same or different from each other, and t is an integer from 1 to 7. J is O, S, NH or NR ⁵¹ , R ⁵¹ is a group selected from an alkyl group with 1 to 3 carbons and a phenyl group) at least one monomer (M3) selected from the group; ,

The composition of claim 16, wherein the aforementioned (M-3) monomer (M3) has the following formula (0) (in formula (0), A and B are each independent, and are a single bond, -O-,- CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O-, or -O-CO-CH=CH-; S is carbon number 1~12 The hydrogen atoms bonded to them may be substituted by halogen groups; T is a single bond or an alkylene group with 1 to 12 carbon atoms, and the hydrogen atoms bonded to them may be substituted by halogen groups; X is Single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O-, or -O-CO-CH=CH-, When the number of X is 2, X can be the same or different from each other; P and Q, each independently, are composed of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and an aliphatic carbon number of 5-8 Cyclic hydrocarbon, and, the group selected from the group formed by their combination; but, when X is -CH=CH-CO-O-, -O-CO-CH=CH-, -CH=CH- is bonded P or Q on the side is an aromatic ring; l1 is 0 or 1; l2 is an integer from 0 to 2; when both l1 and 12 are 0, when T is a single bond, A is also a single bond; when l1 is 1, T is In the case of a single bond, B is also a single bond; G is the following formula (G-1), (G-2), (G-3) and (G-4) (where the dashed line indicates the bonding bond, R ⁵⁰ A group selected from hydrogen atom, halogen atom, C1-C3 alkyl group, and phenyl group. When R ⁵⁰ is a plural number, they may be the same or different from each other, t is an integer from 1 to 7, J is O, S , NH or NR ⁵¹ , R ⁵¹ is the structure represented by the group selected by the alkyl group with 1 to 3 carbons and the phenyl group),

The composition according to claim 17, wherein the aforementioned polymer (A1) further has (M-4) a nitrogen-containing aromatic heterocyclic group, an amino group and a urethane At least one monomer (M4) selected from the group formed by the base; and formed. Such as the composition of claim 1 or 2, wherein the aforementioned polymer (A2) has (M-1) a monomer (M1) having a structure that exhibits photoreactivity and liquid crystallinity; (M-2) has only Liquid crystal structure monomer (M2); and (M-4) monomer having at least one group selected from the group consisting of nitrogen-containing aromatic heterocyclic group, amide group and urethane group (M4); and formed. The composition of claim 19, wherein the aforementioned (M-4) has a monomer having at least one group selected from the group consisting of a nitrogen-containing aromatic heterocyclic group, an amide group, and a urethane group ( M4) is at least one selected from the group consisting of the following formulas MA6~MA8 and MA33,

Such as the composition of claim 17, wherein, when the total of the aforementioned monomer (M1) and the aforementioned monomer (M2) is 100 mol%, the aforementioned polymer (A1) is composed of the aforementioned monomer (M1) as α mol% %(α is 15 or more) and the rest is formed by the aforementioned monomer (M2), The aforementioned polymer (A2) is formed by the aforementioned monomer (M1) being 0.95α mol% or less and the remainder being the aforementioned monomer (M2). A liquid crystal alignment agent characterized by the polymer composition of any one of claims 1-22. A liquid crystal alignment film characterized by being formed by the liquid crystal alignment agent of claim 23. A method for manufacturing a liquid crystal alignment film, characterized by having [I] coating the polymer composition of any one of claims 1 to 22 on a substrate having a conductive film for driving a horizontal electric field to form a coating film The steps; [II] the step of irradiating the coating film obtained in [I] with polarized ultraviolet rays; and [III] the step of heating the coating film obtained in [II]; to obtain a liquid crystal alignment film endowed with alignment control ability. A substrate characterized by the liquid crystal alignment film of claim 24. A method for manufacturing a substrate with a liquid crystal alignment film, which is characterized by coating the polymer composition of any one of claims 1 to 22 on a substrate with a conductive film for driving a horizontal electric field by having [I], The step of forming a coating film; [II] the step of irradiating the coating film obtained in [I] with polarized ultraviolet rays; and [III] the step of heating the coating film obtained in [II]; and obtaining the liquid crystal alignment with the alignment control ability membrane. A liquid crystal display element, which has the characteristics of claim 26 Substrate. A method for manufacturing a liquid crystal display element, characterized by the step of preparing the substrate (first substrate) of claim 26; and coating any one of claims 1-22 on the second substrate by having [I'] The step of forming a coating film from the polymer composition of the item; [II'] the step of irradiating the coating film obtained by [I'] with polarized ultraviolet rays; [III'] the step of heating the coating film obtained by [II']; The step of obtaining a liquid crystal alignment film endowed with alignment control ability to obtain a second substrate having the aforementioned liquid crystal alignment film; and [IV] intervening liquid crystals in such a manner that the liquid crystal alignment films of the first and second substrates are opposed to each other. The step of arranging the aforementioned first and second substrates to obtain a liquid crystal display element; to obtain a liquid crystal display element.