WO2015002292A1 - Polarized ultraviolet-anisotropic material - Google Patents

Abstract

[Problem] To provide a polarized ultraviolet ray-anisotropic material, e.g., a liquid crystal alignment film, a phase difference film or a hologram, which either has no time-dependent change in alignment at all or reduces time-dependent change in alignment and thereby has excellent alignment stability, and which exhibits anisotropy when irradiated with polarized ultraviolet rays. [Solution] The aforementioned problem is solved by means of a material which comprises polymers having a side chain represented by formula (1) (In the formula, A₁ represents -O-, -COO-, -NHCO-, etc., n represents an integer 1-16, some of the methylene groups (-CH₂-) are optionally substituted by -O-, -COO-, -OOC-, -NHCO-, etc., X represents -CH=N- OR -N=CH-, R represents an alkyl group with 1-3 carbon atoms, n₁₁ and n₁₂ each independently represent an integer 0-4, and R₁₁ and R₁₂ each independently represent a linear or branched alkyl group of 1-6 carbon atoms, a halogen atom, etc.), and which is a polarized ultraviolet ray-anisotropic material which exhibits anisotropy when irradiated with polarized ultraviolet rays.

Description

Polarized UV anisotropy material

The present invention relates to a polarized ultraviolet ray anisotropic material having a polymer having a specific N-benzylideneaniline skeleton in the side chain.

The liquid crystal display element is known as a light, thin and low power consumption display device, and has been remarkably developed in recent years. The liquid crystal display element is configured, for example, by sandwiching a liquid crystal layer between a pair of transparent substrates provided with electrodes. In the liquid crystal display element, an organic film made of an organic material is used as the liquid crystal alignment film so that the liquid crystal is in 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 a surface of the substrate that holds the liquid crystal in contact with the liquid crystal, and plays a role of aligning the liquid crystal in a certain direction between the substrates. The liquid crystal alignment film may be required to play a role of controlling the pretilt angle of the liquid crystal in addition to the role of aligning the liquid crystal in a certain direction such as a direction parallel to the substrate. In such a liquid crystal alignment film, the ability to control the alignment of liquid crystal (hereinafter referred to as alignment control ability) is given by performing an alignment treatment on the organic film constituting the liquid crystal alignment film. *

A rubbing method is conventionally known as an alignment treatment method for a liquid crystal alignment film for imparting alignment control ability. However, in the rubbing method of rubbing the surface of the liquid crystal alignment film made of polyimide or the like, generation of dust or static electricity may be a problem. In addition, due to the high definition of the liquid crystal surface element in recent years and the unevenness caused by the corresponding electrodes on the substrate and the switching active element for driving the liquid crystal, the surface of the liquid crystal alignment film cannot be uniformly rubbed with a cloth. In some cases, alignment of the liquid crystal could not be realized. *

Therefore, a photo-alignment method has been actively studied as another alignment treatment method for a liquid crystal alignment film that is not rubbed. There are various photo alignment methods. Anisotropy is formed in the organic film constituting the liquid crystal alignment film by linearly polarized light or collimated light, and the liquid crystal is aligned according to the anisotropy. A decomposition type photo-alignment method is known as a main photo-alignment method. For example, the polyimide film is irradiated with polarized ultraviolet rays, and anisotropic decomposition is caused by utilizing the polarization direction dependence of the ultraviolet absorption of the molecular structure. Then, the liquid crystal is aligned by the polyimide remaining without being decomposed (see, for example, Patent Document 1). *

In addition, photocrosslinking type and photoisomerization type photo-alignment methods are also known. For example, polyvinyl cinnamate is used and irradiated with polarized ultraviolet rays to cause a dimerization reaction (crosslinking reaction) at the double bond portion of two side chains parallel to the polarized light. Then, the liquid crystal is aligned in a direction perpendicular to the polarization direction (see, for example, Non-Patent Document 1). In addition, when a side chain polymer having azobenzene in the side chain is used, irradiation with polarized ultraviolet light causes an isomerization reaction at the azobenzene portion of the side chain parallel to the polarized light, and the liquid crystal is aligned in a direction perpendicular to the polarization direction. Align (for example, see Non-Patent Document 2). *

As in the above example, the liquid crystal alignment film alignment treatment method by the photo alignment method eliminates the need for rubbing, and there is no fear of generation of dust or static electricity. An alignment process can be performed even on a substrate of a liquid crystal display element having an uneven surface, which is a method for aligning a liquid crystal alignment film suitable for an industrial production process.

Japanese Patent No. 3893659

M.M. Shadt et al. , Jpn. J. Appl. Phys. 31, 2155 (1992) K. Ichimura et al. , Chem. Rev. 100, 1847 (2000)

As described above, the photo-alignment method does not require a rubbing process as compared with a rubbing method that has been industrially used as an alignment treatment method for liquid crystal display elements, and thus has a great advantage. And compared with the rubbing method in which the alignment control ability becomes almost constant by rubbing, the photo alignment method can control the alignment control ability by changing the irradiation amount of polarized light. However, in the photo-alignment method, after the liquid crystal display element is formed, the photoreactive group remaining in the liquid crystal alignment film in the element reacts with natural light or the backlight in the liquid crystal display element. Stability may be impaired. In particular, in the case of photo-alignment using isomerization of the azobenzene skeleton, this problem occurs remarkably. *

The object of the present invention is to solve the above-mentioned problems. Specifically, the object of the present invention is a polarized ultraviolet anisotropy material that exhibits no anisotropy over time or has reduced the change over time, has excellent alignment stability, and exhibits anisotropy when irradiated with polarized ultraviolet light. For example, it is to provide a liquid crystal alignment film, preferably a liquid crystal alignment film for a lateral electric field driving type liquid crystal display element, a retardation film, or a hologram. Also, an object of the present invention is to provide a method for producing the above material and a composition for producing the above material.

As a result of intensive studies to achieve the above problems, the present inventors have found the following invention. <1> A side chain represented by the following formula (I) (wherein A ₁ is —O—, —COO—, —NHCO—, —CONH—, —NHCONH—, —NHCOO—, —OCONH— or — N represents an integer of 1 to 16, and a part of the methylene group (—CH ₂ —) is —O—, —COO—, —OOC—, —NHCO—, —CONH—, —NHCONH—. , —NHCOO—, —OCONH—, —C═C— or —C≡C— may be substituted (provided that the methylene group (—CH ₂ —) adjacent to A ₁ or —O— X is —CH═N— or —N═CH—, R is an alkyl group having 1 to 3 carbon atoms, and n ₁₁ and n ₁₂ are each independently an integer of 0 to 4 _represents, in _{R 11} and _{R 12} are each independently, having 1 to 6 carbon atoms, straight-chain or branched-chain Al A polarizing polymer which has an anisotropy when irradiated with polarized ultraviolet light, and a polymer having a sulfur group, a halogen atom, nitro, cyano, a linear or branched alkoxy group having 1 to 6 carbon atoms) Anisotropic material.

<2> In the above <1>, A ₁ represents —O—, —COO— or —OCO—, preferably —O—, n represents an integer of 1 to 8, preferably 6, and the methylene group represents the above It is preferable that R is a methyl group, and n ₁₁ and n ₁₂ are 0. <3> In the above item <1> or <2>, the polymer has the following formulas (21) to (31) (wherein A and B are each independently a single bond, —O—, —CH ₂ — , -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH-CO-O-, or -O-CO-CH = CH-; one of q1 and q2 is 1 Y ₃ is composed of a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocycle, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof. Each of the hydrogen atoms bonded to them is independently substituted with —NO ₂ , —CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms. It is good; _{R 3} is a hydrogen _{atom, -NO 2, -CN, -CH =} C _{CN) 2, -CH = CH-} CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, a C1- 12 represents an alkyl group of 12 or an alkoxy group having 1 to 12 carbon atoms; l represents an integer of 1 to 12, m represents an integer of 0 to 2, provided that in formulas (25) to (26), all The sum of m is 2 or more, and in formulas (27) to (28), the sum of all m is 1 or more, and m1, m2 and m3 each independently represents an integer of 1 to 3; R ₂ represents a hydrogen atom, —NO ₂ , —CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocyclic ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, and Represents an alkyl group or an alkyloxy group; Z ₁ , Z ₂ represents a single bond, —CO—, —CH ₂ O—, —CH═N—, —CF ₂ —), and may further have any one liquid crystalline side chain selected from the group consisting of .

<4> In any one of the above items <1> to <3>, the material is one selected from the group consisting of a liquid crystal aligning agent, a retardation film, and a hologram, preferably a liquid crystal aligning agent or a retardation film. Is preferably used for a liquid crystal aligning agent, most preferably a liquid crystal aligning film for a lateral electric field drive type liquid crystal display element. *

<5> A composition for polarizing ultraviolet anisotropic material, comprising: (A) a polymer having a side chain represented by the above formula (I); and (B) an organic solvent. <6> In the above item <5>, A ₁ represents —O—, —COO— or —OCO—, preferably —O—, n represents an integer of 1 to 8, preferably 6, and the methylene group represents the above It is preferable that R is a methyl group, and n ₁₁ and n ₁₂ are 0. <7> In the above item <5> or <6>, the polymer may further have any one liquid crystalline side chain selected from the group consisting of the above formulas (21) to (31). <8> In any one of the above items <5> to <7>, the material is one selected from the group consisting of a liquid crystal aligning agent, a retardation film, and a hologram, preferably a liquid crystal aligning agent or a retardation film, more preferably A liquid crystal aligning agent, most preferably, a liquid crystal aligning film for a lateral electric field drive type liquid crystal display element is used.

<9> [I] (A) A composition having a side chain represented by the above formula (I); and (B) an organic solvent; A step of forming a coating film; and [II] a step of irradiating the coating film obtained in [I] with polarized ultraviolet rays; A method for producing a polarized ultraviolet anisotropic material. *

<10> In the above item <9>, the method may further include a step of heating the coating film obtained in [III] [II]. <11> In the above <9> or <10>, A ₁ represents —O—, —COO— or —OCO—, preferably —O—, and n represents an integer of 1 to 8, preferably 6. The methylene group is preferably not substituted with the above substituents, preferably R is a methyl group and n ₁₁ and n ₁₂ are 0.

<12> In any one of the above items <9> to <11>, the polymer may further include any one liquid crystalline side chain selected from the group consisting of the above formulas (21) to (31). . <13> In any one of the above items <9> to <12>, the material is one selected from the group consisting of a liquid crystal aligning agent, a retardation film, and a hologram, preferably a liquid crystal aligning agent or a retardation film, more preferably A liquid crystal aligning agent, most preferably, a liquid crystal aligning film for a lateral electric field drive type liquid crystal display element is used. *

<14> A composition for producing a polarized ultraviolet anisotropic material having a monomer represented by the following formula [RM1] or [RM2] (wherein Me represents a methyl group). *

<15> In the above item <14>, the polarized ultraviolet anisotropic material is one selected from the group consisting of a liquid crystal aligning agent, a retardation film, and a hologram, preferably a liquid crystal aligning agent or a retardation film, more preferably a liquid crystal. An alignment agent, most preferably, a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display element is used.

According to the present invention, a polarized ultraviolet anisotropic material, such as a liquid crystal alignment film, which has no or no change in alignment with time, has excellent alignment stability and exhibits anisotropy when irradiated with polarized UV rays, such as a liquid crystal alignment film, Can provide a liquid crystal alignment film, a retardation film, or a hologram for a horizontal electric field drive type liquid crystal display element. In addition to the above effects or in addition to the above effects, the present invention can provide a method for producing the above materials and a composition for producing the above materials.

It is a figure which shows the change of the absorption spectrum when the polymer P1 thin film of Example 3 is irradiated with 313 nm light (intensity: 10 mW / cm ² ). It is a figure which shows the change of the polarization | polarized-light absorption spectrum at the time of irradiating the linearly polarized ultraviolet-ray 313nm to 10 J / cm < ² > to the P1 film prepared in Example 4. FIG. It is a figure which shows the optical path figure (FIG. 3a) at the time of performing the holographic exposure of Example 5, and the height (FIG. 3b and FIG. 3c) of two types of surface relief formed by the holograph.

The present application provides a polarized ultraviolet anisotropic material, a composition for the material, a method for producing the material, a composition used for producing the material, and the like. Hereinafter, it demonstrates in order. <Polarized UV Anisotropy Material> This application is a material having a polymer having a side chain represented by the following formula (I), and provides a polarized UV anisotropy material that exhibits anisotropy when irradiated with polarized UV light. To do. *

In the formula (I), A ₁ represents —O—, —COO—, —NHCO—, —CONH—, —NHCONH—, —NHCOO—, —OCONH— or —OCO—, and n represents an integer of 1 to 16 A part of the methylene group (—CH ₂ —) is —O—, —COO—, —OOC—, —NHCO—, —CONH—, —NHCONH—, —NHCOO—, —OCONH—, —C═ C— or —C≡C— may be substituted (provided that the methylene group (—CH ₂ —) adjacent to A ₁ or —O— is not substituted by these groups), and X is —CH═N -Or -N = CH-, R represents an alkyl group having 1 to 3 carbon atoms, n ₁₁ and n ₁₂ each independently represents an integer of 0 to 4, and R ₁₁ and R ₁₂ each independently represent Straight or branched alkyl group having 1 to 6 carbon atoms, halogen atom, nitro, Cyano represents a linear or branched alkoxy group having 1 to 6 carbon atoms

In particular, in formula (I), A ₁ represents —O—, —COO— or —OCO—, preferably —O—, n represents an integer of 1 to 8, preferably 6, and the methylene group is as defined above. It is preferably not substituted with a substituent, R is a methyl group, and n ₁₁ and n ₁₂ are preferably 0.

The polymer having a side chain represented by the above formula (I) exhibits anisotropy when irradiated with polarized ultraviolet rays. In particular, a polymer having a side chain represented by the above formula (I) exhibits anisotropy when irradiated with polarized ultraviolet light having a wavelength of 100 to 400 nm. Further, the polymer having a side chain represented by the above formula (I) preferably exhibits liquid crystallinity when heated in a temperature range of 40 to 300 ° C. *

The molecular weight of the polymer (A) of the present invention is GPC (Gel Permeation Chromatography) in consideration of the intended material, for example, the strength of the resulting coating film, the workability during coating film formation, and the uniformity of the coating film. The weight average molecular weight measured by the above method is preferably 2,000 to 1,000,000, more preferably 5,000 to 100,000. *

The polymer having a side chain represented by the above formula (I) preferably further has a liquid crystalline side chain having a mesogenic group exhibiting liquid crystallinity. In particular, a liquid crystalline side chain exhibiting liquid crystallinity in a temperature range of 40 to 300 ° C. is preferable. When the target material is a liquid crystal alignment film, it is preferably a liquid crystalline side chain exhibiting liquid crystallinity in a temperature range of 100 to 300 ° C. *

These liquid crystalline side chains may be any one of the liquid crystalline side chains selected from the group consisting of the following formulas (21) to (31). In the formula, A and B are each independently a single bond, —O—, —CH ₂ —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH—CO—O. - or a -O-CO-CH = CH-; q1 and q2 is one the other is 1 is at 0; _{Y 3} is a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing A group selected from the group consisting of a heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, and the hydrogen atoms bonded to them are each independently —NO ₂ , —CN, a halogen group , An alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms; R ₃ is a hydrogen atom, —NO ₂ , —CN, —CH═C (CN) ₂ , -CH = CH-CN, halogen group, monovalent benzene ring, naphthalene A ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocycle, an alicyclic hydrocarbon having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms; 12 represents an integer of 0, m represents an integer of 0 to 2, provided that in formulas (25) to (26), the sum of all m is 2 or more, and in formulas (27) to (28), all And m1, m2 and m3 each independently represents an integer of 1 to 3; R ₂ represents a hydrogen atom, —NO ₂ , —CN, a halogen group or a monovalent benzene ring. , A naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and an alkyl group or an alkyloxy group; Z ₁ and Z ₂ are a single bond, — CO—, —CH ₂ O—, —CH═N—, —CF ₂ — is represented.

The material having a polymer having a side chain represented by the formula (I) is one selected from the group consisting of a liquid crystal aligning agent, a retardation film, and a hologram, preferably a liquid crystal aligning agent or a retardation film. It is preferably used for a liquid crystal aligning agent, most preferably a liquid crystal aligning film for a lateral electric field drive type liquid crystal display element. *

<Composition for polarized ultraviolet anisotropic material> The present application is a composition for polarized ultraviolet anisotropic material having (A) a polymer having a side chain represented by the above formula (I); and (B) an organic solvent. Offer things. *

<< Organic Solvent >> The organic solvent used in the composition for polarizing ultraviolet anisotropic material used in the present invention is not particularly limited as long as it is an organic solvent that dissolves the component (A). Specific examples are given below. N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethylsulfoxide, tetramethylurea, pyridine, Dimethylsulfone, hexamethylsulfoxide, γ-butyrolactone, 3-methoxy-N, N-dimethylpropanamide, 3-ethoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, 1,3 -Dimethyl-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diglyme, 4-hydroxy- -Methyl-2-pentanone, 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 Etc. These may be used alone or in combination. *

The composition for polarized ultraviolet anisotropic material used in the present invention may contain components other than the components (A) and (B). The composition of the present invention may have a polymer exhibiting liquid crystallinity as a component other than the components (A) and (B), or may contain other polymers. Examples of other polymers include, but are not limited to, poly (meth) acrylate, polyamic acid, polyimide, and the like. In 100% by mass of the composition, the content of the other polymer is 0.5 to 90% by mass, preferably 1 to 50% by mass. *

Further, in addition to the components (A) and (B), the composition of the present invention may include, for example, a solvent or a compound that improves the film thickness uniformity and surface smoothness when the composition is applied, In the case where the material is a liquid crystal alignment film or the like, a compound that improves the adhesion between the liquid crystal alignment film and the substrate can be exemplified, but the present invention is not limited thereto. *

Specific examples of the solvent (poor solvent) that improves the uniformity of the film thickness and 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 monoacetate Isopropyl ether, ethylene glycol monobutyl 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, dipro Lenglycol 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 ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl Ether, 1-hexanol, n-hexane, n-pentane, n-octane Diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, Ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 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, lactate methyl ester, lactate ethyl ester, lactate n-propyl ester, lactate n-butyl ester, lactyl isoamyl ester, etc. Examples include solvents having surface tension.

These poor solvents may be used alone or in combination. When the solvent as described above is used, it is preferably 5% by mass to 80% by mass, more preferably 20% by mass, so that the solubility of the entire solvent contained in the composition is not significantly reduced. % To 60% by mass. *

Examples of compounds that improve film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants. More specifically, for example, Ftop (registered trademark) 301, EF303, EF352 (manufactured by Tochem Products), MegaFac (registered trademark) F171, F173, R-30 (manufactured by DIC), Florard FC430, FC431 (Manufactured by Sumitomo 3M), Asahi Guard (registered trademark) AG710 (manufactured by Asahi Glass Company), Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Seimi Chemical Co., Ltd.) It is done. The proportion of these surfactants to be used is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 100 parts by mass of the component (A) in the composition. The amount is preferably from 1 to 1 part by mass. *

When the material is a liquid crystal alignment film or the like, specific examples of the compound that improves the adhesion between the liquid crystal alignment film and the substrate include the following functional silane-containing compounds. For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxy Carbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10- Riethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyl Trimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3- Aminopropyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane and the like can be mentioned. *

Further, when the material is a liquid crystal alignment film or the like, the following phenotypes are used for the purpose of preventing the deterioration of the electrical characteristics due to the backlight when the liquid crystal display element is constructed in addition to improving the adhesion between the substrate and the liquid crystal alignment film. Additives for plast-based or epoxy group-containing compounds may be included in the composition. Specific phenoplast additives are shown below, but are not limited to this structure. *

Specific epoxy group-containing compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6 -Hexanediol diglycidyl ether, glycerin diglycidyl 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, '- diaminodiphenylmethane and the like. *

When a compound that improves adhesion to the substrate is used, the amount used is 0.1 to 30 parts by mass with respect to 100 parts by mass of the component (A) of the polymer contained in the composition. It is preferable that the amount is 1 to 20 parts by mass. *

A photosensitizer can also be used as an additive. Colorless and triplet sensitizers are preferred. As photosensitizers, aromatic nitro compounds, coumarin (7-diethylamino-4-methylcoumarin, 7-hydroxy4-methylcoumarin), ketocoumarin, carbonylbiscoumarin, aromatic 2-hydroxyketone, and amino-substituted, Aromatic 2-hydroxyketones (2-hydroxybenzophenone, mono- or di-p- (dimethylamino) -2-hydroxybenzophenone), acetophenone, anthraquinone, xanthone, thioxanthone, benzanthrone, thiazoline (2-benzoylmethylene-3- Methyl-β-naphthothiazoline, 2- (β-naphthoylmethylene) -3-methylbenzothiazoline, 2- (α-naphthoylmethylene) -3-methylbenzothiazoline, 2- (4-biphenoylmethylene) -3 -Methylbenzothia Phosphorus, 2- (β-naphthoylmethylene) -3-methyl-β-naphthothiazoline, 2- (4-biphenoylmethylene) -3-methyl-β-naphthothiazoline, 2- (p-fluorobenzoylmethylene)- 3-methyl-β-naphthothiazoline), oxazoline (2-benzoylmethylene-3-methyl-β-naphthoxazoline, 2- (β-naphthoylmethylene) -3-methylbenzoxazoline, 2- (α-naphthoylmethylene) ) -3-methylbenzoxazoline, 2- (4-biphenoylmethylene) -3-methylbenzoxazoline, 2- (β-naphthoylmethylene) -3-methyl-β-naphthoxazoline, 2- (4-biphenoyl) Methylene) -3-methyl-β-naphthoxazoline, 2- (p-fluorobenzoylmethylene) -3-methyl-β- Ftoxazoline), benzothiazole, nitroaniline (m- or p-nitroaniline, 2,4,6-trinitroaniline) or nitroacenaphthene (5-nitroacenaphthene), (2-[(m-hydroxy-p -Methoxy) styryl] benzothiazole, benzoin alkyl ether, N-alkylated phthalone, acetophenone ketal (2,2-dimethoxyphenylethanone), naphthalene, anthracene (2-naphthalenemethanol, 2-naphthalenecarboxylic acid, 9-anthracenemethanol And 9-anthracenecarboxylic acid), benzopyran, azoindolizine, melocoumarin, etc. Preferably, aromatic 2-hydroxyketone (benzophenone), coumarin, ketocoumarin, carbonylbiscoumarin, acetophen Non, anthraquinone, xanthone, thioxanthone, and acetophenone Straight tar. *

In addition to those described above, the composition may contain various compounds for the purpose of changing the properties of the obtained material. For example, when the material is a liquid crystal alignment film, for the purpose of changing the electrical properties such as the dielectric constant and conductivity of the liquid crystal alignment film, the dielectric or conductive material, and the hardness of the film when the liquid crystal alignment film is formed, For the purpose of increasing the density, a crosslinkable compound may be added. *

<Production Method of Polarized Ultraviolet Anisotropic Material> The polarized ultraviolet anisotropic material of the present invention can be produced, for example, by the following method. [I] (A) a polymer having a side chain represented by the above formula (I) (wherein A ₁ , n, X, and R have the same definition as above); and (B) an organic solvent; Applying a composition for polarizing ultraviolet anisotropic material having a coating on a substrate to form a coating film; and [II] irradiating the coating film obtained in [I] with polarized ultraviolet light. Thus, a polarized ultraviolet anisotropic material having an orientation control ability can be obtained. The (A) polymer and (B) organic solvent and the composition containing them are as described above. The method may further include a step of heating the coating film obtained in [III] [II].

When a liquid crystal alignment film, particularly a liquid crystal alignment film for a liquid crystal display element, is obtained as a material, a substrate having a conductive film (first substrate) is preferably used as the substrate [I]. In addition, the above [I] and [II], and in some cases [III], may be performed using a substrate (second substrate) with or without a conductive film. Further, in the method of manufacturing a liquid crystal display element, [IV] the first and second substrates obtained above are arranged so that the liquid crystal alignment films of the first and second substrates face each other through the liquid crystal. And obtaining a liquid crystal display element. Thereby, a liquid crystal display element can be obtained. *

Hereinafter, [I] and [II], and [III] and [IV] steps of the production method of the present invention will be described. <Step [I]> Step [I] is a step of applying the composition described above to a substrate to form a coating film. *

<Substrate> The substrate is not particularly limited, but is preferably selected depending on the target material. In the case of a liquid crystal alignment film, particularly a liquid crystal alignment film for a liquid crystal display element, when the liquid crystal display element to be manufactured is a transmissive type, it is preferable to use a highly transparent substrate. In that case, there is no particular limitation, and a glass substrate or a plastic substrate such as an acrylic substrate or a polycarbonate substrate can be used. In consideration of application to a reflective liquid crystal display element, an opaque substrate such as a silicon wafer can also be used. *

Furthermore, when the target material is a liquid crystal alignment film for a liquid crystal display element, the substrate may have a conductive film. Examples of the conductive film include, but are not limited to, ITO (Indium Tin Oxide) and IZO (Indium Zinc Oxide) when the liquid crystal display element is a transmission type. In the case of a reflective liquid crystal display element, examples of the conductive film include a material that reflects light such as aluminum, but are not limited thereto. As a method for forming a conductive film on a substrate, a conventionally known method can be used. *

<< (A) Polymer Production Method >> The polymer (A) includes a photoreactive side chain monomer having a side chain represented by the above formula (I) and, optionally, the above formulas (21) to (31). It can be obtained by polymerizing a liquid crystalline side chain monomer having a side chain represented by The photoreactive side chain monomer having a side chain represented by the formula (I) has a side chain represented by the formula (I) at the side chain site of the polymer when a polymer is formed. A monomer that can form a polymer. More specific examples of the photoreactive side chain monomer include radical polymerizable groups such as hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene, etc. And a structure having a polymerizable group composed of at least one selected from the group consisting of siloxane and a side chain represented by the side chain represented by the above formula (I). *

[Liquid Crystalline Side Chain Monomer] The liquid crystalline side chain monomer is a monomer in which a polymer derived from the monomer exhibits liquid crystallinity and the polymer can form a mesogenic group at a side chain site. As a mesogenic group having a side chain, even if it is a group having a mesogen structure alone such as biphenyl or phenylbenzoate, or a group having a mesogen structure by hydrogen bonding between side chains such as benzoic acid Good. As the mesogenic group possessed by the side chain, the following structure is preferable.

More specific examples of liquid crystalline side chain monomers include hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene and other radical polymerizable groups and siloxane A structure having a polymerizable group composed of at least one selected from the group consisting of and a side chain composed of at least one of the above formulas (21) to (31) is preferable. *

(A) The polymer can be obtained by the polymerization reaction of the photoreactive side chain monomer described above. *

More specifically, the (A) polymer of the present invention can be produced from a composition for producing a polarized ultraviolet anisotropic material having a monomer represented by the following formula [RM1] or [RM2]. The present invention also provides a composition for producing the polarized ultraviolet anisotropic material. *

The polymer (A) of the present invention is a copolymer of a photoreactive side chain monomer that does not exhibit liquid crystallinity and a liquid crystalline side chain monomer, or a photoreactive side chain monomer that exhibits liquid crystallinity and a liquid crystalline side. It can be obtained by copolymerization with chain monomers. Furthermore, it can be copolymerized with other monomers as long as the liquid crystallinity is not impaired. *

Examples of other monomers include industrially available monomers capable of radical polymerization reaction. Specific examples of other monomers include unsaturated carboxylic acid, acrylic ester compound, methacrylic ester compound, maleimide compound, acrylonitrile, maleic anhydride, styrene compound and vinyl compound. *

Specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid and the like. Examples of acrylic acid ester compounds include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, 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-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and , Etc. 8-ethyl-8-tricyclodecyl acrylate. *

Examples of methacrylic acid ester compounds include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl 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 tricyclodecyl methacrylate, and, 8-ethyl-8-tricyclodecyl methacrylate. (Meth) acrylate compounds having a cyclic ether group such as glycidyl (meth) acrylate, (3-methyl-3-oxetanyl) methyl (meth) acrylate, and (3-ethyl-3-oxetanyl) methyl (meth) acrylate are also used. be able to. *

Examples of the vinyl compound include vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether. Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, bromostyrene, and the like. Examples of maleimide compounds include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide. *

The method for producing the polymer (A) of the present embodiment is not particularly limited, and a general-purpose method handled industrially can be used. Specifically, it can be produced by cationic polymerization, radical polymerization, or anionic polymerization using a vinyl group of a liquid crystalline side chain monomer or photoreactive side chain monomer. Among these, radical polymerization is particularly preferable from the viewpoint of ease of reaction control. *

As the polymerization initiator for radical polymerization, a known compound such as a radical polymerization initiator or a reversible addition-cleavage chain transfer (RAFT) polymerization reagent can be used. *

The radical thermal polymerization initiator is a compound that generates radicals by heating to a decomposition temperature or higher. Examples of such radical thermal polymerization initiators include ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide, etc.), hydroperoxides (hydrogen peroxide). , Tert-butyl hydride peroxide, cumene hydroperoxide, etc.), dialkyl peroxides (di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, etc.), peroxyketals (dibutyl peroxycyclohexane, etc.) ), Alkyl peresters (peroxyneodecanoic acid-tert-butyl ester, peroxypivalic acid-tert-butyl ester, peroxy 2-ethylcyclohexa Acid-tert-amyl ester, etc.), persulfates (potassium persulfate, sodium persulfate, ammonium persulfate, etc.), azo compounds (azobisisobutyronitrile, and 2,2'-di (2-hydroxyethyl) And azobisisobutyronitrile). Such radical thermal polymerization initiators can be used singly or in combination of two or more. *

The radical photopolymerization initiator is not particularly limited as long as it is a compound that initiates radical polymerization by light irradiation. Examples of such radical photopolymerization initiators include benzophenone, Michler's ketone, 4,4′-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, 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, benzanthrone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzene Dil-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4,4′-di (t-butylperoxycarbonyl) benzophenone 3,4,4′-tri (t-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2- (4′-methoxystyryl) -4,6-bis (trichloromethyl) -S-triazine, 2- (3 ', 4'-dimethoxystyryl) -4,6-bis (trichloromethyl) -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-di (ethoxycarbonylmethyl)]-2,6 -Di (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2'-chlorophenyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (4'- Methoxyphenyl) -s-triazine, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2-mercaptobenzothiazole, 3,3′-carbonylbis (7-diethylaminocoumarin) ), 2- (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2,4-dichlorophenyl) -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-cyclopentadie -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′-di (methoxycarbonyl) -4,4′-di (t-butylperoxycarbonyl) benzophenone, 3,4 ′ -Di (methoxycarbonyl) -4,3'-di (t-butylperoxycarbonyl) benzophenone, 4,4'-di (methoxycarbonyl) -3,3'-di (t-butylperoxycarbonyl) benzophenone, 2- (3-methyl-3H-benzothiazol-2-ylidene) -1-naphthalen-2-yl-ethanone, or 2- (3-methyl-1, - benzothiazol -2 (3H) - ylidene) -1- (2-benzoyl) ethanone, and the like. These compounds may be used alone or in combination of two or more. *

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

The organic solvent used for the polymerization reaction of the photosensitive side chain polymer capable of exhibiting liquid crystallinity is not particularly limited as long as the generated polymer is soluble. Specific examples are given below. *

N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide , 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 acetate, ethyl cellosolve acetate, butyl Carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethyl Glycol monobutyl 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 ether, diisobutylene, amyl 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, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, Ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropion , 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy-N, N-dimethylpropanamide, 3-ethoxy -N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide and the like.

These organic solvents may be used alone or in combination. Furthermore, even if it is a solvent which does not dissolve the polymer | macromolecule to produce | generate, you may mix and use the above-mentioned organic solvent in the range which the polymer | macromolecule produced | generated does not precipitate. Also, in radical polymerization, oxygen in the organic solvent causes the polymerization reaction to be inhibited. Therefore, it is preferable to use an organic solvent that has been degassed as much as possible. *

The polymerization temperature at the time of radical polymerization can be selected from 30 ° C. to 150 ° C., but is preferably in the range of 50 ° C. to 100 ° C. The reaction can be carried out at any concentration, but if the concentration is too low, it is difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring is difficult. Therefore, the monomer concentration is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 30% by mass. The initial stage of the reaction is carried out at a high concentration, and then an organic solvent can be added. *

In the above-mentioned radical polymerization reaction, the molecular weight of the obtained polymer is decreased when the ratio of the radical polymerization initiator is large relative to the monomer, and the molecular weight of the obtained polymer is increased when the ratio is small, the ratio of the radical initiator is The content is preferably 0.1 mol% to 10 mol% with respect to the monomer to be polymerized. Further, various monomer components, solvents, initiators and the like can be added during the polymerization. *

[Recovery of polymer] When the generated polymer is recovered from the reaction solution obtained by the above-described reaction, the reaction solution is preferably poured into a poor solvent to precipitate the obtained polymer. Examples of the poor solvent used for precipitation include methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, and water. The polymer deposited in a poor solvent and collected can be collected by filtration, and then dried at normal temperature or reduced pressure at room temperature or by heating. Further, when the polymer collected by precipitation is redissolved in an organic solvent and then collected by reprecipitation is repeated 2 to 10 times, impurities in the polymer can be reduced. Examples of the poor solvent at this time include alcohols, ketones, hydrocarbons and the like, and it is preferable to use three or more kinds of poor solvents selected from these because purification efficiency is further improved. *

[Preparation of Composition] The composition of the present invention is preferably prepared as a coating solution so as to be suitable for forming a liquid crystal alignment film. The composition of the present invention is preferably prepared as a solution in which (A) the components of the polymer and others are dissolved in an organic solvent. Here, (A) polymer component and others refer to a polymer having a side chain represented by formula (I) and a resin component containing other polymers. In 100% by mass of the composition of the present invention, the content of the component (A) is 1 to 20% by mass, preferably 3 to 15% by mass, more preferably 3 to 10% by mass. *

The method for applying the above-described composition onto the substrate is not particularly limited. The application method is generally industrially performed by screen printing, offset printing, flexographic printing, or an inkjet method. Other coating methods include a dipping method, a roll coater method, a slit coater method, a spinner method (rotary coating method), or a spray method, and these may be used depending on the purpose. *

After coating the composition on the substrate, the solvent is evaporated at 50 to 200 ° C., preferably 50 to 150 ° C. by a heating means such as a hot plate, a heat circulation oven or an IR (infrared) oven, and the coating film is formed. Obtainable. The thickness of the coating film depends on the target material, but it is 5 to 10,000 nm, preferably 10 to 5000 nm. When used as a liquid crystal alignment film, it is preferably 5 to 300 nm, preferably 10 to 200 nm, and when used as a retardation film or hologram, 500 to 10,000 nm is preferable, and 500 to 5000 nm is more preferable. In addition, it is also possible to provide the process of cooling the board | substrate with which the coating film was formed to room temperature after the [I] process and before the following [II] process. *

<Step [II]> In Step [II], the coating film obtained in Step [I] is irradiated with polarized ultraviolet rays. When irradiating the surface of the coating film with polarized ultraviolet rays, the substrate is irradiated with polarized ultraviolet rays through a polarizing plate from a certain direction. As the ultraviolet rays to be used, ultraviolet rays having a wavelength in the range of 100 nm to 400 nm can be used. Preferably, the optimum wavelength is selected through a filter or the like depending on the type of coating film to be used. Then, ultraviolet rays having a wavelength in the range of 290 nm to 400 nm can be selected and used so that the photoisomerization reaction can be selectively induced. As the ultraviolet light, for example, light emitted from a high-pressure mercury lamp can be used. *

When the step [III] is performed after the step [II], the irradiation amount of polarized ultraviolet rays depends on the coating film to be used. The amount of irradiation is polarized ultraviolet light that realizes the maximum value of ΔA (hereinafter also referred to as ΔAmax), which is the difference between the ultraviolet light absorbance in a direction parallel to the polarization direction of polarized ultraviolet light and the ultraviolet light absorbance in a direction perpendicular to the polarization direction of the polarized ultraviolet light. The amount is preferably in the range of 1% to 70%, more preferably in the range of 1% to 50%. *

<Step [III]> In step [III], the coating film irradiated with ultraviolet rays polarized in step [II] is heated. An orientation control ability can be imparted to the coating film by heating. Heating can be performed using a heating means such as a hot plate, a heat circulation type oven, or an IR (infrared) type oven. The heating temperature can be determined in consideration of the temperature at which the liquid crystallinity of the coating film used is developed. The thickness of the coating film formed after heating is preferably the same as in step [I]. *

By having the above process, the manufacturing method of this invention can implement | achieve the introduction of the anisotropy to a coating film with high efficiency. Therefore, the method of the present invention can produce a material such as a substrate with a liquid crystal alignment film with high efficiency. *

<Step [IV]> When the target material is a liquid crystal alignment film for liquid crystal display elements, a liquid crystal alignment film for liquid crystal display elements can be obtained by using step [IV]. Here, a substrate having a conductive film for driving a lateral electric field is used as the substrate, and a liquid crystal alignment film is formed on the conductive film for driving a lateral electric field by performing the above [I] to [III]. A substrate (first substrate) can be obtained. Further, by performing the above [I] to [III] using a substrate not having the conductive film instead of the substrate having the conductive film for driving the lateral electric field on the substrate, a liquid crystal alignment film having no conductive film is obtained. An attached substrate (second substrate) can be obtained. In the step [IV], the first and second substrates are arranged to face each other with the liquid crystal alignment film facing each other through the liquid crystal, and a liquid crystal cell is manufactured by a known method. This is a step of manufacturing a liquid crystal display element. *

To give an example of the production of a liquid crystal cell or a liquid crystal display element, the first and second substrates described above are prepared, spacers are dispersed on the liquid crystal alignment film of one substrate, and the liquid crystal alignment film surface is on the inside. In this way, the other substrate is bonded and the liquid crystal is injected under reduced pressure, or the liquid crystal is dropped on the liquid crystal alignment film surface on which the spacers are dispersed, and then the substrate is bonded and sealed. , Etc. can be illustrated. At this time, it is preferable to use a substrate having an electrode having a structure like a comb for driving a horizontal electric field as the substrate on one side. The diameter of the spacer at this time is preferably 1 μm to 30 μm, more preferably 2 μm to 10 μm. This spacer diameter determines the distance between the pair of substrates that sandwich the liquid crystal layer, that is, the thickness of the liquid crystal layer. *

The manufacturing method of a board | substrate with a coating film irradiates the polarized ultraviolet-ray, after apply | coating a composition on a board | substrate and forming a coating film. Next, by heating, a highly efficient introduction of anisotropy into the side chain polymer film is realized, and a substrate with a liquid crystal alignment film having a liquid crystal alignment control ability can be manufactured. Hereinafter, the present invention will be specifically described using examples, but the present invention is not limited to the examples.

Abbreviations used in the examples are as follows. (Methacrylic monomer)

<Synthesis Example 1> Synthesis of Compound [RM1]

4-Hydroxybenzaldehyde [A] (100.0 g, 819 mol), p-anisidine [B] (100.9 g, 819 mol) and distilled water (1000 g) were added to a 2 L four-necked flask and stirred at room temperature. . The reaction was monitored by HPLC, and after confirming the completion of the reaction, the precipitated solid was filtered, washed successively with distilled water and ethanol, and the solid was dried under reduced pressure to obtain 175.7 g of Compound [C] (yield). 94%). ¹ H-NMR (400 MHz, DMSO-d6, δ ppm): 10.11 (1H, brs), 8.47 (1H, s), 7.78-7.34 (2H, m), 7.24-7.20 (2H, m), 6.96-6.92 ( 2H, m), 6.89-6.87 (2H, m), 3.77 (3H, s).

In a 2 L four-necked flask, compound [C] obtained above (175.7 g, 773 mmol), 6-chloro-1-hexanol (116.2 g, 851 mmol), potassium carbonate (128.3 g, 928 mmol), potassium iodide (1.28 g, 7.73 mmol), N, N-dimethylformamide (hereinafter abbreviated as “DMF”) (880 g) were added, and the mixture was heated and stirred at 80 ° C. The reaction was traced by HPLC, and after confirming the completion of the reaction, the reaction solution was cooled to near room temperature, and then poured into 4 L of distilled water. The precipitated solid was filtered off, washed successively with methanol and ethyl acetate, and the solid was dried under reduced pressure to obtain 196.6 g of Compound [D] (yield 78%). ¹ H-NMR (400 MHz, DMSO-d6, δ ppm): 8.40 (1H, s), 7.83-7.80 (2H, m), 7.22-7.19 (2H, m), 6.97-6.91 (4H, m), 4.01 ( 2H, t), 3.82 (3H, s), 3.66 (2H, t), 1.86-1.79 (2H, m), 1.65-1.57 (2H, m), 1.55-1.40 (4H, m).

The compound [D] obtained above (196.6 g, 600 mmol), triethylamine (85.1 g, 841 mmol), tetrahydrofuran (hereinafter abbreviated as THF) (1100 g) was added to a 2 L four-necked flask, and the reaction solution was cooled. . A solution of methacrylic acid chloride (75.3 g, 720 mmol) in THF (100 g) was added dropwise thereto with care so that the internal temperature did not exceed 10 ° C. After completion of the dropwise addition, the reaction solution was brought to 23 ° C. and further reacted. The reaction was monitored by HPLC, and after confirming the completion of the reaction, the reaction solution was poured into 7.2 L of distilled water, the precipitated solid was filtered, washed successively with distilled water and a mixed solvent of ethyl acetate / hexane, and the solid was dried under reduced pressure. As a result, 168 g of the compound [RM1] was obtained (yield 71%). ¹ H-NMR (400 MHz, DMSO-d6, δ ppm): 8.52 (1H, s), 7.86-7.82 (2H, m), 7.26-7.20 (2H, m), 7.04-7.02 (2H, m), 6.97- 6.95 (2H, m), 6.02-6.01 (1H, m), 5.66-5.65 (1H, m), 4.10 (2H, t), 4.03 (2H, t), 3.76 (3H, s), 1.87-1.87 ( 3H, m), 1.76-1.72 (2H, m), 1.66-1.63 (2H, m), 1.51-1.40 (4H, m).

<Synthesis Example 2> Synthesis of Compound [RM2]

In a 3 L four-necked flask, compound 4-nitrophenol [E] (300.0 g, 2.16 mol), 6-chloro-1-hexanol (324.1 g, 2.37 mol), potassium carbonate (358.2 g, 2. 59 mol), potassium iodide (3.59 g, 21.6 mmol) and DMF (1500 g) were added, and the mixture was heated and stirred at 80 ° C. The reaction was traced by HPLC, and after confirming the completion of the reaction, the reaction solution was cooled to near room temperature, and then poured into 4 L of distilled water. The precipitated solid was filtered off, washed successively with methanol and ethyl acetate, and the solid was dried under reduced pressure to obtain 506.4 g of compound [F] (yield 98%). ¹ H-NMR (400 MHz, CDCl ₃ , δ ppm): 8.22-8.18 (2H, m), 6.96-6.92 (2H, m), 4.06 (2H, t), 3.68 (2H, t), 1.88-1.81 (2H , m), 1.68-1.38 (6H, m).

Compound [F] (198.0 g, 828 mmol), THF (1200 g) and distilled water (800 g) are added to a 3 L four-necked flask, tin chloride (392.0 g, 2.07 mol) is added, and the mixture is heated and stirred at 70 ° C. Went. After confirming the completion of the reaction, the reaction mixture was concentrated by an evaporator to reduce the THF almost by half, and the residue was poured into 2 L of ethyl acetate. Thereto was neutralized by adding sodium bicarbonate while paying attention to foaming. After the precipitated solid was removed by filtration, the filtrate was concentrated with an evaporator to obtain 163.1 g of Compound [G] (yield 94%). ¹ H-NMR (400 MHz, DMSO-d6, δ ppm): 6.60-6.58 (2H, m), 6.48-6.45 (2H, m), 4.53 (2H, brs), 4.32 (1H, t), 3.76 (2H, t), 2.26 (2H, t), 1.62-1.56 (2H, m), 1.40-1.23 (6H, m).

Compound [G] (100.0 g, 478 mmol), p-anisaldehyde (65.1 g, 478 mmol), and ethanol (1000 g) were added to a 2 L four-necked flask, and the reaction was performed under heating to reflux. After completion of the reaction, the reaction solution was allowed to cool to room temperature, the precipitated solid was filtered and washed with ethanol, and then the solid was dried under reduced pressure to obtain 112.4 g of Compound [H] (yield 72%). ¹ H-NMR (400 MHz, DMSO-d6, δ ppm): 8.50 (1H, s), 7.84-7.79 (2H, m), 7.21-7.17 (2H, m), 7.04-7.00 (2H, m), 6.93- 6.90 (2H, m), 4.33 (1H, t), 3.95 (2H, t), 3.79 (3H, s), 3.37 (2H, t), 1.71-1.64 (2H.m), 1.44-1.29 (6H, m).

The compound [H] obtained above (105.6 g, 323 mmol), triethylamine (48.6 g, 480 mmol), and THF (570 g) were added to a 2 L four-necked flask, and the reaction solution was cooled. A solution of methacrylic acid chloride (40.5 g, 387 mmol) in THF (70 g) was added dropwise thereto with care so that the internal temperature did not exceed 10 ° C. After completion of the dropwise addition, the reaction solution was brought to 23 ° C. and further reacted. The reaction is traced by HPLC, and after confirming the completion of the reaction, the reaction solution is poured into 4 L of distilled water, the precipitated solid is filtered, washed successively with distilled water and a mixed solvent of ethyl acetate / hexane, and the solid is dried under reduced pressure. Thus, 105 g of compound [RM2] was obtained (yield 82%). ¹ H-NMR (400MHz, DMSO-d6, δppm): 8.54 (1H, s), 7.87-84 (2H, m), 7.25-7.21 (2H, m), 7.07-7.05 (2H, m), 6.96- 6.93 (2H, m), 6.02-6.01 (1H, d), 5.67-5.66 (1H, m), 4.11 (2H, t), 3.97 (2H, t), 3.83 (3H, s), 1.88-1.87 ( 3H, m), 1.76-1.61 (4H, m), 1.48-1.39 (4H, m).

<Organic solvent> THF: tetrahydrofuran NMP: N-methyl-2-pyrrolidone BC: butyl cellosolve. <Polymerization initiator> AIBN: 2,2'-azobisisobutyronitrile

<Synthesis Example 3-Preparation of Liquid Crystal Alignment Agent (A1)> After RM1 (11.8 g, 30.0 mmol) was dissolved in THF (70.0 g) and deaerated with a diaphragm pump, AIBN (0. 04 g, 0.9 mmol) was added and degassed again. Thereafter, the mixture was reacted at 60 ° C. for 12 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to diethyl ether (1000 ml), and the resulting precipitate was filtered. This precipitate was washed with diethyl ether and dried under reduced pressure in an oven at 40 ° C. to obtain a methacrylate polymer powder. 54.0 g of NMP was added to 6.0 g of the obtained powder, and the mixture was stirred at room temperature for 3 hours. Further, 40.0 g of BCS was added to this solution and stirred at room temperature for 1 hour to obtain a polymer solution (A1) having a solid content concentration of 6.0 wt%. This polymer solution was used as a liquid crystal alignment agent (A1) for forming a liquid crystal alignment film as it was. *

<Synthesis Example 4-Preparation of Liquid Crystal Alignment Agent (A2)> The solid content concentration was 6.0 wt. By the same method as in <Synthesis Example 3> except that RM2 was used instead of RM1 in <Synthesis Example 3> above. % Polymer solution (A2) was obtained. This polymer solution was used as a liquid crystal alignment agent (A2) for forming a liquid crystal alignment film as it was. *

<Example 1> [Preparation of liquid crystal cell] Using the liquid crystal aligning agent (A1) obtained in <Synthesis Example 3>, a liquid crystal cell was prepared according to the following procedure. The substrate was a glass substrate having a size of 30 mm × 40 mm and a thickness of 0.7 mm, on which comb-like pixel electrodes formed by patterning an ITO film were arranged. The pixel electrode has a comb-like shape configured by arranging a plurality of dog-shaped electrode elements whose central portion is bent. The width in the short direction of each electrode element is 10 μm, and the distance between the electrode elements is 20 μm. Since the pixel electrode forming each pixel is formed by arranging a plurality of bent-shaped electrode elements in the central portion, the shape of each pixel is not rectangular, but in the central portion like the electrode elements. It has a shape that bends and resembles a bold-faced koji. Each pixel is divided into upper and lower portions with a central bent portion as a boundary, and has a first region on the upper side of the bent portion and a second region on the lower side. When the first region and the second region of each pixel are compared, the formation directions of the electrode elements of the pixel electrodes constituting them are different. That is, when the alignment processing direction of the liquid crystal alignment film described later is used as a reference, the electrode element of the pixel electrode is formed to form an angle of + 15 ° (clockwise) in the first region of the pixel, and in the second region of the pixel. The electrode elements of the pixel electrode are formed so as to form an angle of −15 ° (clockwise). That is, in the first region and the second region of each pixel, the directions of the rotation operation (in-plane switching) of the liquid crystal induced by the voltage application between the pixel electrode and the counter electrode are mutually in the substrate plane. It is comprised so that it may become a reverse direction. *

The liquid crystal aligning agent (A1) obtained in <Synthesis Example 3> was spin-coated on the prepared substrate with electrodes. Subsequently, it dried for 90 second with a 70 degreeC hotplate, and formed the liquid crystal aligning film with a film thickness of 100 nm. Next, the coating film surface was irradiated with ultraviolet rays of 313 nm via a polarizing plate and then heated on a hot plate at 110 ° C. for 10 minutes to obtain a substrate with a liquid crystal alignment film. Further, a coating film was similarly formed on a glass substrate having a columnar spacer with a height of 4 μm on which no electrode was formed as a counter substrate, and an orientation treatment was performed. A sealant (XN-1500T manufactured by Kyoritsu Chemical Co., Ltd.) was printed on the liquid crystal alignment film of one substrate. Next, the other substrate was bonded so that the liquid crystal alignment film faces each other and the alignment direction was 0 °, and then the sealing agent was thermally cured to produce an empty cell. A liquid crystal cell having a configuration of an IPS (In-Plane Switching) mode liquid crystal display element is injected into this empty cell by a vacuum injection method by injecting liquid crystal MLC-2041 (manufactured by Merck), sealing the injection port. Obtained. When the obtained liquid crystal cell was baked at 120 ° C. for 30 minutes, it was confirmed that good alignment was exhibited. *

<Example 2> [Preparation of liquid crystal cell] <Example 1 except that the liquid crystal aligning agent (A2) obtained in <Synthesis Example 4> was used instead of the liquid crystal aligning agent (A1) in <Example 1>. A liquid crystal cell was produced by the same method as above. When the obtained liquid crystal cell was baked at 120 ° C. for 30 minutes, it was confirmed to show good alignment. *

Synthesis Example 5 << Synthesis of RM2 (MBA6M) >> RM2 (abbreviated as “MBA6M” in the following scheme and this Synthesis Example 5) was synthesized according to the following scheme. *

<< Synthesis of N-Boc-Hydroxyaniline >> 300 ml of methanol was placed in a 500 ml Erlenmeyer flask, and 11.4 g (0.104 mol) of 4-aminophenol was added and dissolved with stirring, and triethylamine (Et ₃ N) was added thereto. 30 ml (0.215 mol) was added. 25 g (0.115 mol) of di-tert-butyl dicarbonate was added and stirred at room temperature for 18 hours. The completion of the reaction was confirmed by thin layer chromatogram (TLC), and the reaction solution was acidified with dilute hydrochloric acid. The solvent was distilled off under reduced pressure in several portions in a 300 ml eggplant flask. To the obtained substance was added 250 ml of ethyl acetate, and the organic phase was extracted, washed four times with 50 ml of saturated brine, dehydrated with anhydrous sodium sulfate, filtered, and then the solvent was distilled off under reduced pressure to obtain a brown solid. Although recrystallization was performed with ethyl acetate / hexane, but the brown color could not be removed, the product was purified by silica gel column chromatography (silica gel: 250 g, developing solvent: ethyl acetate only), but the purified product was brown. Yield: 19.6 g; Yield: 90.1 mol%; Melting point: 143 ° C.

<< Synthesis of N-BOC-6HA >> 17.5 g (83.7 mmol) of N-BOC-4-hydroxyaniline is placed in a 300 ml three-flask and dissolved by adding 100 ml of dimethylformamide (DMF). Chloro-1-hexanol (13.7 g, 102 mmol), K ₂ CO ₃ (22.5 g, 163 mmol) and KI were added in 4 cups of spatula and refluxed in an oil bath set at 100 ° C. for 3 hours. The completion of the reaction was confirmed by TLC, the reaction solution was extracted with diethyl ether (100 ml × 3 times), and the solvent was distilled off under reduced pressure. Purification by silica gel column chromatography (silica gel 400 g, developing solvent: ethyl acetate / hexane = 1/1) and recrystallization gave a pinkish white solid. Yield: 12.6 g; Yield: 48.8 mol%; Melting point: 78 ° C.

<< Synthesis of N-BOC-M6HA >> To a 1000 ml three-necked flask, 14 g (46 mmol) of N-BOC-6HA was added and dissolved in 150 ml of tetrahydrofuran (THF), 5.6 g (55 mmol) of triethylamine (Et ₃ N), polymerization Hydroquinone as an inhibitor was added for 4 cups of spatula and stirred. In an ice bath, 5.8 g (56 mmol) of methacrylic acid chloride was diluted with 150 ml of THF and slowly added dropwise with a dropping funnel. The mixture was stirred for 1 hour in an ice bath and then stirred at room temperature for about 16 hours. After completion of the reaction, the reaction solution was filtered and the solvent was distilled off under reduced pressure. The obtained liquid was dissolved in 300 ml of ethyl acetate and washed with saturated brine (200 ml × 3 times). The organic phase was dried over Na ₂ SO ₄ and filtered, and the solvent was distilled off under reduced pressure. After purification by silica gel column chromatography (silica gel: 300 g, developing solvent: ethyl acetate / hexane = 1/1), recrystallization with ethyl acetate / hexane gave a white solid. Yield: 7.6 g; Yield: 44 mol%; Melting point: 64 ° C.

<< Synthesis of M6HA >> N-BOC-M6HA 4.0 g (11 mmol) was added to a 50 ml sample bottle, HCl (about 1 mol / l, solvent: ethyl acetate) 15 ml and concentrated hydrochloric acid 3 ml were added and stirred for about 9 hours. . After completion of the reaction, the organic layer was extracted by adding 12 ml of 2 mol / l NaOH aqueous solution. The solvent was distilled off under reduced pressure and used as such in the next synthesis. *

<< Synthesis of RM2 (MBA6M) >> A yellow solid was obtained by adding 1.5 g (11 mmol) of p-anisaldehyde to M6HA obtained above. Recrystallization from ethyl acetate / hexane gave yellow crystals. Yield: 1.6 g; Yield: 34%; Melting point: 82 ° C. *

Synthesis Example 6 << Synthesis of RM1 >> RM1 (abbreviated as “Compound 3” or “3” in the following scheme and in this Synthesis Example 6) was synthesized according to the following scheme. *

<< Synthesis of Compound 1 >> In a recovery flask, 10 g (82 mmol) of 4-hydroxybenzaldehyde, 13 g (98 mmol) of 6-chloro-1-hexanol and 23 g (164 mmol) of K ₂ CO ₃ , 4 cups of spatula, and 14 ml of DMF Then, the mixture was refluxed for 5 hours in an oil bath at 90 ° C. The reaction solution was extracted with diethyl ether / water. The organic layer was dehydrated with anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained solid was purified by silica gel column chromatography (silica gel: 200 g, developing solvent: ethyl acetate / hexane = 1/1). White solid, yield: 10 g (45 mmol); yield: 46 mol%; melting point: 50 ° C.

<< Synthesis of Compound 2 >> In a three-necked flask, 6.0 g (27 mmol) of Compound 1 obtained above, 11 g (127 mmol) of methacrylic acid, 1.3 g (7.6 mmol) of p-toluenesulfonic acid, and 0.001 of hydroquinone. 8 g (7.6 mmol) and 45 ml of chloroform were added, and a Dean-Stark apparatus was assembled and refluxed in an oil bath at 90 ° C. for 4 hours. The reaction solution was evaporated under reduced pressure, washed with hexane, and the filtrate was extracted with diethyl ether / water. The organic layer was dehydrated with anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained solution was washed again with hexane, and the filtrate was distilled off under reduced pressure. Yellow liquid, yield: 8.0 g (28 mmol). *

<< Synthesis of RM1 (Compound 3) >> In a three-necked flask, 8.0 g (28 mmol) of the compound 2 obtained above, 3.4 g (28 mmol) of p-anisidine, 1 cup of polymerization inhibitor spatula, 40 ml of chloroform was added, a Dean Stark apparatus was assembled, and the mixture was refluxed for 3 hours in an oil bath at 90 ° C. The reaction solution was evaporated under reduced pressure, purified by preparative column chromatography (developing solvent: ethyl acetate / hexane), and recrystallized from hexane. Pale yellow solid, yield: 0.60 g (1.5 mmol); yield: 5.6 mol%; melting point: 70 ° C. *

<< Synthesis of Polymer P1 from RM1 (Compound 3) >> Polymer P1 was synthesized according to the following scheme. *

Into a polymerization tube, 0.6 g (1.5 mmol) of the compound 3 obtained above, 2,2′-azobisisobutyronitrile (AIBN) 3.0 mg (0.018 mmol), and THF 5 ml were placed for 30 minutes. After purging with nitrogen, the mixture was reacted in an oil bath at 55 ° C. for 24 hours. The mixture was allowed to cool to room temperature, precipitated in diethyl ether, and suction filtered. The obtained solid was dissolved in THF, reprecipitated in diethyl ether, and then dried under reduced pressure to obtain polymer P1 (Mn = 21,000, Mw / Mn = 1.9). Yield: 0.35 g; Yield: 58 wt%; Thermal properties: G70N100I. *

<Polymer P1 Thin Film> Polymer P1 (Mn = 21,000, Mw / Mn = 1.9) exhibited a nematic liquid crystal phase at 41 to 111 ° C. Polymer P1 (0.3 g) was dissolved in 10 ml of methylene chloride to form a solution, and the solution was spin-coated on a quartz substrate to obtain a thin film (film thickness: 100 to 750 nm) of polymer P1. Using this thin film, the behavior of light-induced reorientation and holography were evaluated. *

<Example 3><Visible ultraviolet region absorption spectrum of polymer P1 thin film> The polymer P1 thin film was transparent in the visible region, and exhibited a photoreaction upon irradiation with ultraviolet rays. FIG. 1 is a diagram showing a change in absorption spectrum when a polymer P1 thin film is irradiated with light of 313 nm (intensity: 10 mW / cm ² ). Varying the amount of irradiation from 0 J / cm ² to 300 J / cm ^2, was observed that the absorption at a wavelength of 283nm and 332nm is smaller changes. In particular, the change was gradual until the irradiation dose reached 50 J / cm ^2, but when the irradiation dose exceeded 100 J / cm ² , the peak at 332 nm disappeared and a new peak appeared around 260 nm. After light irradiation, the thin film was transparent in the visible range. Further, the thin film after irradiation (irradiation amount> 100 J / cm ² ) became insoluble in the organic solvent. At the beginning of light irradiation, photoisomerization represented by the following formula (X) is the main part of the photoreaction, but when further irradiated, photoisomerization and other photoreactions such as photocrosslinking have occurred. Conceivable.

<Example 4><Possibility of S-value measurement and application to retardation film> Axially selective photoreaction of P1 film was induced by irradiation with linearly polarized ultraviolet light 313 nm, and molecular reorientation occurred at the same time. . FIG. 2 is a diagram showing a change in polarization absorption spectrum of a P1 film irradiated with 10 J / cm ^{2 of} linearly polarized ultraviolet light 313 nm. After irradiation, the absorbance As in the direction perpendicular to the electric field vector of polarized ultraviolet light increased, but the absorbance Ap in the direction parallel to the electric field vector of polarized ultraviolet light decreased. This suggests that molecular reorientation in the direction perpendicular to the electric field vector of polarized ultraviolet light was induced after axial selective photoanisotropy occurred. The S value at 332 nm was 0.41, and the birefringence value (Δn) at 514 nm was 0.11. From these results, it was found that the P1 film can be applied to a retardation film. Note that S _λ which is an S value at a certain wavelength λ is As (absorbance in the direction perpendicular to the electric field vector of polarized ultraviolet light (λ)) and A _p (parallel to the electric field vector of polarized ultraviolet light (λ)). (Absorbance) is obtained by the following equation. In addition, it calculates | requires separately in the following i) or ii) by the magnitude of the measured value of As and the measured value of Ap.

<Example 5> <Evaluation of holography> Holographic exposure was performed using a 325 nm He-Cd laser (20 mW / 5 mmφ, each beam) using two beams having various polarizations (for holographic exposure). (See Figure 3a for optical path diagram). The grating pitch was 3.15 μm and the two beams had an angle of 5.9 °. FIG. 3b shows a polarization optical microscope image of an intensity holographic exposure P1 film using two p-polarized (pp) beams for 210 seconds. The periodic emission line (Λ = 3.15 μm) coincided with the molecular reorientation region perpendicular to the lattice vector. Further, the surface undulation was formed at a height of 78 nm. Similar results were obtained when two s-polarized (ss) intensity holography and two circularly polarized (2CP) were used. However, the height of the surface relief depends on the polarization, and in the case of ss, the height was 20 nm, and in the case of 2CP, the height was 60 nm. *

Polarization holography simultaneously formed both surface relief formation and periodic molecular reorientation according to the interference polarization pattern. When two circularly polarized beams having opposite circularly polarized light (± CP) are used, a periodic bright line with a half pitch (Λ = 1.58 μm) is observed in the polarization optical microscope image, and the formed surface relief The height was 200 nm (FIG. 3c). From these results, it was found that the P1 film can be applied to holograms.

Claims (15)

A side chain represented by the following formula (I) (wherein A ₁ represents —O—, —COO—, —NHCO—, —CONH—, —NHCONH—, —NHCOO—, —OCONH— or —OCO—). N represents an integer of 1 to 16, and a part of the methylene group (—CH ₂ —) is —O—, —COO—, —OOC—, —NHCO—, —CONH—, —NHCONH—, —NHCOO. —, —OCONH—, —C═C— or —C≡C— may be substituted (provided that methylene group (—CH ₂ —) adjacent to A ₁ or —O— is substituted for these groups) X represents —CH═N— or —N═CH—, R represents an alkyl group having 1 to 3 carbon atoms, n ₁₁ and n ₁₂ each independently represents an integer of 0 to 4, ₁₁ and R ₁₂ are each independently a linear or branched alkyl group having 1 to 6 carbon atoms, A material having a polymer having a halogen atom, nitro, cyano, or a straight-chain or branched-chain alkoxy group having 1 to 6 carbon atoms, and exhibiting anisotropy when irradiated with polarized ultraviolet light. material.

A ₁ is —O—, —COO— or —OCO—, n is an integer of 1 to 8, n ₁₁ and n ₁₂ are 0, R
The material according to claim 1, wherein is a methyl group. The polymer has the following formulas (21) to (31) (wherein A and B are each independently a single bond, —O—, —CH ₂ —, —COO—, —OCO—, —CONH—). , -NH-CO -, - CH = CH-CO-O-, or an -O-CO-CH = CH-; q1 and q2 are the one and the other one is 0; _{Y 3} is a monovalent A group selected from the group consisting of a benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, and is bonded to them. Each hydrogen atom may be independently substituted with —NO ₂ , —CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms; R ₃ represents 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 heterocycle, alicyclic hydrocarbon having 5 to 8 carbon atoms, alkyl group having 1 to 12 carbon atoms, or 1 to 12 carbon atoms L represents an integer of 1 to 12, m represents an integer of 0 to 2, provided that in formulas (25) to (26), the sum of all m is 2 or more, In (27) to (28), the sum of all m is 1 or more, and m1, m2, and m3 each independently represents an integer of 1 to 3; R ₂ represents a hydrogen atom, —NO ₂ , — CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocyclic ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, and an alkyl group or an alkyloxy group; Z _{1, Z 2} is a single bond, -CO -, - CH ₂ -, - CH = N -, - CF 2 -. A representative) material according to claim 1 or 2 wherein further comprising any one liquid crystalline side chain selected from the group consisting of.

The material according to any one of claims 1 to 3, wherein the material is used in one kind selected from the group consisting of a liquid crystal aligning agent, a retardation film, and a hologram. (A) A side chain represented by the following formula (I) (wherein A ₁ is —O—, —COO—, —NHCO—, —CONH—, —NHCONH—, —NHCOO—, —OCONH— or — N represents an integer of 1 to 16, and a part of the methylene group (—CH ₂ —) is —O—, —COO—, —OOC—, —NHCO—, —CONH—, —NHCONH—. , —NHCOO—, —OCONH—, —C═C— or —C≡C— may be substituted (provided that the methylene group (—CH ₂ —) adjacent to A ₁ or —O— X is —CH═N— or —N═CH—, R is an alkyl group having 1 to 3 carbon atoms, and n ₁₁ and n ₁₂ are each independently an integer of 0 to 4 R ₁₁ and R ₁₂ each independently represents a straight or branched alkyl having 1 to 6 carbon atoms. A polymer having a hydrogen group, a halogen atom, nitro, cyano, a linear or branched alkoxy group having 1 to 6 carbon atoms; and (B) a composition for polarizing ultraviolet anisotropic material having an organic solvent .

6. The composition according to claim 5, wherein A ₁ is —O—, —COO— or —OCO—, n is an integer of 1 to 8, n ₁₁ and n ₁₂ are 0, and R is a methyl group. . The polymer (A) is represented by the following formulas (21) to (31), wherein A and B are each independently a single bond, —O—, —CH ₂ —, —COO—, —OCO—, -CONH -, - NH-CO - , - CH = CH-CO-O-, or -O-CO-CH = CH- represents a; q1 and q2 are the one and the other is 0 in 1; _{Y 3} is A group selected from the group consisting of a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocycle, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, and Each hydrogen atom bonded to may be independently substituted with —NO ₂ , —CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms; R ₃ represents 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 heterocycle, alicyclic hydrocarbon having 5 to 8 carbon atoms, alkyl group having 1 to 12 carbon atoms, or 1 carbon atom Represents an alkoxy group of ~ 12; l represents an integer of 1 to 12, m represents an integer of 0 to 2, provided that in formulas (25) to (26), the sum of all m is 2 or more In formulas (27) to (28), the sum of all m is 1 or more, and m1, m2 and m3 each independently represents an integer of 1 to 3; R ₂ represents a hydrogen atom, —NO ₂ , -CN, halogen group, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocycle, alicyclic hydrocarbon having 5 to 8 carbon atoms, and alkyl group or alkyloxy group. It represents; _Z 1, _{Z 2} is a single bond, -CO -, - C _{2 O -, - CH = N} -, - CF 2 -. The representative) according to claim 5 or 6 composition according further comprises any one liquid crystalline side chain selected from the group consisting of.

The composition according to any one of claims 5 to 7, wherein the material is used in one selected from the group consisting of a liquid crystal aligning agent, a retardation film, and a hologram. [I] (A) A side chain represented by the following formula (I) (wherein A ₁ is —O—, —COO—, —NHCO—, —CONH—, —NHCONH—, —NHCOO—, —OCONH) -Represents -OCO-, n represents an integer of 1 to 16, and a part of the methylene group (-CH _2- ) is -O-, -COO-, -OOC-, -NHCO-, -CONH-, —NHCONH—, —NHCOO—, —OCONH—, —C═C— or —C≡C— may be substituted (provided that the methylene group (—CH ₂ —) adjacent to A ₁ or —O— is X is —CH═N— or —N═CH—, R is an alkyl group having 1 to 3 carbon atoms, and n ₁₁ and n ₁₂ are each independently 0 to 4 of an _integer, each independently _{R 11} and _{R 12,} straight-chain or branched-chain having 1 to 6 carbon A polymer having an alkyl group, a halogen atom, nitro, cyano, a linear or branched alkoxy group having 1 to 6 carbon atoms); and (B) a composition for polarizing ultraviolet anisotropic material having an organic solvent And applying a polarized ultraviolet ray to the coating film obtained in [I] and [II] to form an anisotropy by irradiation with polarized ultraviolet rays. A method for producing a polarized ultraviolet anisotropic material, wherein the polarized ultraviolet anisotropic material shown is obtained.

[III] The method according to claim 9, further comprising a step of heating the coating film obtained in [II]. _{11. The method according to} claim 9, wherein A ₁ is —O—, —COO— or —OCO—, n is an integer of 1 to 8, n ₁₁ and n ₁₂ are 0, and R is a methyl group. Method. The polymer (A) is represented by the following formulas (21) to (31), wherein A and B are each independently a single bond, —O—, —CH ₂ —, —COO—, —OCO—, -CONH -, - NH-CO - , - CH = CH-CO-O-, or -O-CO-CH = CH- represents a; q1 and q2 are the one and the other is 0 in 1; _{Y 3} is A group selected from the group consisting of a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocycle, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, and Each hydrogen atom bonded to may be independently substituted with —NO ₂ , —CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms; R ₃ represents 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 heterocycle, alicyclic hydrocarbon having 5 to 8 carbon atoms, alkyl group having 1 to 12 carbon atoms, or 1 carbon atom Represents an alkoxy group of ~ 12; l represents an integer of 1 to 12, m represents an integer of 0 to 2, provided that in formulas (25) to (26), the sum of all m is 2 or more In formulas (27) to (28), the sum of all m is 1 or more, and m1, m2 and m3 each independently represents an integer of 1 to 3; R ₂ represents a hydrogen atom, —NO ₂ , -CN, halogen group, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocycle, alicyclic hydrocarbon having 5 to 8 carbon atoms, and alkyl group or alkyloxy group. It represents; _Z 1, _{Z 2} is a single bond, -CO -, - C _{2 O -, - CH = N} -, - CF 2 -. A representative) The method of any one of claims 9-11, further comprising any one liquid crystalline side chain selected from the group consisting of.

The method according to any one of claims 9 to 12, wherein the material is used in one selected from the group consisting of a liquid crystal aligning agent, a retardation film, and a hologram. A composition for producing a polarized ultraviolet anisotropic material having a monomer represented by the following formula [RM1] or [RM2].

The composition according to claim 14, wherein the polarized ultraviolet anisotropic material is used as one selected from the group consisting of a liquid crystal aligning agent, a retardation film, and a hologram.

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